CA2156929C - Basic calcium/zinc mixed soaps - Google Patents
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Abstract
Calcium/zinc mixed soaps are provided corresponding to the formula:
(CaO)n .cndot. Zn(OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 0.1 to 2.5, the basic calcium/zinc mixed soaps being dissolved or suspended in typical lubricants for halogen-containing plastics, prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as already defined, and typical lubricants with low melt viscosities for halogen-containing plastics in a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap. Such soaps are useful as stabiliser compositions for halogen-containing thermoplastics which contain basic calcium/zinc mixed soaps dissolved or suspended in lubricants. Also provided is a process for the production of the basic calcium/zinc mixed soaps.
(CaO)n .cndot. Zn(OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 0.1 to 2.5, the basic calcium/zinc mixed soaps being dissolved or suspended in typical lubricants for halogen-containing plastics, prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as already defined, and typical lubricants with low melt viscosities for halogen-containing plastics in a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap. Such soaps are useful as stabiliser compositions for halogen-containing thermoplastics which contain basic calcium/zinc mixed soaps dissolved or suspended in lubricants. Also provided is a process for the production of the basic calcium/zinc mixed soaps.
Description
WO 94/19308 1 ~ g g 8CT/Ep94/00458 $asic ca.lcium/zinc mired soaps Field of the Iaveation The present invention relates generally to halogen-containing thermoplastics and, more particularly, to stabilizer compositions for such plastics which contain basic calcium/zinc mixed soaps dissolved or suspended in lubricants, to a process tar th.e production of the basic calcium/zinc mixed soaps and t-c their use as stabilizers in halogen-containing thermoplastics.
Background of tha Tnventioa It is known that halogen-containing plastics, more particularly chlorine-containing plastics, such as polyvinyl chloride CPVC), or molding compounds produced from them tend to undergo degradation or decomposition as reflected, for example, in color changes under heat ~con~-ditions or on exposure to ultraviolet light. To counter-act this, stabilizer mixtures containing lead, tin, barium and/or cadmium compounds are normally added. For example, DE-A-34 44 259 describes basic lead soap systems of the 2Pbo~Pb (fatty acid residue)2 type. Far physiolog-ical reasons, there is a need to replace lead-containing stabilizers as far as possible. This applies in particu-lar to halogen-containing thermoplastics which come into contact with fooda. Alternatives tv lead-containing stabilizers ors, four example, calcium and zinc compounds.
A review of calcium/zinc stabilizers can be found in Gachter/Miiller, Ruaststvff-Additive, tad Eda.tioa, Carl-Hanser-verlag, Munchen/Wien, pages 222 to 224 (19a3).
Mast calcium/zinc stabilizers are physical mixtures of calcium and zinc soaps of higher fatty acids containing 8 to 22 carbon atoms. In these calcium/zinc soaps, the fatty acid residue has a lubricating effect while the metal component is z-esponsible for the actual stabilizing effect. In order to achieve high stabilization, it is important on.the one hand to introduce high contents of Ma these soaps into the halogen-containing plastics. How-ever, any increase in the amount of metal soap introduced automatically means an increase in the amount of fatty acid residues introduced which can lead to unwanted overlubrication. In addition, calcium and zinc soaps are dust-emitting products which inter alia can harm person-nel involved in their handling.
To avoid overlubrication, attempts have been made partly to replace the calcium soaps, which have a strong lubricating effect, particularly in the melt, by calcium oxide or calcium hydroxide which does not contain any fatty acid. Unfortunately, corresponding mixtures with zinc soaps are no weaker in their lubricating effect than mixtures of calcium and zinc soaps.
In DE-A-38 0~ 192, it is proposed to use basic metal soaps with the composition (MO)n~M(RCOO)2, in which MO is an oxide from the group consisting of CaO, ZnO, MgO, Ba0 and PbO, M is one of the metals mentioned and RCOO is a fatty acid residue, as a stabilizer/lubricant composition for the plastics industry. These basic metal soaps are obtained by reaction of powder-form fatty acids with powder-form metal oxides in the presence of water and/or.
an acid. Unfortunately, this solid-state reaction leads to reaction mixtures which still contain large quantities of unreacted educts (for example Ca0) in addition to small quantities of basic metal soaps. Accordingly, these reaction mixtures are also unsuitable for avoiding overlubrication to the required extent.
Summary of the Invention The problem addressed by the present invention was to provide lead-free stabilizers which would have a high content of the metals responsible for the actual stabil-izing effect, but a small content of fatty acid residues.
In addition, the stabilizers would be accessible in high yields so that secondary products which could give rise to overlubrication would only be present in very small ~~ 56929 ~O 94/19308 3 PCT/k1P94/00458 amounts, if at all. In addition, the stabilizers would emit very little dust and would be compatible with typical additives for' halogen-containing plastics.
These requirements are satisfied by basic calcium/
zinc mixed soaps with a composition corresponding to formula (I) which have been produced by melt-phase reaction in the presence of typical lubricants for halogen-containing pl.astiGS which have low viscosities in molten form.
l0 . Accordingly, the present invention relates to basic calcium/zinc mixed soaps corresponding to formula (I):
( Ca0 ) ~ ~ Z n ( OOCRl ) 2 ( 1 ) 15~ in which Rl represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 cartoon atoms or ketoa.l.kyl radicals containing 11 to 21 carbon atoms and 2U n is a number of 0.1 tv 2.5, the basic calcium/zinc mixed soaps being dissolved or suspended in typical lubricants for halogen-containing plastics, prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)z, 25 where R1 is as already defined; and typical lubricants with low melt viscosities for halogen-containing plastics irt a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap.
D~eta~.led Description of the Itmex~.tion The group RlCOO- in formula (I) is derived from saturated and/or unsaturated monocarboxylic acids con-taining 8 to 22 carbon atoms or from saturated or un-saturated hydroxycarbaxylic acids containing 8 to 22 carbon atoms or from ketofatty acids containing 12 to 22 carbon atoms. The carboxylic acids and/or hydroxy-carboxylic acids may_ be of natural and/or synthetic ~y~~~~~
origin. Examples of suitable monocarboxylic acids are lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic, acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid and erucic acid. Ex-amples of suitable hydroxymonocarboxylic acids are ric:in-oleic acid and 12-hydroxystearic acid. In a particularly preferred embodiment, the group R1C00- is derived from technical mixtures of the fatty acids mentioned which are obtainable in the form of the technical mixtures typic:al-ly encountered in ol.eochemistry after the pressure hydro-lysis of oils and fats of animal or vegetable origin, such as coconut oil, palm kernel oil, sunflower oil, rape oil, rapeseed oil and coriander oil and beef tallow.
However, the group R1C00- may also be a branched fatty acid residue, for example the residue of 2-ethyl hexanoic acid, isopalmitic acid or isostearic acid. The carboxy-lic acid residues R:1C00- may also be derived from keto-fatty acids containing 12 to 22 carbon atoms. Typical and preferred representatives of these ketofatty acids :ZO are the various isomers of ketostearic acid which are described in Acta Chemica 8candinavica 6, 1157 to 1174 (1952). Of these isomeric ketostearic acids, 4-, 9(10) and 12-ketostearic acids are particularly preferred because they can be obtained particularly easily from natural raw materials.
In a particularly preferred embodiment, the group R1C00- in formula (I) stands for saturated fatty acid residues and/or ketofatty acid residues of the fatty acids or ketofatty acids described above.
In one advantageous embodiment of the invention, n in formula (I) is a whole or broken number of 1 to 1.5, i.e. preferred basic calcium/zinc mixed soaps have the composition (Ca0) 1-1.5' Zn (OOCR1) Z. The exact structural composition of the calcium/zinc mixed soaps of formula :35 (I) in their preferred embodiments is not known. How-~~~~929 ever, it is certain that they are not physical mixtures, but rather chemical mixtures because very little, if any, free calcium hydroxide or free calcium oxide could still be detected. Proof was provided by investigating the quantities of free calcium oxide observed when the basic calcium/zinc mixed soaps dissolved or suspended in lubricants are stored for 3 hours in a heating cabinet.
Comparison of the basic calcium/zinc mixed soaps accard-ing to the invention with the mixed soaps produced i.n a solid-state reaction in accordance with DE-A-38 06 192 shows that free calcium oxide sediments in varying amounts during storage. The purity of the basic calcium/
zinc mixed soaps can be estimated from the results of the tests thus carried out. The calcium/zinc mixed saaps according to the invention are dissolved or suspended in typical lubricants for halogen-containing plastics in a purity of more than 85~ by weight. The balance to 1.00%
is unreacted calcium oxide or calcium hydroxide - calcu-lated without lubricant.
