US3499868A

US3499868A - Vinyl resin stabilizers

Info

Publication number: US3499868A
Application number: US612103A
Authority: US
Inventors: Michel Roussos; Yves Bourgeois; Bruno Jasse
Original assignee: Melle Bezons SA
Current assignee: Melle Bezons SA
Priority date: 1966-02-11
Filing date: 1967-01-27
Publication date: 1970-03-10
Anticipated expiration: 1987-03-10
Also published as: GB1159558A; DE1694910C3; FR1480162A; DE1694910B2; DE1694910A1

Description

Int. Cl. cosr 45/58 US. Cl. 26045.75 15 Claims ABSTRACT OF THE DISCLOSURE Chlorine containing vinyl resins are stabilized by incorporating therein a biscyclohexanol and at least one member of the group consisting of tribasic lead sulfate, dibasic lead phthalate and dibasic lead phosphite.

This invention relates to a method for stabilizing chlorine-containing vinyl resins, in particular polyvinyl chloride and copolymers of vinyl chloride, stabilizing compositions to be used in the method and resins stabilized by means of said compositions.

It is known that certain antioxidant phenolic compounds stabilize plasticized or non plasticized chlorinecontaining resins more efiiciently if they already contain stabilizers which are acceptors of hydrochloric acid.

Thus, stabilizing systems which comprise, firstly metallic soaps of lead, barium or cadmium, and, secondly, phenolic antioxidants have been described.

In particular, the stabilizing effect of alkylidene-4,4'- bis-phenols has been used together with the metallic soaps for the manufacture of vinyl plastics.

We have now discovered that the use of alkylidene-4, 4-biscyclohexanols together with at least one member of the group consisting of tribasic lead sulfate, dibasic lead phthalate and dibasic lead phosphite give chlorine-containing vinyl plastic compositions a distinctly higher degree of stability than do the corresponding bisphenols.

According to the present invention there is provided, a method of stabilizing a chlorine-containing vinyl resin, which comprises incorporating into said resin a biscyclohexanol of the formula:

HO OH wherein R and R are hydrogen or alkyl radicals containing from 1 to 18 carbon atoms, R and R are hydrogen or alkyl radicals containing from 1 to 4 carbon atoms and m and n are integers from 1 t 4.

The invention also relates to compositions for stabilizing chlorine-containing vinyl resins, which contain such biscyclohexanols, e.g., mixtures of the stabilizers with a plasticizer, and t0 chlorine-containing vinyl resins which contain such biscyclohexanols.

The following biscyclohexanols are particularly suitable for stabilizing the vinyl resins: isopropylidene-4,4- biscyclohexanol, isobutylidene-4,4-biscyclohexanol, methylhexyldi-(4-hydroxycyclohexyl) methane, hexyl-di-(4- hydroxycyclohexyl)-methane, dimethyldi (2,6-dimethyl- 4-hydroxycyclohexyl)-methane and di-(2,6-di-tert. butyl- 4-hydroxycyclohexyl -methane.

The stabilizers may be used in various ways. Thus the biscyclohexanols may be incorporated with a vinyl resin and the other ingredients in a mixer, which may be, for example, a kneader, a heating cylinder, an extruder or a turbulent mixer. Alternatively, and more easily, the biscyclohexanols may be dissolved in the plasticizers, if de- 3,499,868 Patented Mar. 10, 1970 sired at an elevated temperature, which are added to the resins when pliable resin blend are desired.

The biscyclohexanols according to the invention are easily prepared by hydrogenation from the corresponding bisphenols by known methods.

For example, isopropylidene-4,4-biscyclohexanol can be obtained from isopropylidene-4,4'-bisphenol. The preparation and properties of the higher homologues of this product have been described, for instance, by J. C. Sheehan and G. D. Lanbach (Journal of American Chemical Society, 72, 2478248l1950).

According to a preferred embodiment of the invention, isopropylidene-4,4-biscyclohexanol is used as the stabilizer; it has the advantage of being a relatively inexpensive product, which is commercially available for other uses in the plastic field, for instance the manufacture of polyester resins. This product is generally called hydrogenated bisphenol-A, which term will be hereinafter used.

It has also been found that the stabilizing activity of the biscyclohexanols of the invention is generally more pronounced with the stabilizers which have the highest hydroxyl content. This is the case, for instance, when hydrogenated bisphenol-A is used, rather than its higher homologues.

It is known that certain plasticizers, for example the esters of oxo-alcohols, have an intrinsic susceptibility to ageing. These plasticizers deteriorate after prolonged storage and repeated handling; this becomes apparent when they are used for the manufacture of vinyl compositions.

According to one embodiment of the invention, between 20 and 20,000 parts per million (p.p.m.) of the above-mentioned biscyclohexanols are incorporated with a commercial plasticizer for the resin. The advantages of this addition will be apparent from the example given hereinafter.

It has also been found that the stabilizing effect of the biscyclohexanols is more marked in vinyl mixtures containing basic or normal salts of lead as metallic stabilizers.

