DE1258085B - Lubricant in vinyl polymers in the manufacture of moldings - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

C08f

German KL: 39 b -22/06

Number:
File number:
Registration date:
Display day:

1,258,085
S77542IVc / 39b
January 15, 1962
4th January 1968

The invention relates to the use of partial esters with a free hydroxyl group consisting of a polyhydric alcohol with more than 3 carbon atoms and at least three primary hydroxyl groups by partial esterification with a monocarboxylic acid with more than 7 carbon atoms, the derived from an animal or vegetable oil, fat or wax, as a lubricant in vinyl polymers, especially polyvinyl chloride, in the production of moldings optionally together with a metal stabilizer, in particular a lead stabilizer.

The manufacture of objects from thermoplastic vinyl polymers such as polyvinyl chloride and polystyrene, for example by extrusion, often presents considerable difficulties. this probably because of the fact that such polymers retain a high melt viscosity, so that when Heat to remain tough when heated close to their decomposition temperature. When molding the vinyl polymer are therefore a very high pressure and a correspondingly powerful device are necessary. It is known, these difficulties by adding lubricants, e.g. long-chain alcohols, fats or Fatty acids, although this affects other properties of the vinyl polymer will.

It was z. B. proposed to polyvinyl chloride as partial esters of polyhydric alcohols Lubricant in addition to a stabilizer made of a metal compound, e.g. glycerol monostearate dibasic lead stearate.

In contrast, the esters proposed according to the invention represent an improved lubricant. Together with the vinyl polymers, these lubricants provide molding compounds with reduced water absorption and better physical properties. When using lead salts as stabilizers, the Reduced extractability of these compounds.

The following vinyl polymers in which the partial esters are used as lubricants are mentioned: Polystyrene, styrene copolymers, such as styrene-acrylonitrile copolymers, Styrene-butadiene copolymers, polymethyl methacrylate and polyolefins. It has been found that the invention to be used Lubricants especially for compounds containing halogenated hydrocarbon polymers, in particular Polyvinyl chloride, contain and for polyolefins, especially polyethylene and polypropylene are useful. They are particularly useful for rigid polyvinyl chloride compositions, i.e. compositions that are im contain essentially no plasticizer.

Lubricants in vinyl polymers at the
Manufacture of moldings

Applicant:

Shell Internationale Research Maatschappij N.V., The Hague

Representative:

Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse

and Dr. E. Frhr. v. Pechmann, patent attorneys,. .

8000 Munich 90, Schweigerstr. 2

Named as inventor: ■

Stuart Squires, Sale, Cheshire; . · I

Kenneth Goodier, .-.

Davenham, Northwich, Cheshire
(Great Britain)

Claimed priority:

Great Britain January 17, 1961, ...

dated May 16, 1961 (1893)

The partial esters can be of any polyhydric alcohol having more than 3 carbon atoms and at least three primary hydroxyl groups, e.g., pentaerythritol, are derived. A the preferred alcohol is trimethylol propane. The monocarboxylic acid portion of the partial ester (i.e. the Monocarboxylic acid with more than 7 carbon atoms), derived from an animal or vegetable Oil, fat or wax, can be made from a fatty acid with more than 7 carbon atoms, preferably with more than 10 carbon atoms, especially from 14 to 18 carbon atoms, especially stearic and oleic acid, although other acids such as lauric acid, palmitic and Castor acid can also be used. The partial ester should contain a free hydroxyl group. Trimethylol propane distearate and dioleate are new compounds and excellent lubricants, which give the thermoplastic vinyl polymers the desired properties. The partial Esters have the following formula:

HO · CH ₂ · R (CH ₃ OR ') "

where R is a radical derived from the polyhydric alcohol, R 'is an acyl radical of the above monocarboxylic acid and η is an integer, at least 2.

709 717/655

The esterification of the polyhydric alcohols can be carried out in a known manner, e.g. by transesterification, whereby a low molecular weight alkyl ester the monocarboxylic acid is reacted with the polyhydric alcohol. Usable in the esterification Catalysts are, for example, metal hydroxides, alcoholates, lead or tin oxides.

