DE3048659A1 - 1,2,4-Tri:azole(s) e.g. 1,4-bis:(1,2,4-tri:azol-3-yl-mercapto)-butane - used as heat- and light-stabiliser for chlorine-contg. thermoplastics - Google Patents

Abstract

Stabilised compsns. contain a Cl-contg. thermoplastic polymer and, as stabiliser, a 1,2,4-triazole cpd. having formula (I) or (II). R1 is H, OH, 1-6C alkoxy, carboxy, 2-6C alkoxycarbonyl, mercapto, 1-6C-alkylthio or -S-CH2-COOH or -S-CH2-COO-1-6C alkyl; X is thio, methylene, -COO- or -S-CH2-COO- bonded to the alkyl by the ester-O atom; m is 1-20; n is 1 or 2; R2, if monovalent, is H, OH or mercapto, and if divalent, a covalent bond, imino, 1-6C alkyl-imino, oxy, thio or methylene. R3 is H, amino, mercapto or 1-12C alkyl-thio. If R3 is H; R4 is H, -COOR5, in which R5 is H, 1-8C-alkyl, or -S-R6. R6 is e.g. H, 1-12C alkyl, -CH2-COO-1-8C-alkyl or 1-12C-alkyl-thio. (I) where R1 is OH, 1-6C alkoxy, carboxy, 2-6C alkoxycarbonyl, -S-CH2-COOH or -S-CH2-COO-1-6 C-alkyl, are new. Stabilised compsns. comprising a Cl-contg. thermoplastic, (I) or (II) and an epoxy plasticiser are also new. The Cl-contg. thermoplastics can be polyvinylidene chloride and vinyl chloride (co)polymers, esp. suspension-, bulk and washed, i.e. emulsifier-depleted emulsion polymers. (I) and (II) act as heat- and light-stabilisers and act synergetically with epoxy gp.-contg. plasticisers.

Description

Stabilized compositions

The present invention relates to stabilized compositions, which contain 1,2,4-triazole compounds, optionally in a synergistic combination with epoxy plasticizers and new 1,2,4-triazole compounds and their use to stabilize chlorine-containing thermoplastics.

Thermoplastics containing chlorine, such as polyvinyl chloride, suffer under exposure to heat and light undesirable changes leading to discoloration and lead to deterioration in mechanical properties. To this damage off, it is known to use chlorine-containing thermoplastics triazole stabilizers to add.

DE-AS 1 144 477 describes the use of 3-amino-1,2,4-triazoles as thermal stabilizers for chlorine-containing thermal loads while from DE-AS 1 217 062 the use of halogen-containing triazoles for the same purpose is known. Further Triazoles are suitable as stabilizers, which are already used in other areas Amino-1,2,4-triazole carboxylic acids are, for example. from GB-PS 816 531 as intermediate products known for polyester production. DE-OS 1 9 @ 6 S47 describes the use of triazole amides as antioxidants in polyo: efinen.

The use of mercapto-triazoles in lubricating oil composition is known from DE-OS 2,814,458.

Since the well-known thermal stabilizers the diverse technical Requirements such as stability of the connections, physiological tolerance, tolerance with the substrate, low volatility, not fully sufficient, there is still interest of new, effective stabilizers.

It has now been found that certain triazoles contain chlorine-containing thermoplastics Provide surprisingly good light and heat stability and at the same time the disadvantages of the known triazole stabilizers have little or no.

The present invention thus provides a stabilized composition containing a chlorine-containing thermoplastic polymer and, as a stabilizer, a triazole of the formula I or formula II where R1 is hydrogen, hydroxy, C 1-C6 alkoxy, carboxy, C2-C6 alkoxycarbonyl, mercapto, C1-C6 alkylthio or a group -S-CH2-COOH or -S-C112-COO-alkyl CC 1-C6), X is thio, methylene, the -COO- or -S-CH2-COO- group, each bonded to the alkyl through the ester oxygen atom, m is an integer from 1 to 20, n is 1 or 2, R2 if monovalent , Is hydrogen, hydroxy or mercapto and, if divalent, is a direct bond, imino, C1-C6 alkylimino, oxy, thio or methylene, R3 is hydrogen, amino, mercapto or Cl-Cl2 alkylthio and, if R3 is hydrogen, R4 Hydrogen, -COOR5, where R5 is hydrogen, Cl-C8 alkyl or CH2-COO-alkyl (C1-C8), or -S-R6, where R6 is hydrogen, Cl-C12 alkyl, -CH2-COO-alkyl (C1- C8) or Cl-C12 alkylthio or where X 'represents the group -CO-NR-alkylene-NH-CO-, -CO-alkylene-S-alkylene-CO- each having 1-12 carbon atoms in the alkylene chain or for C1-C12) alkylene if R3 is NH2, R4 C1 -c4 alkyl, mercapto, C1-C4 alkylthio or -S-alkylene- with 1-12 carbon atoms in the alkylene chain, if R3 is mercapto, R4 is optionally substituted phenyl, and if R3 is Cl-Cl2 alkylthio, R4 is C1-C4 alkyl, 12 alkylthio or optionally substituted phenyl.