In this respect, the method of the invention is particularly advantageous for the manufacture of vinyl compositions to be used for electrical insulation, because lead salts are particularly useful as stabilizers in this case.

The following examples which are given by way of illustration only show that the stabilizing effect of the biscyclohexanols of the invention is obtained at very low concentration of the biscyclohexanol.

EXAMPLE 1 The following ingredients were introduced into a vane mixer:

Parts Polyvinyl chloride Lucovyl DS 1300trademark) Isooctyl phthalate 46 Dielectric-type kaolin 9 Lead stabilizers 6.6

The lead stabilizers comprise a mixture of 45% of tribasic lead sulphate, 45 of dibasic lead phthalate and 10% of dibasic lead phosphite.

The mixture was then gelled by passing it through a press at l25145 C.

The insulation resistance was measured on 10 metres of this cable after immersion of the cable for 2 'hours in water having measurement temperatures of 20 C. or 60 C., 100 volts being applied for 2 minutes.

Ageing was carried out in a ventilated oven for 5 days at 80 C. To measure the mechanical properties, a strip 9 to 10 mm. thick was extruded at ISO- C.; the standard test pieces were cut from this strip (type H2).

(A) isooctyl phthalate containing 200 ppm. of hydrogenated bisphenol-A (B) isooctyl phthalate containing 200 ppm. of bisphenol-A, and

(C) isooctyl phthalate not containing any stabilizer.

The following results were obtained:

ELECTRICAL PROPERTIES Kilometric resistance Kilometric resistance (M9) at 20 G. (M9) at 60 C.

Ageing Vari- Ageing Vari- Before after ation, Before after ation, ageing 5 days percent ageing 5 days percent A 1, G 1, 500 -6. 25 2O B 1,250 550 56 22 3. 7 S2 C 1, 200 500 58. 5 19 3. 5 81. 5

MECHANICAL PROPERTIES BL (kg/cm?) E1. (percent) Ageing Vari- Ageing Vari- Bet'ore after ation, Before after ation ageing 5 days percent ageing 5 days percent A 256 244 4. 5 318 302 5 B 246 183 336 178 -47 C 244 185 -24 304 180 40. 5

These results show the distinctly higher resistance to ageing of mixture A containing the stabilizer according to the present invention.

EXAMPLE 2 The same composition as in Example 1 was used, except that isooctyl phthalate was replaced weight for weight by isodecyl phthalate. The operating conditions were similar. In Formula A, the isodecyl phthalate contained 200 ppm. of hydrogenated bisphenol-A; in Formula B, it contained 200 p.p.m. of bisphenol-A; in Formula C, it was used alone. The electrical and mechanical measurements, and ageing were carried out as in Example 1.

RESULTS ELECTRICAL PROPERTIES Kilometric resistance Kilometric resistance (MSZ) at 20 C. (Me) at 60 C.

Ageing Vari- Ageing Vari- Before after ation, Before after ation, ageing 5 days percent ageing 5da3s percent A 1, 900 1,000 47.5 18 17.5 -0.5 B 1, 400 275 -S0.5 20 4.9 -75.5 c 1,300 250 -s0.5 15.5 4.1 73.5

MECHANICAL PROPERTIES BL (kg/em!) El. (percent) Ageing Vari- Ageing Vari- Bcfore after ation, Before after ation, ageing .Sdays percent ageing Sdays percent A 264 260 1. 5 349 324 7 B 268 103 26.5 346 190 45 C 268 201 -25 332 201 -39 EXAMPLE 3 The same composition as in Example 1 was used, except that Alfol 8-10 phthalate (trademark) was used as a plasticizer. Alfols are linear commercial alcohols obtained by the polymerization of ethylene. The operating conditions were similar. In Formula A, the Alfol 8-10 4t phthalate contained 290 ppm. of hydrogenated bisphenol-A; in Formula B, it was used alone. The electrical measurements and ageing were carried out as in Example 1.

RESULTS ELE CTRICAL PROPERTIES Kilometrie resistance Kilomctric resistance (M9) at 20 G. (M9) at 60 C.

Ageing Vari- Ageing Vari- Before after ation, Before after ation, ageing 5 days percent ageing 5 days percent EXAMPLE 4 The procedure employed was similar to that of Example 3, but the Alfol 810 phthalate was treated beforehand with activated alumina, to purify same and improve its electrical properties. The same formulae were compared, A with 200 p.p.m. of hydrogenated bisphenol- A in the plasticizer and B without stabilization of the plasticizer Electrical measurements and ageing were carried out as in Example 1.

RESULTS ELECTRICAL PROPERTIES Kilometrie resistance Kilometric resistance (M9) at 20 0. (M9) at 60 C.

Ageing Vari- Ageing Vari- Before after ation, Before after ation ageing 5 days percent ageing 5 days percent EXAMPLE 5 The same composition was used, except that 2-ethylhexyl phthalate was used as the plasticizer; the procedure followed was similar. In Formula A, the 2-ethylhexyl phthalate contained 200 p.p.m. of hydrogenated bisphenol-A; in Formula B it contained 200 p.p.m. of bisphenol-A; in Formula C, it was used alone. Electrical measurements and ageing were carried out as in Example 1.