>.0 The basic calcium/zinc mixed soaps are dissolved or suspended in lubricants which are typical of the thermo-plastic halogen-containing thermoplastics and which have low melt viscosities. Particularly preferred lubricants have a Hoppler viscosity in the melt at 80~C of less than 150 mPa~s. In a particularly preferred embodiment, the basic calcium/zinc mixed soaps are dissolved or suspended in one or more lubricants selected from the group con-sisting of a) fatty alcohols containing 8 to 22 carbon atoms, a0 b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms arid 2 to 6 hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to formula (II):
RZ-CO-R3 ( I I ) in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon .L 0 atoms , f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, such as polyethylene waxes and .L5 paraffins, h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
The compounds listed above are compounds known per se for halogen-containing plastics which are commercially :?0 available.
In a particularly preferred embodiment, the basic calcium/zinc mixed soaps are present in the described lubricants typical of halogen-containing thermoplastics in quantities of 10 to 60~ by weight and preferably in :?5 quantities of 20 to 50~ by weight, based on the mixture of basic calcium/zinc mixed soaps and lubricant, in dissolved or suspended form. The expression used in this connection that the calcium/zinc mixed soaps are present in "dissolved" or "suspended" form means that the basic :30 calcium/zinc mixed soaps have been produced in a melt containing the usual lubricants.
The basic calcium/zinc mixed soaps may be used as sole stabilizer component or in admixture with stabil-izers known from the prior art. Known stabilizers are 35 optionally surface-modified hydrotalcites which are commercially available under the name of Alcamizer~ from Kyowa Chemical. Int., synthetic crystalline sodium sili-cates, for example of the NaA type described in DE-~r-24 12 837, and/or basic calcium/aluminium hydroxyphosph:ites according to DE-C-39 41 902. The hydrotalcites marketed by Kyowa have a BET surface of less than 30 mZ/g and are usually surface-modified with dispersants, such as sodium stearate. However, it is also possible to use hydrotal-cites with larger surfaces or with other surface modify-ing agents, such as the hydrotalcites described in DE-A-41 17 034 and DE-A-41 17 035. In addition, basic mag-nesium/zinc mixed soaps with a composition corresponding to the formula (Mg0)xZn(OOCR)Z, where x is a number of 0.1 to 2.5 and R may be an alkyl radical, may be used as stabilizers. Basic magnesium/zinc mixed soaps such as these are produced from zinc soaps corresponding to the formula Zn(OOCR)Z and 0.1 to 2.5 moles of magnesium oxide or hydroxide per mole of zinc soap in a melt-phase reaction in accordance with one of applicants' ear:Lier applications, preferably in the presence of catalytic quantities of acids and, more particularly, at tempera-tures above the melting temperature and below the decom-position temperature of the zinc soap. In a particularly preferred embodiment, the basic calcium/zinc mixed soaps according to the invention are used together with the hydrotalcites and/or basic magnesium/zinc mixed soaps.
The present invention also relates to a process for the production of basic calcium/zinc mixed soaps corre sponding to formula (I), characterized in that calcium oxide or calcium hydroxide is added to a melt containing zinc soaps corresponding to formula (III) Zn(oOCRl)2, where R1 is as already defined, and the lubricants with low melt viscosities typical of halogen-containing thermoplastics, the reaction mixture being heated above its melting point in the presence of catalytic quantities of acid until the free calcium oxide or calcium hydro~:ide has reacted off. Calcium oxide or calcium hydroxide is added to the melt in quantities of 0.1 to 2.5 moles per mole of zinc soap corresponding to formula (III). In general, the catalytic quantities of acids are added at the same time as the calcium oxide or calcium hydroxide.
The reaction mixture obtained is kept in the melt until almost all the calcium oxide or calcium hydroxide has reacted off. The end of the reaction is indicated by a :LO clear or cloudy melt which no longer contains any solid particles visible to the naked eye. As described above, the conversion may be determined by determining the unreacted calcium oxide or calcium hydroxide in storage.
In a particularly preferred embodiment, 1 to 1.5 moles of :L5 calcium oxide or ca:Lcium hydroxide are added per mole: of zinc soap. In another preferred embodiment, acids are present in quantities of 0.001 to 0.1~ by weight, based on the reaction mixture. Typical acids are short-chain monocarboxylic acids containing 1 to 3 carbon atoms, such 20 as acetic acid, and mineral acids of which the anions are compatible with the plastics to be stabilized, such as phosphoric acid. The temperature at which the reaction between calcium hydroxide or calcium oxide with the zinc soaps takes place in the presence of the typical lubri-:~5 cants mentioned is above the melting temperatures and below the decomposition temperatures of the zinc soaps.
In general, the decomposition temperatures are in the range from 100 to 180°C, depending on the melting paint and the decomposition point of the zinc soap selected.
:30 For reactions of zinc stearate, the temperatures are of the order of 150°C. The reaction of the calcium oxide or calcium hydroxide with the zinc soaps is carried out: in the presence of the lubricants already mentioned to reduce the viscosity of the melt. Thus, the absence of :35 these compounds would result in the formation o:E a ~2~6929 reaction mixture which would have such a high viscosity at the melting temperature of the zinc soaps that it would be virtually impossible to stir so that the reac-tion could only be completed only partly, if at all. The quantities of :lubricant present in the melt are selected so that 40 to 90% by weight and preferably 50 to 80a; by weight of the mixture obtained consists of lubricant, 10 to 60~ by weight and preferably 20 to 50 o by weight. of the mixture being the basic calcium/zinc mixed soaps.
:LO The zinc soaps of formula (III) used in the process could either be commercially obtained or may even be produced in situ by reacting carboxylic acids, hydroxy-carboxylic acids or ketofatty acids corresponding to formula R1COOH with zinc salts, preferably with zinc :15 oxide, in a malar ratio of about 2:1. The reaction is preferably carried out by initially melting the car-boxylic acids R1COOH and adding the zinc salts, par-ticularly zinc oxide, to the resulting melt. The reac-tion is continued until the fatty acids have almost :?0 completely reacted. The substantially complete reaction can be recognized by determining the acid value in accordance with DIN 53402. The reaction may also be accelerated by the presence of catalytic quantities of acids. The acids may be used in quantities of 0.001. to 25 0.1% by weight, based on the reaction mixture. Shart-chain monocarboxylic acids and mineral acids may also be used.
In the preferred embodiment of the process according to the invention, the carboxylic acids R1COOH are initial-30 ly introduced and melted together with the lubricants.
The zinc salts are added to the resulting melt in such stoichiometric quantities that zinc soaps corresponding to formula (III) are initially formed. Catalytic quan-tities of acids are preferably present. The calcium :35 oxide or calcium hydroxide is then added in corresponding ~~.~~~?9 molar quantities to the resulting melt of zinc soaps and lubricants. This second reaction step is also preferably carried out in the presence of catalytic quantities of acids. Where calcium hydroxide is added, the water of reaction formed is continuously removed from the reaction mixture. On completion of the reaction, the basic cal-cium/zinc mixed soaps accumulate in the form of a solu-tion or suspension .in the usual lubricants, preferably in the lubricants a) to h). The reaction product obtained l0 is a dust-free solid which, if desired, may be further processed, for example by spraying.
If the basic calcium mixed soaps according to the invention are used with other stabilizers known from the prior art, such as the hydrotalcites or basic magnesium/
zinc mixed soaps, the known stabilizers are added to the final mixture of basic calcium/zinc mixed soaps and typical lubricants, preferably the lubricants a) to h).
The present invention also relates to the use of basic calcium/zinc mixed soaps corresponding to formula (I) - dissolved or suspended in typical lubricants for halogen-containing plastics - according to claim 1 as stabilizers for halogen-containing thermoplastics, more particularly PVC. For the use according to the inven-tion, the quantity of basic calcium/zinc mixed soaps dissolved or suspended in lubricants is from 0.05 to 5 parts by weight arid preferably 0.2 to 2 parts by weight, expressed as basic calcium/zinc mixed soap in solution or suspension in lubricants and based on 100 parts by weight of halogen-containing plastics. If other stabilizers known from the prior art are used together with the basic calcium/zinc mixed soaps according to the invention, they are used in typical quantities; for example, hydrotal-cites may be used in quantities of 0.1 to 0.5 part by weight and, the basic calcium/zinc mixed soaps in quanti-:35 ties of 0.05 to 5 parts by weight per 100 parts by weight ~1~~~~9 of halogen-containing plastics. If desired, other lubri-cants, release agents, plasticizers and/or co-stabilizers known from the prior art, such as the lubricants a) to h), or esters of epoxidized fatty acids with monofunc-tional alkanols or with polyols, 8-diketones, such as benzoyl stearoyl methane, hydroxyfunctional isocyanurates and/or secondary and/or tertiary esters of phosphorous acid, such as dialkylaryl phosphites. These additional additives may be incorporated in typical quantities in the thermoplastic halogen-containing plastics.