R1 can be Cl-C6 alkoxy, C2-C6 alkoxycarbonyl, Cl-C6 alkylthio or a group -S-CH2-COO-alkyl (Cl-C6), in which the respective alkyl radical is straight-chain or branched, e.g. methyl, ethyl, isopropyl, tert-butyl or n-hexyl, preferably methyl and ethyl, particularly preferably ethyl.

R1 is preferably hydrogen. X is preferably thio or the group -S-CH2-COO-, especially thio.

If R2 is alkylimino, the alkyl radical can be straight-chain or branched be and contain 1-6 carbon atoms, such as, B. Methyl, isopropyl, tert-butyl or n-hexyl, preferably methyl, isopropyl or tert-butyl, particularly preferably methyl.

R2, if monovalent, is preferably hydrogen and, if divalent, prefers a direct bond.

Preference is given to compounds of the formula 1 in which R1 and R2 are hydrogen, X is thio and n is the number 1, and compounds in which R1 is hydrogen, X is thio, R2 is a direct bond and n is the number 2.

R3 is preferably hydrogen or amino.

If R is substituents with c -c alkyl radicals, 4 14 these can straight-chain or branched, e.g. methyl, ethyl, isopropyl, sec-butyl or tert-butyl, especially methyl or ethyl.

If R4 signifies substituents with C1-C8 alkyl radicals, these can straight-chain or branched, e.g. methyl, ethyl, isopropyl, 2-methylpentyl, n-octyl or isooctyl, preferably methyl or isooctyl, particularly preferably isooctyl.

R4 Ci "means C12 alkyl or mean R3 and R4 Cl-Cl2 alkylthio ' they are substituents with straight-chain or branched alkyl radicals, such as methyl, isopropyl, tert-butyl, n-hexyl, n-octyl, isooctyl or n-dodecyl, preferably n-octyl and n-dodecyl, particularly preferably n-dodecyl.

R4 is preferably C1-C12 alkylthio.

If X 'denotes the group -CO-NH-alkylene-NH-CO-, the alkylene radical can Contain L-12 carbon atoms and be straight-chain or branched. Straight-chain is preferred with 1-8 carbon atoms, particularly preferred is hexamethylene.

If X 'denotes the group -CO-alkylene-S-alkylene-CO-, the alkylene radical can Contain 1-12 C atoms and be straight-chain or branched. Straight-chain is preferred with 1-8 carbon atoms, particularly preferred is 1,2-ethylene.

If X 'is C1-C12 alkylene, it can be straight-chain or branched be. X 'is preferably straight-chain with 1-4 C atoms, methylene is particularly preferred.

If R4 is the group -S-alkylene the alkylene radical can contain 1-12 carbon atoms and be straight or branched. Straight-chain with 1-8 carbon atoms is preferred, 1,2-ethylene is particularly preferred.

If R3 is MerkaptA, then R4 is optionally substituted phenyl. The substituents are hydroxy, halogen and C1-C4 alkyl, such as methyl, ethyl, t-butyl, in question. R4 is preferably phenyl, 4-hydroxyphenyl or 4-t-butylphenyl. Particularly 4-hydroxyphenyl is preferred.

If R3 is Cl-Cl2 alkylthio, then R4 can optionally be substituted Represent phenyl. Hydroxy, halogen and C 1 -C 4 alkyl, such as Methyl, ethyl, t-butyl are possible. R4 is preferably phenyl or alkylphenyl. Particularly 4-t-butylphenyl is preferred.