RESULTS ELECTRICAL PROPERTIES Kilometrie resistance Kilometric resistance (M9) at 20 G. (M9) at 60 C.

Ageing Vari- Ageing Vari- Before after ation, Before after ation, ageing 5days percent ageing 5days percent EXAMPLE 6 The following formulation was used:

Parts CPV (Lucovyl DS 1300) 62 Z-ethylhexyl sebacate 16.5 2-ethylhexyl phthalate 15.5 Lead stabilizers 3 Fillers 3.7

In the first case (A) the Z-ethylhexyl sebacate and 2-ethy1-hexyl phthalate both contained 200 p.p.m. of hydrogenated bisphenol-A; in the second case (B), they contained 200 ppm. of bisphenol-A; in the third case (C), they contained 3% of trinonylphenyl phosphite. The procedure followed was similar to and the electrical measurements and ageing were carried out as in Example 1.

RESULTS ELECTRICAL PROPERTIES Kilometric resistance Kilometric resistance (M52) at 20 (M9) at 60 C.

Ageing Vari- Ageing Vari- Before after ation, Before after ation,

ageing 5 days percent ageing 5 days percent A 700 615 12 4.8 4.7 2 B 650 550 15 4. 5 3. 8 15. 5 C 570 275 51. 5 4. 2 2. 5 -40. 5

EXAMPLE 7 Methylhexyldi (4 hydroxycyclohexyl)-methane was used in an amount of 200 p.p.m. in the plasticizer instead of hydrogenated bisphenol-A, according to the conditions set forth in Example 1. Increased resistance to ageing according to the evolution of the mechanical properties was observed.

EXAMPLE 8 500 p.p.m., in relation to the plasticizer, of dimethyldi- (2,6-dimethyl-4hydroxycyclohexyl)methane were used instead of hydrogenated bisphenol-A, according to the conditions of Example 1, with a similar increase in the resistance to ageing.

What we claim is:

1. A stabilized resinous composition comprising (a) a chlorine-containing vinyl resin, (b) a biscyclohexanol of the formula:

wherein R and R are hydrogen or alkyl radicals containing from 1 to 18 atoms, R and R are hydrogen or alkyl radicals containing from 1 to 4 carbon atoms and m and n are integers from 1 to 4 and (c) at least one substance selected from the group consisting of tribasic lead sulfate, dibasic lead phthalate and dibasic lead phosphite.

2. A composition according to claim 1 in which the biscyclohexanol is isopropylidene-4,4'biscyclohexanol.

3. A composition according to claim 1 in which the biscyclohexanol is isobutylidene-4,4'-biscyclohexanol.

4. A composition according to claim 1 in which the biscyclohexanol is methylhexyldi-(4-hydroxycyclohexyl)- methane.

5. A composition according to claim 1 in which the biscyclohexanol is hexyldi (4 hydroxycyclohexyl)- methane.

6. A composition according to claim 1 in which the biscyclohexanol is dimethyldi (2,6-dimethyl-4-hydroxycyclohexyD-methane.

7. A composition according to claim 1 in which the biscyclohexanol is di (2,6-di-tert.-butyl-4-hydr0xycycloheXyl)-methane.

8. A composition according to claim 1 in which the amount of the biscyclohexanol in the composition is from 20 to 20,000 parts per million based on the weight of the chlorine-containing vinyl resin.

9. A stabilizing composition for a chlorine-containing vinyl resin which comprises a biscyclohexanol of the formula:

wherein R and R are hydrogen or alkyl radicals containing from 1 to 18 carbon atoms, R and R are hydrogen or alkyl radicals containing from 1 to 4 carbon atoms and m and n are integers from 1 to 4 and at least one substance selected from the group consisting of tribasic lead sulfate, dibasic lead phthalate and dibasic lead phosphite.

10. A composition according to claim 9 in which the biscyclohexanol is isopropylidene-4,4'biscyclohexanol.

11. A composition according to claim 9 in which the biscyclohexanol is isobutylidene-4,4'biscyclohexanol.

12. A composition according to claim 9 in which the biscyclohexanol is methylhexyldi-(4-hydroXycycloheXyl) methane.

13. A composition according to claim 9 in which the biscyclohexanol is hexyldi (4 hydroxycyclohexybmethane.

14. A composition according to claim 9 in which the biscyclohexanol is dimethyldi-(2,6-dimethyl-4-hydroxycycloheXyl)-methane.

15. A composition according to claim 9 in which the biscyclohexanol is di-(2,6-di-tert.-butyl-4-hydroxycycloheXyl)-methane.

References Cited UNITED STATES PATENTS 1/1953 Fischer et a1. 260-4595 OTHER REFERENCES DONALD E. CZAJA, Primary Examiner V. P. HOKE, Assistant Examiner US. Cl. X.R.