The molding compound usually contains 0.5 to 5 parts by weight, per 100 parts by weight of vinyl polymer, of partial esters, preferably 1 to 3 parts by weight. Other additives can optionally be added e.g. pigments, fillers and stabilizers. It was found that the invention too The lubricant using a molding compound with reduced water absorption and extractability the metal stabilizer furnace, if any, deliver. In the case of the relatively cheap lead stabilizers, the advantage offered in this way is obvious. So in water-conducting '; lead stabilized polyvinyl chloride pipes have the tendency of stabilizer; to leach out of the pipes to be reduced when using the esters proposed according to the invention. Own the pipes a, longer service life. The other properties the molded article such as tensile strength and impact resistance are generally also improved, as can be seen from the following.

example

A number of blends are made by dry blending 100 parts by weight of polyvinyl chloride (K value of 65, determined in ethylene dichloride, produced by an emulsion process) with 2 parts by weight tribasic lead sulfate, 1 part by weight calcium stearate and partial esters, as in the Table indicated, manufactured. "

Physical property

2 parts by weight: GMS 'lubricant

Parts by weight 11.5 parts by weight I 2 parts by weight I 2 weight GMS TMPDS I TMPDS parts GDS

Tensile strength (kg / cm ² ) 560

Strain (%) .' 47 to 50

Impact resistance

(C har ρ y, kg · cm / cm ² ) 1.08 to 1.29 1.29 to 1.50

Water adsorption

(% after 24 hours at 100 ^° C.) 2.18 to 2.30 lead extractability

(after 48 hours). 0.19

GMS = glycerol monostearate

GDS = glycerol distearate

TMPDS = trimethylol propane distearate! 560 to 575

30th

0.86. to 1.08
1.25

595 to 610 70

1.50 to 1.72

1.20 to 1.30

0.10.

580 30 to 40

0.86 1.59

The water absorption is determined by immersing test strips (7.5 x 2.5 x 1.5 cm) in boiling water for 24 hours Obtain water and measure weight gain.

The extractability of lead is determined by immersing the test panels (4.4 x 4.4 cm) in distilled Water adjusted to pH 4.7 with acetic acid. The lead content of the extraction liquid is then measured after 48 hours (in Parts by weight per 1,000,000).

The above results show that trimethylol propane distearate has the following advantages in comparison to glycerine monostearate in polyvinyl chloride mixtures has:

1. Reduction of water absorption,

2. reduction in the extractability of lead,

3. Equally good or better physical or

mechanical properties.

55

The tests with glycerol distearate show that the physical properties (impact resistance) suffer, although the water absorption to a value between that of glycerol monostearate and Trimethylol propane distearate is decreased. Will also. Polyvinyl chloride containing Glycerine distearate is extruded, so you get pipes of only sufficient appearance, while one Pipes of good appearance are obtained when the mixture containing glycerol monostearate is used; with trimethylol propane distearate an even better appearance and a lighter color of the extruded one is obtained Pipe. This improvement in appearance is related to the use of trimethylol propane distearate applies to both the molding powder and the extruded tube. The extrusion of Polyvinyl chloride compositions containing trimethylol propane distearate can be carried out without difficulty will.

Claims (3)

Patent claims: 1. Use of partial esters with a free hydroxyl group derived from a polyvalent Alcohol with more than 3 carbon atoms and at least three primary hydroxyl groups by partial esterification with a monocarboxylic acid with more than 7 carbon atoms, derived from an animal or vegetable oil, fat or wax have been used as lubricants in vinyl polymers in the production of moldings optionally together with a metal stabilizer. 2. Embodiment according to claim 1, characterized in that the partial ester is trimethylol propane distearate or dioleate is used. 3. Embodiment according to claim 1 or 2, characterized in that the partial ester in an amount of 0.5 to 5, preferably 1 to 3 parts by weight per 100 parts by weight of vinyl polymer is used. 709 717/655 12.67 © Bundesdruckerei Berlin