Halogen-containing plastics in the context of the invention are, above all, chlorine-containing homopoly-mers and copolymers of vinyl chloride. Preferred copoly-mers are polymers of at least 50~ by weight of vinyl chloride and other polymerizable monomers, such as vinyl esters, methacrylates, fumarates, butadiene and vinyli-dene chloride. However, polyvinyl chloride homopolymers with K values of 60 to 70, which can be produced by emulsion, suspension or bulk polymerization, are par-ticularly preferred. The PvC may of course also be modified with impact modifiers and flow modifiers.
Where the stabilizers according to the invention are used, PVC compounds in particular do not show any signs of overlubrication despite the metal content of calcium and zinc required for stabilization. This can be seen in particular in extruders where the buildup of pressure is lower than for mixtures of calcium oxide and zinc soaps or calcium soaps and zinc soaps. Accordingly, very much more of 'the stabilizers according to the invention may be used in the plastic without any danger of overlubr:ica-tion. Lastly, the basic calcium/zinc mixed soaps accord-ing to the invention are dust-free solids which may read-ily be further processed and which are easy to handle.
~~.~~~?~
E x a m p 1 a s A) Production of the basic calcium/zinc soaps Percentages are percentages by weight.
Example 1: Ca0~Zn-Z-ethyl hexanoate (40%) with glycerol distearate (60%) 56.7 g (0.39 mole) of 2-ethyl hexanoic acid and 120 g of glycerol distearate were introduced into a four necked spherical flask equipped with a stirrer, ther mometer and descending condenser. 15.9 g (0.195 mole) of zinc oxide were added in portions to the molten mixture, after which vacuum was applied. The vacuum was con-tinuously increased until, after about 1 hour, a vacuum of about 30 hPa was reached. After a total of 1.5 hours, the acid value as measured in accordance with DIN 53402 was below 4. After venting, 14.4 g (0.195 mole) of cal-cium hydroxide and 0.05 g of 99% acetic acid were added in the second reaction step. The reaction was over after 2.5 hours under a vacuum of about 30 hPa. A yellowish, brittle wax-like mass with a melting point of 75°C was obtained.
Example 2: Ca0~zinc oleate (40%) with glycerol dioleate (60%) 65.9 g (0.24 mole) of technical oleic acid, 120 g of glycerol dioleate and 0.05 g of 99$ acetic acid were initially introduced into the reaction flask as in Example 1. 9.6 g (0.12 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
8.7 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction step, after which the further procedure was as in Example 1. A
yellowish brown-tinged vaseline-like mass with a melting point of 69°C was obtained.
Example 3: Ca0~Zn-12-hydroxystearate (40%) with hydrogen-ated castor oil (60%) 67.2 g (0.22 mole) of 12-hydroxystearic acid, 120 g of hydrogenated castor oil and 0.05 g of 99~ acetic acid were initially introduced into the reaction flask as in Example 1. 8.'7 g (0.11 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
8.0 g (0.11 mole) of calcium hydroxide and 0.05 g' of acetic acid were added in the second reaction step, after which the further procedure was as in Example 1. A
brownish wax-like mass with a melting point of 132°C was obtained.
Example 4: Ca0~Zn stearate (40%) with glycerol tri-stearate (60%) 6.5 g (0.24 mole) of technical stearic acid, 12 0 g of glycerol tristearate and 0.05 g of 99~ acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (().12 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second process step as in Example l, after which the further procedure was as in Example 1. A brownish, hard wax-like mass with a melting point of 106°C was obtained.
Example 5: Ca0~Zn stearate (40%) with tallow fatty alcohol (60%) 65.5 g (0.24 mole) of technical stearic acid, 120 g of tallow fatty alcohol and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (0.12 mole) of zinc oxide were added to the molten mixture and vacuum was applied. In the second reaction step, 9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added and reacted as described r, ~ e~
in Example 1. A yellow wax-like mass with a melting point of 108°C was obtained.
Example 6: Ca0~Zn stearate (40%) with tallow fatty alcohol stearate 65.5 g (0.24 mole) of technical stearic acid, 120 g of tallow fatty alcohol stearate and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (0.12 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction step, after which the further procedure was as in Example 1. A
yellowish, hard wax-like mass with a melting point of 115°C was obtained.
Example 7: 1.5 Ca0~Zn stearate (20%) with pentaerythritol distearate (60%) 31.4 g (0.116 mole) of technical stearic acid, 80 g of Penta~ distearate and 0.05 g of acetic acid were initially introduced into the reaction flask as in Example 1. 4.7 g (0.058 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
In the second reaction step, another 80 g of Penta~
distearate and - after it had melted - 6.5 g (0.088 mole) of calcium hydroxide and 0.05 g of acetic acid 'were introduced into the reaction mixture. The reaction was continued as in Example 1. A yellow wax-like mass with a melting point of 110°C was obtained.
Example 8: Ca0~Zn stearate (40%) with glycerol distearate (60%) 65.5 g (0.24 mole) of technical stearic acid, 120 g of glycerol distearate and 0.05 g of 99o acetic acid were initially introduced into the reaction flask as in t Example 1. 9.8 g (0.12 mole) of zinc oxide were intro-duced into the molten mixture in portions and vacuum was applied. 9.1 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction step, 5 after which the reaction was continued as in Example 1.
A pale yellowish wax-like mass with a melting point of 95°C was obtained.
TM
Example 9: Ca0~Zn stearate (30%) with Paraffin FP 90-100 10 (70%) 65.5 g (0.24 mole) of technical stearic acid, 186.7 g of paraffin and 0.05 g of acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (0.12 mole) of zinc oxide were added in portions to the 15 molten mixture and vacuum was applied. 9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction stage, after which the reaction was continued as in Example 1. A yellow wax-like mass with a melting point of 127°C was obtained.
Example 10: Ca0~Zn-12-ketostearate (50%) with glycerol distearate (50%) 83.4 g (0.28 mole) of 12-ketostearic acid, 100 g of glycerol distearate and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 11.3 g (0.14 mole) of zinc oxide were added in portions to the melt and vacuum was applied. In the second reaction step, 10.3 g (0.14 mole) of calcium hydroxide and 0.05 g of acetic acid were added, after which the reaction was continued as in Example 1. A pale yellowish, hard wax-like mass with a melting point of 115°C was obtained.
z~.~~~929 Example 11: 2 Ca0~Zn stearate (40%) with glycerol di-stearate (60%) 60.4 g (0.22 mole) of technical stearic acid, 120 g of glycerol distearate and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 9.1 g (0.11 mole) of zinc oxide were intro-duced into the molten mixture at 140 to 150°C and vacuum was applied. 16.6 c~ (0.22 mole) of calcium hydroxide and 0.05 g of 99~ acetic acid were added in the second reaction step, after which the reaction was continued as in Example 1. A pale yellowish wax-like mass with a melting point of 95°C was obtained.
B) Comparison of the free quantity of calcium oxide B1) 150 g of the. basic calcium/zinc mixed soap of Example A8) according to the invention, correspond-ing to 40% of Ca0~zinc stearate in 60% of glycerol distearate B2) 60 g of the basic calcium/zinc mixed soap according to Example 1 of DE-A-38 06 192 were homogenized in 90 g of glycerol distearate until a fine-particle, homogeneous solids mixture was present.
B1) and B2) were melted and transferred to a glass beaker. The glass beaker was then stored in a heating cabinet for 3 hours at 140°C. After cooling of the melt, the glass beaker was removed. Product was scraped off from the top and middle of the solidified melt and from the sediment. The scrapings were investigated for their ash content, i.e. calcium and zinc oxide, in accordance with DIN EN7 and a ratio was formed between the result obtained and the theoretical quantity of zinc oxide and calcium oxide (8.4a).
In the case of B1), no phase separation was observed ~1~69'9 in the molten state.
Determination of the ash content revealed the following quantities of calcium and zinc oxide:
top: 8.2% middle: 8.2% bottom: 8.7%
In other words, in relation to the theoretical content of calcium and zinc oxide of 8.4%, 8.4 - 8.2% - 0.2% had sedimented from the melt. Assuming that the entire :10 sediment is calcium oxide and that, of the 8.4% of calcium and zinc oxides, 3.4% is calcium oxide, the free calcium oxide content on the basis of the relation 0.2 ~ 100 = 5.8 is 5.8% which could collect as sediment.