Further preferred forms of the invention are stabilized compositions which, as the triazole of the formula I, are either 1,4-bis- (1,2,4-triazol-3-yl-mercapto) -butane or the compound of the formula IV contain.

Another object of the invention are new compounds of Formula I, in which R1 is C1-C6 alkoxy, carboxy, C2-C6 alkoxycarbonyl or a group -S-CH2-COOH or -S-CH2-COO-alkyl (Cl-C6), and X, R2, m and n are the aforementioned Have meaning.

R1 can be c -c alkoxy, C -C alkoxycarbonyl 'C -C 16 26 16 alkylthio or a group -S-CH2-COO-alkyl (C1-C6), in which the respective alkyl radical can be straight or branched, e.g.

Methyl, ethyl, isopropyl, tert-butyl or n-hexyl, preferably methyl and ethyl, particularly preferably ethyl.

R1 is preferably -S-CH2-COOH or -S-CH2-COO-alkyl (C1-C6), in particular -S-CH2-COO-alkyl (C1-C6).

16 16 X is preferably thio or -S-CH2-COO-, in particular -S-CH2-COO-.

R2, if monovalent, is preferably hydrogen and if divalent, prefers a direct bond.

A preferred compound of the formula I according to the invention is that 1,4-bis- (1,2,4-triazo1-3-yl-mercapto) -butane.

The compounds of the formulas I and II can be prepared according to per se Methods are prepared, such as in GB-PS 816 531, DD-PS 59 288, DE-OS 1 926 547, as well as in K. Potts, Chemical Reviews, 1961, 87 ff and in J.H. Boyer, rfeterocyclic Compounds (R.C. Elderfied, ed.) Vol. 7, 384 ff (1961).

If X in the compound of the formula I is thio, -COO- or -S-CH2-COO-, the compounds can, in particular, by reacting a compound of the formula III with a compound of the formula where R1, R2, X and m are as defined above and Y is a reactive group.

The reactive group Y is halogen, especially bromine, if X is thio, or hydroxy, if X is the group -COO- or -S-CH2-COO-.

Preferred compounds of the formula I and II are 1. 1,2,4-triazole-3-mercapto-iso-octane 2. 1,4-bis- (1,2-triazol-3-y1-mercapto) butane.

The compounds of the formula I and II impart chlorine-containing thermoplastics Light and scratch stability. Simultaneous use of epoxy groups containing Plasticizers leads to a surprising synergistic effect of the triazole stabilizers, i.e. to a much stronger than expected effect.

Another object of the present invention is thereafter a stabilized composition containing a chlorine-containing thermoplastic, a Stabilizer of formula I or II and an epoxy plasticizer.

Of the plasticizers containing epoxy groups, the esters become olefinic unsaturated acids with mono- or polyfunctional alcohols preferred, their Double bonds were epoxidized. The acids preferably contain 12 to 22 carbon atoms and the alcohols have 1 to 30, especially 1 to 20, carbon atoms. Preferred acids are particularly Oleic acid as well as elaidic acid or linoleic acid. Preferred plasticizers are epoxidized Butyl or isooctyl oleate, but especially epoxidized soybean oil.

The triazoles of the formula I and the formula II are the ones to be stabilized chlorine-containing thermoplastics before processing in conventional facilities in general in amounts of 0.05 to 5, preferably 0.1 to 3 percent by weight, based on the chlorinated Incorporated thermoplastics.

The plasticizers can be used in amounts as required for adjustment required properties in plasticized, chlorine-containing thermoplastics are. When used only as a co-stabilizer, they are generally used in quantities of at least 0.05 percent by weight, preferably 0.05 to 10, in particular 0.1 to 5 percent by weight used, based on the chlorine-containing thermoplastic.

It has proven advantageous to use the triazoles of the formula I and of the formula II and the plasticizers containing epoxy groups in a ratio of about 1: 0.5 to 1:10, preferably 1: 1 to 1: 8 to be used.

The following may be mentioned as chlorine-containing thermoplastics: polyvinylidene chloride and preferably polymers made from or based on vinyl chloride. Are preferred Suspension and bulk polymers and washed-out, i.e. low-emulsifier emulsion polymers. The polyvinyl chloride can be plasticized or rigid PVC.