Background of tha Tnventioa It is known that halogen-containing plastics, more particularly chlorine-containing plastics, such as polyvinyl chloride CPVC), or molding compounds produced from them tend to undergo degradation or decomposition as reflected, for example, in color changes under heat ~con~-ditions or on exposure to ultraviolet light. To counter-act this, stabilizer mixtures containing lead, tin, barium and/or cadmium compounds are normally added. For example, DE-A-34 44 259 describes basic lead soap systems of the 2Pbo~Pb (fatty acid residue)2 type. Far physiolog-ical reasons, there is a need to replace lead-containing stabilizers as far as possible. This applies in particu-lar to halogen-containing thermoplastics which come into contact with fooda. Alternatives tv lead-containing stabilizers ors, four example, calcium and zinc compounds.
A review of calcium/zinc stabilizers can be found in Gachter/Miiller, Ruaststvff-Additive, tad Eda.tioa, Carl-Hanser-verlag, Munchen/Wien, pages 222 to 224 (19a3).
Mast calcium/zinc stabilizers are physical mixtures of calcium and zinc soaps of higher fatty acids containing 8 to 22 carbon atoms. In these calcium/zinc soaps, the fatty acid residue has a lubricating effect while the metal component is z-esponsible for the actual stabilizing effect. In order to achieve high stabilization, it is important on.the one hand to introduce high contents of Ma these soaps into the halogen-containing plastics. How-ever, any increase in the amount of metal soap introduced automatically means an increase in the amount of fatty acid residues introduced which can lead to unwanted overlubrication. In addition, calcium and zinc soaps are dust-emitting products which inter alia can harm person-nel involved in their handling.
To avoid overlubrication, attempts have been made partly to replace the calcium soaps, which have a strong lubricating effect, particularly in the melt, by calcium oxide or calcium hydroxide which does not contain any fatty acid. Unfortunately, corresponding mixtures with zinc soaps are no weaker in their lubricating effect than mixtures of calcium and zinc soaps.
In DE-A-38 0~ 192, it is proposed to use basic metal soaps with the composition (MO)n~M(RCOO)2, in which MO is an oxide from the group consisting of CaO, ZnO, MgO, Ba0 and PbO, M is one of the metals mentioned and RCOO is a fatty acid residue, as a stabilizer/lubricant composition for the plastics industry. These basic metal soaps are obtained by reaction of powder-form fatty acids with powder-form metal oxides in the presence of water and/or.
an acid. Unfortunately, this solid-state reaction leads to reaction mixtures which still contain large quantities of unreacted educts (for example Ca0) in addition to small quantities of basic metal soaps. Accordingly, these reaction mixtures are also unsuitable for avoiding overlubrication to the required extent.
Summary of the Invention The problem addressed by the present invention was to provide lead-free stabilizers which would have a high content of the metals responsible for the actual stabil-izing effect, but a small content of fatty acid residues.
In addition, the stabilizers would be accessible in high yields so that secondary products which could give rise to overlubrication would only be present in very small ~~ 56929 ~O 94/19308 3 PCT/k1P94/00458 amounts, if at all. In addition, the stabilizers would emit very little dust and would be compatible with typical additives for' halogen-containing plastics.
These requirements are satisfied by basic calcium/
zinc mixed soaps with a composition corresponding to formula (I) which have been produced by melt-phase reaction in the presence of typical lubricants for halogen-containing pl.astiGS which have low viscosities in molten form.
l0 . Accordingly, the present invention relates to basic calcium/zinc mixed soaps corresponding to formula (I):
( Ca0 ) ~ ~ Z n ( OOCRl ) 2 ( 1 ) 15~ in which Rl represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 cartoon atoms or ketoa.l.kyl radicals containing 11 to 21 carbon atoms and 2U n is a number of 0.1 tv 2.5, the basic calcium/zinc mixed soaps being dissolved or suspended in typical lubricants for halogen-containing plastics, prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)z, 25 where R1 is as already defined; and typical lubricants with low melt viscosities for halogen-containing plastics irt a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap.
D~eta~.led Description of the Itmex~.tion The group RlCOO- in formula (I) is derived from saturated and/or unsaturated monocarboxylic acids con-taining 8 to 22 carbon atoms or from saturated or un-saturated hydroxycarbaxylic acids containing 8 to 22 carbon atoms or from ketofatty acids containing 12 to 22 carbon atoms. The carboxylic acids and/or hydroxy-carboxylic acids may_ be of natural and/or synthetic ~y~~~~~
origin. Examples of suitable monocarboxylic acids are lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic, acid, lauroleic acid, myristoleic acid, palmitoleic acid, oleic acid and erucic acid. Ex-amples of suitable hydroxymonocarboxylic acids are ric:in-oleic acid and 12-hydroxystearic acid. In a particularly preferred embodiment, the group R1C00- is derived from technical mixtures of the fatty acids mentioned which are obtainable in the form of the technical mixtures typic:al-ly encountered in ol.eochemistry after the pressure hydro-lysis of oils and fats of animal or vegetable origin, such as coconut oil, palm kernel oil, sunflower oil, rape oil, rapeseed oil and coriander oil and beef tallow.
However, the group R1C00- may also be a branched fatty acid residue, for example the residue of 2-ethyl hexanoic acid, isopalmitic acid or isostearic acid. The carboxy-lic acid residues R:1C00- may also be derived from keto-fatty acids containing 12 to 22 carbon atoms. Typical and preferred representatives of these ketofatty acids :ZO are the various isomers of ketostearic acid which are described in Acta Chemica 8candinavica 6, 1157 to 1174 (1952). Of these isomeric ketostearic acids, 4-, 9(10) and 12-ketostearic acids are particularly preferred because they can be obtained particularly easily from natural raw materials.
In a particularly preferred embodiment, the group R1C00- in formula (I) stands for saturated fatty acid residues and/or ketofatty acid residues of the fatty acids or ketofatty acids described above.
In one advantageous embodiment of the invention, n in formula (I) is a whole or broken number of 1 to 1.5, i.e. preferred basic calcium/zinc mixed soaps have the composition (Ca0) 1-1.5' Zn (OOCR1) Z. The exact structural composition of the calcium/zinc mixed soaps of formula :35 (I) in their preferred embodiments is not known. How-~~~~929 ever, it is certain that they are not physical mixtures, but rather chemical mixtures because very little, if any, free calcium hydroxide or free calcium oxide could still be detected. Proof was provided by investigating the quantities of free calcium oxide observed when the basic calcium/zinc mixed soaps dissolved or suspended in lubricants are stored for 3 hours in a heating cabinet.
Comparison of the basic calcium/zinc mixed soaps accard-ing to the invention with the mixed soaps produced i.n a solid-state reaction in accordance with DE-A-38 06 192 shows that free calcium oxide sediments in varying amounts during storage. The purity of the basic calcium/
zinc mixed soaps can be estimated from the results of the tests thus carried out. The calcium/zinc mixed saaps according to the invention are dissolved or suspended in typical lubricants for halogen-containing plastics in a purity of more than 85~ by weight. The balance to 1.00%
is unreacted calcium oxide or calcium hydroxide - calcu-lated without lubricant.
>.0 The basic calcium/zinc mixed soaps are dissolved or suspended in lubricants which are typical of the thermo-plastic halogen-containing thermoplastics and which have low melt viscosities. Particularly preferred lubricants have a Hoppler viscosity in the melt at 80~C of less than 150 mPa~s. In a particularly preferred embodiment, the basic calcium/zinc mixed soaps are dissolved or suspended in one or more lubricants selected from the group con-sisting of a) fatty alcohols containing 8 to 22 carbon atoms, a0 b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms arid 2 to 6 hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to formula (II):
RZ-CO-R3 ( I I ) in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon .L 0 atoms , f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, such as polyethylene waxes and .L5 paraffins, h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
The compounds listed above are compounds known per se for halogen-containing plastics which are commercially :?0 available.
In a particularly preferred embodiment, the basic calcium/zinc mixed soaps are present in the described lubricants typical of halogen-containing thermoplastics in quantities of 10 to 60~ by weight and preferably in :?5 quantities of 20 to 50~ by weight, based on the mixture of basic calcium/zinc mixed soaps and lubricant, in dissolved or suspended form. The expression used in this connection that the calcium/zinc mixed soaps are present in "dissolved" or "suspended" form means that the basic :30 calcium/zinc mixed soaps have been produced in a melt containing the usual lubricants.