As comonomers for thermoplastics based on vinyl chloride may be mentioned: vinylidene chloride, transdichloroethane, ethylene, propylene, butylene, Maleic acid, acrylic acid, fumaric acid or itaconic acid.

Before, during or after the addition of the stabilizer mixture according to the invention Depending on the intended use of the molding compound, further additives can be incorporated.

The production of the stabilized thermoplastics according to the invention takes place according to known processes by incorporating the stabilizers and, if appropriate further stabilizers in the polymer. A homogeneous mixture of stabilizer and PVC can be obtained, for example, using a two-roll mixer at 150-210DC. Depending on the intended use of the molding compound, before or with the incorporation of the stabilizer8, other additives, such as lubricants, are preferred Montan waxes or glycerine esters, other plasticizers, fillers, modifiers, such as impact additives, pigments, light stabilizers, UV absorbers or antioxidants. The molding compound can contain other co-stabilizers, such as trialkyl phosphites and triaryl phosphites, which may optionally be substituted with alkyl. Long-chain trialkyl phosphites or triphenyl phosphites are preferably used with long-chain alkyl radicals. The thermoplastics according to the invention can according to the customary shaping processes for this purpose, e.g.

processed into molded parts by extrusion, injection molding or calendering will. They can also be used as plastisols.

The triazole stabilizers according to the invention and their synergistic properties effective compositions with epoxy plasticizers ensure excellent thermostabilizing effect.

The following examples serve to explain the invention in more detail.

Example 1: Preparation of 1,4-bis- (1,2,4-triazol-3-yl-merkapto) butane To 0.12 mol of 3-mercapto-1,2,4-triazole dissolved in methanol, 0.12 mol of methanolic Potassium hydroxide and 0.05 mol of dibromobutane were added dropwise and then refluxed heated.

After the reaction mixture has cooled, the liquid components become by Filtration separated. The residue is washed with ice water, filtered off and dried over CaC12. The product obtained has a melting point of 141-1430C.

Analysis: C H N S calculated: 37.5Z 4.7% 32.8% 25.0Z found: 36.7Z 4.8Z 31.4% 24.0% Example 2: Preparation of 1,2,4-triazole-3-mercaptoacetic acid isooctyl ester 0.1 mol of 1,2,4-triazole-3lnercaptoacetic acid are in a; approx. 5-fold excess added to 2-ethylhexanol and stirred at 80 ° C. while passing in HCl. After 6 hours the reaction mixture is cooled to about 200C, poured into ice water and then separated the organic phase. The aqueous phase is washed with ether and added to the organic phase. After drying with sodium sulfate, the solution becomes filtered off and evaporated. The resulting product is a yellow, viscous one Oil.

Example 3: Preparation of 5-amino-1,2,4-triazal-3-carboxylic acid isooctyl ester 0.2 mol of 5-amino-1,2,4-triazole-3-carboxylic acid, dissolved in methanol, are mixed with 0., 2 Moles of sodium methylate are added and the mixture is refluxed for 2 hours. Then will the reaction mixture to approx.

Cooled 200C and evaporated to dryness. The residue is with 0.3 mol of isooctyl bromoacetate is added and the mixture is heated at 1000C for 2 hours. To The mixture is cooled to room temperature, washed with ether, filtered off, washed with water and, after filtering off, the residue over potassium hydroxide dried. The product has a melting point of 120 ° C.

Example 4: Testing for thermal stability A dry blend consisting of 100 parts of S-PVC (K value 64), 20 parts of dioctyl phthalate, 4 parts of epoxidized soybean oil (Reoplast 39), 0.5 parts of tridecyl phosphite stabilizer and 1.5 parts of triazole stabilizer Rolled on a mixing mill for 5 minutes at 1700c and then test film pieces 0.3 mm thick.

The film samples are thermally stressed in an oven at 1800C and every 15 minutes on a sample of the Yellowness Index (YI) according to ASTM D 1925-70 certainly.

The results are summarized in the table below. Yellowness n ex . . . after exposure time Triazole stabilizer Walz: 15 seconds after exposure slide 15 min 30 min 45 min. I tT (CII -S- = r! 6 14 23 to 100 L4 HH ff. 4 17 47 100 Y -Si-octyl 4 17 47> 100 H

Claims (16)

Claims 1. A stabilized composition containing a chlorine-containing thermoplastic polymer and, as a stabilizer, a triazole of the formula 1 or formula II wherein R1 is hydrogen, hydroxy, C1-C6 alkoxy, carboxy, C2-C6 alkoxycarbonyl, mercapto, C1-C6 alkylthio or a group -S-CH2-COOH or -S-CH2-COO-alkyl (Cl-C6), X Thio, methylene, the group -COO- or -S-CH2-COO-, each bonded to the alkyl through the ester oxygen atom, m is an integer from 1 to 20, n is 1 or 2, R2, if monovalent, Is hydrogen, hydroxy or mercapto and, if divalent, is a direct bond, imino, C 1 -C 6 alkylimino, oxy, thio or methylene, R3 is hydrogen, amino, mercapto or C1-C12 alkylthio and, if R3 is hydrogen, R4 Hydrogen, -COOR5, where R5 is hydrogen, C18 alkyl or -CH2-COO-alkyl (C1-C8), or -S-R6, where R6 is hydrogen, 1 Coli: 12 alkyl, -CH2-COO-alkyl (C1- C8) or C1-C12 alkylthio or where X 'is for the group -CO-NH-alkylene-NH-CO-, -CO-alkylene-S-alkylene-CO- each having 1-12 carbon atoms in the alkylene chain or for (Cl-C12) alkylene if 1 12 R3 is NH2, R4 is C1-C4 alkyl, mercapto, C1-C4 alkylthio or -S-alkylene with 1-12 C atoms in the alkylene chain is, if R3 is mercapto, R4 is optionally substituted phenyl, and if R3 is Cl-Cl2 alkylthio, R4 is C1-C4 alkyl, -c 12 alkylthio or optionally substituted phenyl. 2. Stabilized composition according to claim 1 of the formula I thereby characterized in that R1 is hydrogen, hydroxy, C 1-C6 alkoxy, carboxy, C2-C6 alkoxycarbonyl or a group -S-CH2-COOH or -S-CH2-COO-alkyl (Cl-C6). 2 16 3. Stabilized composition according to claim 1 of the formula I, characterized in that X is thio or the group -S-CH2-COO-. 4. Stabilized composition according to claim 1, formula I, characterized characterized in that R1 is hydrogen. 5. Stabilized composition according to claim 1, of formula I, characterized in that R1 and R2 are hydrogen, X is thio and n is the number 1. 6. Stabilized composition according to claim 1, of formula I, characterized in that R1 is hydrogen, X is thio, R2 is a direct bond and n means the number 2. 7. Stabilized composition according to claim 1, of the formula I, characterized in that R1 and R2 are hydrogen, X is the group -S-CH2-COO- and n mean the number 1. 8. Stabilized composition according to claim 1 of formula II, characterized in that R3 is amino and R4 is C1-C4 alkylthio. 9. Stabilized composition according to claim 1, of formula II, characterized in that R3 is hydrogen. 10. Stabilized composition according to claim 1, containing as Triazole of the formula I, 1,4-bis- (1,2,4-triazol-3-ylinercapto) -butane. 11. A stabilized composition according to claim 1, containing the compound of the formula IV as the triazole of the formula II 12. Compounds of formula 1 according to claim 1, characterized in that R1 is hydroxy, C1-c6 alkoxy, carboxy, C2-C6 alkoxycarbonyl or a group -S-CH2-COOR or -S-CH2-COO-alkyl (Cl-C6) X is thio, methylene, the group -COO- or -S-CH2-COO-, in each case through the ester oxygen atom is bonded to the alkyl, m is an integer from 1 to 20, n is 1 or 2 can, R2, if monovalent, signifies hydrogen, hydroxy or mercapto and, if divalent, a direct bond, imino, C1-C6 alkylamino, oxy, thio or methylene is. 13. Compounds of the formula I according to claim 1, characterized in that that R1 is -S-CH2-COO-alkyl (Cl-C6). 14. Compound of formula I according to claim 1, characterized in that that it is 1,4-bis- (1,2,4-triazol-3-ylmercapto-mercapto) -butane. 15. Use of the compound of formula I and II according to claim 1 as stabilizers for chlorine-containing thermoplastic polymer. 16. Stabilized composition containing a chlorine-containing thermoplastic, a stabilizer of formula I or II and an epoxy plasticizer.