The basic calcium/zinc mixed soaps may be used as sole stabilizer component or in admixture with stabil-izers known from the prior art. Known stabilizers are 35 optionally surface-modified hydrotalcites which are commercially available under the name of Alcamizer~ from Kyowa Chemical. Int., synthetic crystalline sodium sili-cates, for example of the NaA type described in DE-~r-24 12 837, and/or basic calcium/aluminium hydroxyphosph:ites according to DE-C-39 41 902. The hydrotalcites marketed by Kyowa have a BET surface of less than 30 mZ/g and are usually surface-modified with dispersants, such as sodium stearate. However, it is also possible to use hydrotal-cites with larger surfaces or with other surface modify-ing agents, such as the hydrotalcites described in DE-A-41 17 034 and DE-A-41 17 035. In addition, basic mag-nesium/zinc mixed soaps with a composition corresponding to the formula (Mg0)xZn(OOCR)Z, where x is a number of 0.1 to 2.5 and R may be an alkyl radical, may be used as stabilizers. Basic magnesium/zinc mixed soaps such as these are produced from zinc soaps corresponding to the formula Zn(OOCR)Z and 0.1 to 2.5 moles of magnesium oxide or hydroxide per mole of zinc soap in a melt-phase reaction in accordance with one of applicants' ear:Lier applications, preferably in the presence of catalytic quantities of acids and, more particularly, at tempera-tures above the melting temperature and below the decom-position temperature of the zinc soap. In a particularly preferred embodiment, the basic calcium/zinc mixed soaps according to the invention are used together with the hydrotalcites and/or basic magnesium/zinc mixed soaps.
The present invention also relates to a process for the production of basic calcium/zinc mixed soaps corre sponding to formula (I), characterized in that calcium oxide or calcium hydroxide is added to a melt containing zinc soaps corresponding to formula (III) Zn(oOCRl)2, where R1 is as already defined, and the lubricants with low melt viscosities typical of halogen-containing thermoplastics, the reaction mixture being heated above its melting point in the presence of catalytic quantities of acid until the free calcium oxide or calcium hydro~:ide has reacted off. Calcium oxide or calcium hydroxide is added to the melt in quantities of 0.1 to 2.5 moles per mole of zinc soap corresponding to formula (III). In general, the catalytic quantities of acids are added at the same time as the calcium oxide or calcium hydroxide.
The reaction mixture obtained is kept in the melt until almost all the calcium oxide or calcium hydroxide has reacted off. The end of the reaction is indicated by a :LO clear or cloudy melt which no longer contains any solid particles visible to the naked eye. As described above, the conversion may be determined by determining the unreacted calcium oxide or calcium hydroxide in storage.
In a particularly preferred embodiment, 1 to 1.5 moles of :L5 calcium oxide or ca:Lcium hydroxide are added per mole: of zinc soap. In another preferred embodiment, acids are present in quantities of 0.001 to 0.1~ by weight, based on the reaction mixture. Typical acids are short-chain monocarboxylic acids containing 1 to 3 carbon atoms, such 20 as acetic acid, and mineral acids of which the anions are compatible with the plastics to be stabilized, such as phosphoric acid. The temperature at which the reaction between calcium hydroxide or calcium oxide with the zinc soaps takes place in the presence of the typical lubri-:~5 cants mentioned is above the melting temperatures and below the decomposition temperatures of the zinc soaps.
In general, the decomposition temperatures are in the range from 100 to 180°C, depending on the melting paint and the decomposition point of the zinc soap selected.
:30 For reactions of zinc stearate, the temperatures are of the order of 150°C. The reaction of the calcium oxide or calcium hydroxide with the zinc soaps is carried out: in the presence of the lubricants already mentioned to reduce the viscosity of the melt. Thus, the absence of :35 these compounds would result in the formation o:E a ~2~6929 reaction mixture which would have such a high viscosity at the melting temperature of the zinc soaps that it would be virtually impossible to stir so that the reac-tion could only be completed only partly, if at all. The quantities of :lubricant present in the melt are selected so that 40 to 90% by weight and preferably 50 to 80a; by weight of the mixture obtained consists of lubricant, 10 to 60~ by weight and preferably 20 to 50 o by weight. of the mixture being the basic calcium/zinc mixed soaps.
:LO The zinc soaps of formula (III) used in the process could either be commercially obtained or may even be produced in situ by reacting carboxylic acids, hydroxy-carboxylic acids or ketofatty acids corresponding to formula R1COOH with zinc salts, preferably with zinc :15 oxide, in a malar ratio of about 2:1. The reaction is preferably carried out by initially melting the car-boxylic acids R1COOH and adding the zinc salts, par-ticularly zinc oxide, to the resulting melt. The reac-tion is continued until the fatty acids have almost :?0 completely reacted. The substantially complete reaction can be recognized by determining the acid value in accordance with DIN 53402. The reaction may also be accelerated by the presence of catalytic quantities of acids. The acids may be used in quantities of 0.001. to 25 0.1% by weight, based on the reaction mixture. Shart-chain monocarboxylic acids and mineral acids may also be used.
In the preferred embodiment of the process according to the invention, the carboxylic acids R1COOH are initial-30 ly introduced and melted together with the lubricants.
The zinc salts are added to the resulting melt in such stoichiometric quantities that zinc soaps corresponding to formula (III) are initially formed. Catalytic quan-tities of acids are preferably present. The calcium :35 oxide or calcium hydroxide is then added in corresponding ~~.~~~?9 molar quantities to the resulting melt of zinc soaps and lubricants. This second reaction step is also preferably carried out in the presence of catalytic quantities of acids. Where calcium hydroxide is added, the water of reaction formed is continuously removed from the reaction mixture. On completion of the reaction, the basic cal-cium/zinc mixed soaps accumulate in the form of a solu-tion or suspension .in the usual lubricants, preferably in the lubricants a) to h). The reaction product obtained l0 is a dust-free solid which, if desired, may be further processed, for example by spraying.
If the basic calcium mixed soaps according to the invention are used with other stabilizers known from the prior art, such as the hydrotalcites or basic magnesium/
zinc mixed soaps, the known stabilizers are added to the final mixture of basic calcium/zinc mixed soaps and typical lubricants, preferably the lubricants a) to h).
The present invention also relates to the use of basic calcium/zinc mixed soaps corresponding to formula (I) - dissolved or suspended in typical lubricants for halogen-containing plastics - according to claim 1 as stabilizers for halogen-containing thermoplastics, more particularly PVC. For the use according to the inven-tion, the quantity of basic calcium/zinc mixed soaps dissolved or suspended in lubricants is from 0.05 to 5 parts by weight arid preferably 0.2 to 2 parts by weight, expressed as basic calcium/zinc mixed soap in solution or suspension in lubricants and based on 100 parts by weight of halogen-containing plastics. If other stabilizers known from the prior art are used together with the basic calcium/zinc mixed soaps according to the invention, they are used in typical quantities; for example, hydrotal-cites may be used in quantities of 0.1 to 0.5 part by weight and, the basic calcium/zinc mixed soaps in quanti-:35 ties of 0.05 to 5 parts by weight per 100 parts by weight ~1~~~~9 of halogen-containing plastics. If desired, other lubri-cants, release agents, plasticizers and/or co-stabilizers known from the prior art, such as the lubricants a) to h), or esters of epoxidized fatty acids with monofunc-tional alkanols or with polyols, 8-diketones, such as benzoyl stearoyl methane, hydroxyfunctional isocyanurates and/or secondary and/or tertiary esters of phosphorous acid, such as dialkylaryl phosphites. These additional additives may be incorporated in typical quantities in the thermoplastic halogen-containing plastics.
Halogen-containing plastics in the context of the invention are, above all, chlorine-containing homopoly-mers and copolymers of vinyl chloride. Preferred copoly-mers are polymers of at least 50~ by weight of vinyl chloride and other polymerizable monomers, such as vinyl esters, methacrylates, fumarates, butadiene and vinyli-dene chloride. However, polyvinyl chloride homopolymers with K values of 60 to 70, which can be produced by emulsion, suspension or bulk polymerization, are par-ticularly preferred. The PvC may of course also be modified with impact modifiers and flow modifiers.
Where the stabilizers according to the invention are used, PVC compounds in particular do not show any signs of overlubrication despite the metal content of calcium and zinc required for stabilization. This can be seen in particular in extruders where the buildup of pressure is lower than for mixtures of calcium oxide and zinc soaps or calcium soaps and zinc soaps. Accordingly, very much more of 'the stabilizers according to the invention may be used in the plastic without any danger of overlubr:ica-tion. Lastly, the basic calcium/zinc mixed soaps accord-ing to the invention are dust-free solids which may read-ily be further processed and which are easy to handle.
~~.~~~?~
E x a m p 1 a s A) Production of the basic calcium/zinc soaps Percentages are percentages by weight.
Example 1: Ca0~Zn-Z-ethyl hexanoate (40%) with glycerol distearate (60%) 56.7 g (0.39 mole) of 2-ethyl hexanoic acid and 120 g of glycerol distearate were introduced into a four necked spherical flask equipped with a stirrer, ther mometer and descending condenser. 15.9 g (0.195 mole) of zinc oxide were added in portions to the molten mixture, after which vacuum was applied. The vacuum was con-tinuously increased until, after about 1 hour, a vacuum of about 30 hPa was reached. After a total of 1.5 hours, the acid value as measured in accordance with DIN 53402 was below 4. After venting, 14.4 g (0.195 mole) of cal-cium hydroxide and 0.05 g of 99% acetic acid were added in the second reaction step. The reaction was over after 2.5 hours under a vacuum of about 30 hPa. A yellowish, brittle wax-like mass with a melting point of 75°C was obtained.
Example 2: Ca0~zinc oleate (40%) with glycerol dioleate (60%) 65.9 g (0.24 mole) of technical oleic acid, 120 g of glycerol dioleate and 0.05 g of 99$ acetic acid were initially introduced into the reaction flask as in Example 1. 9.6 g (0.12 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
8.7 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction step, after which the further procedure was as in Example 1. A
yellowish brown-tinged vaseline-like mass with a melting point of 69°C was obtained.
Example 3: Ca0~Zn-12-hydroxystearate (40%) with hydrogen-ated castor oil (60%) 67.2 g (0.22 mole) of 12-hydroxystearic acid, 120 g of hydrogenated castor oil and 0.05 g of 99~ acetic acid were initially introduced into the reaction flask as in Example 1. 8.'7 g (0.11 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
8.0 g (0.11 mole) of calcium hydroxide and 0.05 g' of acetic acid were added in the second reaction step, after which the further procedure was as in Example 1. A
brownish wax-like mass with a melting point of 132°C was obtained.
Example 4: Ca0~Zn stearate (40%) with glycerol tri-stearate (60%) 6.5 g (0.24 mole) of technical stearic acid, 12 0 g of glycerol tristearate and 0.05 g of 99~ acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (().12 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second process step as in Example l, after which the further procedure was as in Example 1. A brownish, hard wax-like mass with a melting point of 106°C was obtained.
Example 5: Ca0~Zn stearate (40%) with tallow fatty alcohol (60%) 65.5 g (0.24 mole) of technical stearic acid, 120 g of tallow fatty alcohol and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (0.12 mole) of zinc oxide were added to the molten mixture and vacuum was applied. In the second reaction step, 9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added and reacted as described r, ~ e~
in Example 1. A yellow wax-like mass with a melting point of 108°C was obtained.
Example 6: Ca0~Zn stearate (40%) with tallow fatty alcohol stearate 65.5 g (0.24 mole) of technical stearic acid, 120 g of tallow fatty alcohol stearate and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (0.12 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction step, after which the further procedure was as in Example 1. A
yellowish, hard wax-like mass with a melting point of 115°C was obtained.
Example 7: 1.5 Ca0~Zn stearate (20%) with pentaerythritol distearate (60%) 31.4 g (0.116 mole) of technical stearic acid, 80 g of Penta~ distearate and 0.05 g of acetic acid were initially introduced into the reaction flask as in Example 1. 4.7 g (0.058 mole) of zinc oxide were added in portions to the molten mixture and vacuum was applied.
In the second reaction step, another 80 g of Penta~
distearate and - after it had melted - 6.5 g (0.088 mole) of calcium hydroxide and 0.05 g of acetic acid 'were introduced into the reaction mixture. The reaction was continued as in Example 1. A yellow wax-like mass with a melting point of 110°C was obtained.
Example 8: Ca0~Zn stearate (40%) with glycerol distearate (60%) 65.5 g (0.24 mole) of technical stearic acid, 120 g of glycerol distearate and 0.05 g of 99o acetic acid were initially introduced into the reaction flask as in t Example 1. 9.8 g (0.12 mole) of zinc oxide were intro-duced into the molten mixture in portions and vacuum was applied. 9.1 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction step, 5 after which the reaction was continued as in Example 1.
A pale yellowish wax-like mass with a melting point of 95°C was obtained.
TM
Example 9: Ca0~Zn stearate (30%) with Paraffin FP 90-100 10 (70%) 65.5 g (0.24 mole) of technical stearic acid, 186.7 g of paraffin and 0.05 g of acetic acid were initially introduced into the reaction flask as in Example 1. 9.9 g (0.12 mole) of zinc oxide were added in portions to the 15 molten mixture and vacuum was applied. 9.0 g (0.12 mole) of calcium hydroxide and 0.05 g of acetic acid were added in the second reaction stage, after which the reaction was continued as in Example 1. A yellow wax-like mass with a melting point of 127°C was obtained.
Example 10: Ca0~Zn-12-ketostearate (50%) with glycerol distearate (50%) 83.4 g (0.28 mole) of 12-ketostearic acid, 100 g of glycerol distearate and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 11.3 g (0.14 mole) of zinc oxide were added in portions to the melt and vacuum was applied. In the second reaction step, 10.3 g (0.14 mole) of calcium hydroxide and 0.05 g of acetic acid were added, after which the reaction was continued as in Example 1. A pale yellowish, hard wax-like mass with a melting point of 115°C was obtained.
z~.~~~929 Example 11: 2 Ca0~Zn stearate (40%) with glycerol di-stearate (60%) 60.4 g (0.22 mole) of technical stearic acid, 120 g of glycerol distearate and 0.05 g of 99% acetic acid were initially introduced into the reaction flask as in Example 1. 9.1 g (0.11 mole) of zinc oxide were intro-duced into the molten mixture at 140 to 150°C and vacuum was applied. 16.6 c~ (0.22 mole) of calcium hydroxide and 0.05 g of 99~ acetic acid were added in the second reaction step, after which the reaction was continued as in Example 1. A pale yellowish wax-like mass with a melting point of 95°C was obtained.
B) Comparison of the free quantity of calcium oxide B1) 150 g of the. basic calcium/zinc mixed soap of Example A8) according to the invention, correspond-ing to 40% of Ca0~zinc stearate in 60% of glycerol distearate B2) 60 g of the basic calcium/zinc mixed soap according to Example 1 of DE-A-38 06 192 were homogenized in 90 g of glycerol distearate until a fine-particle, homogeneous solids mixture was present.
B1) and B2) were melted and transferred to a glass beaker. The glass beaker was then stored in a heating cabinet for 3 hours at 140°C. After cooling of the melt, the glass beaker was removed. Product was scraped off from the top and middle of the solidified melt and from the sediment. The scrapings were investigated for their ash content, i.e. calcium and zinc oxide, in accordance with DIN EN7 and a ratio was formed between the result obtained and the theoretical quantity of zinc oxide and calcium oxide (8.4a).
In the case of B1), no phase separation was observed ~1~69'9 in the molten state.
Determination of the ash content revealed the following quantities of calcium and zinc oxide:
top: 8.2% middle: 8.2% bottom: 8.7%
In other words, in relation to the theoretical content of calcium and zinc oxide of 8.4%, 8.4 - 8.2% - 0.2% had sedimented from the melt. Assuming that the entire :10 sediment is calcium oxide and that, of the 8.4% of calcium and zinc oxides, 3.4% is calcium oxide, the free calcium oxide content on the basis of the relation 0.2 ~ 100 = 5.8 is 5.8% which could collect as sediment.
3.4 The degree of conversion is thus 100% - 5.8% = 94.2% of basic calcium/zinc mixed soaps.
In the case of B2), it was apparent even during storage of the melt that a thick sediment had formed, :20 leaving the supernatant melt clear. Determination of the ash content revealed the following quantities of calcium and zinc oxide:
top: 5.6%: middle: 5.6%; sediment: 21.7%, i.e. in rela tion to the theoretical content of 8.4% of calcium and zinc oxide, 8.4 - 5.6 - 2.8% had sedimented from the melt. Since this could not all be calcium oxide, the sediment was titrated with Titriplex~ 3 to determine the calcium content. Converted to calcium oxide, a value of 1.17% was obtained, i.e. 1.17% ~ 100% = 34.4% of the 3.4 quantity of calcium oxide theoretically present are con-tained as free calcium oxide in the product B2).
C) Performance tests 100 Parts by weight of suspension PVC with a K value of 68 (Corvic S 68/173~) were mixed with the compounds ~I~~9~9 listed in Table 1 in the quantities shown there (in parts by weight; phr). Ca0~zinc stearate (40~) in glycerol distearate (60%) according to Example A8) was tested in Examples Cl) and C2) according to the invention. A
mixture of calcium stearate and zinc stearate and also calcium hydroxide and zinc stearate was used for compari-son. The quantity of comparison mixture was selected so that the Ca and zinc contents corresponded to those of Example A8).
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In the case of B2), it was apparent even during storage of the melt that a thick sediment had formed, :20 leaving the supernatant melt clear. Determination of the ash content revealed the following quantities of calcium and zinc oxide:
top: 5.6%: middle: 5.6%; sediment: 21.7%, i.e. in rela tion to the theoretical content of 8.4% of calcium and zinc oxide, 8.4 - 5.6 - 2.8% had sedimented from the melt. Since this could not all be calcium oxide, the sediment was titrated with Titriplex~ 3 to determine the calcium content. Converted to calcium oxide, a value of 1.17% was obtained, i.e. 1.17% ~ 100% = 34.4% of the 3.4 quantity of calcium oxide theoretically present are con-tained as free calcium oxide in the product B2).
C) Performance tests 100 Parts by weight of suspension PVC with a K value of 68 (Corvic S 68/173~) were mixed with the compounds ~I~~9~9 listed in Table 1 in the quantities shown there (in parts by weight; phr). Ca0~zinc stearate (40~) in glycerol distearate (60%) according to Example A8) was tested in Examples Cl) and C2) according to the invention. A
mixture of calcium stearate and zinc stearate and also calcium hydroxide and zinc stearate was used for compari-son. The quantity of comparison mixture was selected so that the Ca and zinc contents corresponded to those of Example A8).
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l~M M riri IIltf7 O G1 d' d' O O O O O O ~-i1 I 1 I I I
rl O
U rl i.1 O 11Y
G) N ./-1 ~
rl N flf ~
W N N S-Y
'O
'ri .EJ f~
r1 b N -. it a~
O
O O ~ 1-t r-i t~ !~ >~ ~ ~ N U7 td O 1r O ~-.O !~ O
.~1 .~.~f~ ~ N ~ ~ cU O
cd .a, U x H -~v ~ x +~ a~
w rl rti ~- ~ .~ U .~N b ~
0l n, tc1of-.1 N +~ ~ N
O .~r 01 U ~,"r-I~.,f~fr1 N ~ ~.l ~-I
-rl ~ rl~ 'y f~
Ql rl 'C~N' FtiU7 .Lirif~fri O '~f ri ~ ~'O ~ '~~~N ttJ fd 'n' ltS
4..1 o of x -~ ,~ o fa+~ s~ a~ 1~ a~ o a~ a~
-.~
~n o rr v a~ ~ ro~n +~ rd +~ i'Ib .~
b ~ ~ ~ o -~
a~ ~ ~ ~ ~ b ~ o ~ ~ ~ ro, .~
O W I ~ U ?~ >'arn fa ~ rtiN ~ .~O >~
en N Gl ~ O ~ f.~T3 ~ cd O O
o~ +~ +~ O ~- rtf~ ~r rlo O N +~ ~ +~ >~
O
.-i.1 U ~f -~-1 1~ .C;?if~ ~ ~ N ",..1"u7 ~ ~ UI
r-1 w o ,~ s~ x a ,-rI o a~ m a~ -~I -~I'~1a~
w n 41 'C3 ?, ~0 ~-ih ~r U7 N U O ~ U U U U U :~
a~ .-I O U S.~ +~ cd 2f,sG-~ O ~-r.t~rtfs~ ~ s~ ~-1~-1t~
b S-~ ~ U -.i,~ ?,r-~1l.~y -~ cU 7<-.irti-rlc~f~d cd ~
W G4 ~ H U x ~ H t~1U U W N U t~ U U ~:
~
i The composition shown in Table 1 was processed to a molding compound. The molding compound obtained was processed in a cM mmercial twin-screw extruder (Reifen-hauser BT 55/16 twin-screw extruder). The following 5 parameters were selected for the production of rectan-gular pipes (63x3 mm):
Cylinder temperature: 170 / 170 / 170 / 150 / 150°C
Head temperature: 155 / 170 / 170°C
Screw: K 6/2 10 Screw speed: 25 r.p.m.
The melt pressure 2 (in bar) building up in front of the mold was determined during processing. In addition, utilization of the machine capacity (in %) was read off.
The results are set out in Table 2.
Table 2:
Parameter Cl) C2) Comp. Comp. Comp.
Melt pressure 2 319 301 270 270 249 Capacity utilization 51 46 42 36 39 Table 2 shows that the melt pressure building up in front of the mold is distinctly higher in the Examples according to the invention than in the Comparison Exam-ples. Given good utilization of machine capacity, this indicates a good lubricating effect is present without overlubrication occurring (low melt pressure 2).
In~addition, dynamic stability was tested on 1x1 cm test specimens taken from 0.5 mm thick strips. To this end, the 1x1 cm test specimens were placed in a heating cabinet with rotating shelves at 180°C. After 15 min-utes, samples were removed. Dark brown discoloration indicates the end of stability. The compositions C1) and Comp. 4) from Table 1 were tested.
~~ ~69~9 i~t0 94/19308 21 PCT/Ep94/oo458 TablB 3:
Example End of stability in minutes Col~p . 12 0 1G Table 3 shows that the dynamic stabilities of the Examples containing the stabilizers according to the invention are better than mixtures of zinc soaps and calcium oxide (Comp. 4).
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to t=he embodiments o:~ the invention described specifically above. Such equivalents are intended to be encompassed in the scope o~ the fol..lowing claims.
-.~
~n o rr v a~ ~ ro~n +~ rd +~ i'Ib .~
b ~ ~ ~ o -~
a~ ~ ~ ~ ~ b ~ o ~ ~ ~ ro, .~
O W I ~ U ?~ >'arn fa ~ rtiN ~ .~O >~
en N Gl ~ O ~ f.~T3 ~ cd O O
o~ +~ +~ O ~- rtf~ ~r rlo O N +~ ~ +~ >~
O
.-i.1 U ~f -~-1 1~ .C;?if~ ~ ~ N ",..1"u7 ~ ~ UI
r-1 w o ,~ s~ x a ,-rI o a~ m a~ -~I -~I'~1a~
w n 41 'C3 ?, ~0 ~-ih ~r U7 N U O ~ U U U U U :~
a~ .-I O U S.~ +~ cd 2f,sG-~ O ~-r.t~rtfs~ ~ s~ ~-1~-1t~
b S-~ ~ U -.i,~ ?,r-~1l.~y -~ cU 7<-.irti-rlc~f~d cd ~
W G4 ~ H U x ~ H t~1U U W N U t~ U U ~:
~
i The composition shown in Table 1 was processed to a molding compound. The molding compound obtained was processed in a cM mmercial twin-screw extruder (Reifen-hauser BT 55/16 twin-screw extruder). The following 5 parameters were selected for the production of rectan-gular pipes (63x3 mm):
Cylinder temperature: 170 / 170 / 170 / 150 / 150°C
Head temperature: 155 / 170 / 170°C
Screw: K 6/2 10 Screw speed: 25 r.p.m.
The melt pressure 2 (in bar) building up in front of the mold was determined during processing. In addition, utilization of the machine capacity (in %) was read off.
The results are set out in Table 2.
Table 2:
Parameter Cl) C2) Comp. Comp. Comp.
Melt pressure 2 319 301 270 270 249 Capacity utilization 51 46 42 36 39 Table 2 shows that the melt pressure building up in front of the mold is distinctly higher in the Examples according to the invention than in the Comparison Exam-ples. Given good utilization of machine capacity, this indicates a good lubricating effect is present without overlubrication occurring (low melt pressure 2).
In~addition, dynamic stability was tested on 1x1 cm test specimens taken from 0.5 mm thick strips. To this end, the 1x1 cm test specimens were placed in a heating cabinet with rotating shelves at 180°C. After 15 min-utes, samples were removed. Dark brown discoloration indicates the end of stability. The compositions C1) and Comp. 4) from Table 1 were tested.
~~ ~69~9 i~t0 94/19308 21 PCT/Ep94/oo458 TablB 3:
Example End of stability in minutes Col~p . 12 0 1G Table 3 shows that the dynamic stabilities of the Examples containing the stabilizers according to the invention are better than mixtures of zinc soaps and calcium oxide (Comp. 4).
Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to t=he embodiments o:~ the invention described specifically above. Such equivalents are intended to be encompassed in the scope o~ the fol..lowing claims.
Claims (21)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A composition of matter comprising a basic calcium/zinc mixed soap having the formula:
(CaO)n .cndot. Zn(OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 0.1 to 2.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap.
(CaO)n .cndot. Zn(OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 0.1 to 2.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap.
2. A composition as claimed in claim 1 wherein n is a number from 1 to 1.5.
3. A composition as claimed in claim 1 wherein said lubricant is selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
4. A composition as claimed in claim 3 wherein said hydrocarbon waxes are selected from the group consisting of polyethylene waxes and paraffins.
5. A composition as claimed in claim 1 wherein said lubricant is selected from the group consisting of 1) fatty alcohols containing 8 to 22 carbon atoms, 2) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, 3) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to 6 hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, and 4) paraffins.
6. A composition as claimed in claim 1 wherein the amount of said basic calcium/zinc mixed soap is 10 to 60% by weight of said composition.
7. A composition as claimed in claim 1 wherein the amount of said basic calcium/zinc mixed soap is 20 to 50% by weight of said composition.
8. A composition as claimed in claim 1 wherein said lubricant has a Höppler viscosity in a melt at 80°C of less than 150 mPa.cndot.s.
9. A composition of matter comprising a basic calcium/zinc mixed soap having the formula:
(CaO)n .cndot. Zn (OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 1 to 1.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 1 to 1.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap, said calcium/zinc mixed soap being present in said composition in a quantity of from 20% to 50% by weight of said composition, and said lubricant having a Höppler viscosity in a melt at 80°C of less than 150 mPa .cndot.s and being selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
(CaO)n .cndot. Zn (OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 1 to 1.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 1 to 1.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap, said calcium/zinc mixed soap being present in said composition in a quantity of from 20% to 50% by weight of said composition, and said lubricant having a Höppler viscosity in a melt at 80°C of less than 150 mPa .cndot.s and being selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
10. A process for the production of basic calcium/zinc mixed soaps, said process comprising:
1) adding calcium oxide or calcium hydroxide to a melt containing a zinc soap having the formula:
Zn(OOCR1)2, in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and a lubricant for a halogen-containing thermoplastic, the quantity of calcium oxide or calcium hydroxide being 0.1 to 2.5 moles per mole of said zinc soap, and 2) heating the reaction mixture above its melting point until the free calcium oxide or calcium hydroxide has been removed;
wherein said reaction mixture is heated in the presence of an acid in a quantity of 0.001 to 0.1 % by weight, based on said reaction mixture.
1) adding calcium oxide or calcium hydroxide to a melt containing a zinc soap having the formula:
Zn(OOCR1)2, in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and a lubricant for a halogen-containing thermoplastic, the quantity of calcium oxide or calcium hydroxide being 0.1 to 2.5 moles per mole of said zinc soap, and 2) heating the reaction mixture above its melting point until the free calcium oxide or calcium hydroxide has been removed;
wherein said reaction mixture is heated in the presence of an acid in a quantity of 0.001 to 0.1 % by weight, based on said reaction mixture.
11. A process as claimed in claim 10 wherein said quantity of calcium oxide or calcium hydroxide is 1 to 1.5 moles per mole of said zinc soap.
12. A process as claimed in claim 10 wherein said lubricant is selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
13. A process as claimed in claim 10 further comprising, prior to step 1), forming said zinc soap by steps comprising melting carboxylic acids having the formula R1COOH with said lubricant and then adding zinc salts to the resulting melt in such stoichiometric quantities that said zinc soap is formed.
14. A process for the production of basic calcium/zinc mixed soaps, said process comprising:
1) adding calcium oxide or calcium hydroxide to a melt containing a zinc soap having the formula:
Zn(OOCR1)2, in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and a lubricant for a halogen-containing thermoplastic, the quantity of calcium oxide or calcium hydroxide being 1 to 1.5 moles per mole of said zinc soap, and 2) heating the reaction mixture above its melting point in the presence of acid in quantities of 0.001 to 0.1% by weight, based on said reaction mixture until the free calcium oxide or calcium hydroxide has been removed, wherein said lubricant has a Höppler viscosity in a melt at 80°C of less than 150 mPa.cndot.s and is selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
1) adding calcium oxide or calcium hydroxide to a melt containing a zinc soap having the formula:
Zn(OOCR1)2, in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and a lubricant for a halogen-containing thermoplastic, the quantity of calcium oxide or calcium hydroxide being 1 to 1.5 moles per mole of said zinc soap, and 2) heating the reaction mixture above its melting point in the presence of acid in quantities of 0.001 to 0.1% by weight, based on said reaction mixture until the free calcium oxide or calcium hydroxide has been removed, wherein said lubricant has a Höppler viscosity in a melt at 80°C of less than 150 mPa.cndot.s and is selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000.
15. In a method of stabilizing a halogen-containing thermoplastic, the improvement comprising the use as a stabilizer of a composition of matter comprising a basic calcium/zinc mixed soap having the formula:
(CaO)n .cndot. Zn (OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 0.1 to 2.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap; and heating the reaction mixture above its melting point until the free calcium oxide or calcium hydroxide has been removed;
wherein said reaction mixture is heated in the presence of an acid in a quantity of 0.001 to 0.1% by weight, based on said reaction mixture.
28a
(CaO)n .cndot. Zn (OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 0.1 to 2.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 0.1 to 2.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap; and heating the reaction mixture above its melting point until the free calcium oxide or calcium hydroxide has been removed;
wherein said reaction mixture is heated in the presence of an acid in a quantity of 0.001 to 0.1% by weight, based on said reaction mixture.
28a
16. A method as claimed in claim 15 wherein said halogen-containing thermoplastic is PVC.
17. A method as claimed in claim 15 wherein the quantity of basic calcium/zinc mixed soap is from 0.05 to 5 parts by weight per 100 parts by weight of halogen-containing thermoplastic.
18. A method as claimed in claim 15 wherein the quantity of basic calcium/zinc mixed soap is from 0.2 to 2 parts by weight per 100 parts by weight of halogen-containing thermoplastic.
19. A method as claimed in claim 15 wherein said halogen-containing thermoplastic is a copolymer of at least 50% by weight of vinyl chloride copolymerized with other polymerizable monomers.
20. A method as claimed in claim 16 wherein said halogen-containing thermoplastic is a polyvinyl chloride homopolymers with K values of 60 to 70.
21. In a method of stabilizing a halogen-containing thermoplastic, the improvement comprising the use as a stabilizer of a composition of matter comprising a basic calcium/zinc mixed soap having the formula:
(CaO)n .cndot. Zn (OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 1 to 1.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 1 to 1.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap, and heating the reaction mixture above its melting point until the free calcium oxide or calcium hydroxide has been removed;
said calcium/zinc mixed soap being present in said composition in a quantity of from 20% to 50% by weight of said composition, and said lubricant having a Höppler viscosity in a melt at 80°C of less than 150 mPa .cndot.s and being selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000;
wherein said reaction mixture is heated in the presence of an acid in a quantity of 0.001 to 0.1% by weight, based on said reaction mixture.
(CaO)n .cndot. Zn (OOCR1)2 in which R1 represents one or more alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl radicals containing 7 to 21 carbon atoms or ketoalkyl radicals containing 11 to 21 carbon atoms and n is a number of 1 to 1.5, the basic calcium/zinc mixed soap being dissolved or suspended in a lubricant for a halogen-containing plastic, said composition having been prepared by adding calcium oxide or calcium hydroxide to a melt containing zinc soaps Zn(OOCR1)2, where R1 is as defined above, and a lubricant for a halogen-containing plastic, said calcium oxide or calcium hydroxide being added in a quantity of 1 to 1.5 moles of calcium oxide or calcium hydroxide per mole of zinc soap, and heating the reaction mixture above its melting point until the free calcium oxide or calcium hydroxide has been removed;
said calcium/zinc mixed soap being present in said composition in a quantity of from 20% to 50% by weight of said composition, and said lubricant having a Höppler viscosity in a melt at 80°C of less than 150 mPa .cndot.s and being selected from the group consisting of:
a) fatty alcohols containing 8 to 22 carbon atoms, b) esters of monofunctional alkanols containing 1 to 22 carbon atoms with fatty acids containing 8 to 34 carbon atoms, c) full esters of dicarboxylic acids containing 3 to 6 carbon atoms with monofunctional alkanols containing 8 to 22 carbon atoms, d) partial and full esters of polyols containing 2 to 15 carbon atoms and 2 to hydroxyl groups with fatty acids containing 8 to 34 carbon atoms, e) fatty ketones corresponding to the formula:
in which R2 and R3 may be the same or different and represent alkyl groups containing 5 to 21 carbon atoms, f) diamides of fatty acids containing 8 to 22 carbon atoms with alkylenediamines containing 2 to 6 carbon atoms, g) hydrocarbon waxes, and h) oxidized polyethylene waxes with a number average molecular weight of 3,000 to 9,000;
wherein said reaction mixture is heated in the presence of an acid in a quantity of 0.001 to 0.1% by weight, based on said reaction mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4305944A DE4305944A1 (en) | 1993-02-26 | 1993-02-26 | Basic calcium / zinc mixed soaps |
| DEP4305944.9 | 1993-02-26 | ||
| PCT/EP1994/000458 WO1994019308A1 (en) | 1993-02-26 | 1994-02-18 | Alkaline calcium/zinc mixed soaps |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2156929A1 CA2156929A1 (en) | 1994-09-01 |
| CA2156929C true CA2156929C (en) | 2006-04-04 |
Family
ID=36143227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002156929A Expired - Fee Related CA2156929C (en) | 1993-02-26 | 1994-02-18 | Basic calcium/zinc mixed soaps |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2156929C (en) |
-
1994
- 1994-02-18 CA CA002156929A patent/CA2156929C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CA2156929A1 (en) | 1994-09-01 |
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