Modified silicon oil for wax-free die casting lubricants

Abstract

The present invention relates to a mixture of polyalkylsiloxanes obtainable through a hydrosilylation reaction wherein a mixture of monounsaturated olefins is reacted with an amount of one or more polyalkylhydrosiloxanes in the presence of a hydrosilylation catalyst. Furthermore, the invention concerns polyalkylsiloxane comprising alkyl side chains consisting of linear or branched alkyl groups with 40 to 60 carbon atoms, with 16 to 30 carbon atoms, and 6 to 15 carbon atoms. In addition, the present invention relates to water-based compositions suitable for use in metal casting processes as a mold release agent comprising a mixture of polyalkylsiloxanes, a non-ionic surfactant having a HLB value of at least 8, and less than 20 wt.-% of waxes. In addition, the present invention relates to the use of the polyalkylsiloxanes and mixtures of polyalkylsiloxanes.

Claims

1. A mixture of polyalkylsiloxanes obtained through a hydrosilylation reaction wherein a mixture of monounsaturated olefins consisting of: 1-20 mol % of olefins with 40 to 60 carbon atoms, 1-20 mol % of olefins with 16 to 30 carbon atoms, and 60-98 mol % of olefins with 6 to 15 carbon atoms is reacted with an amount of one or more polyalkylhydrosiloxanes in the presence of a hydrosilylation catalyst wherein each of the one or more polyalkylhydrosiloxanes comprises a repeating unit according to the general structure (I): ##STR00007## wherein n indicates the number of repeating units and ranges from 5 to 10,000; wherein the residue R.sup.1 is selected from linear or branched alkyl groups with less than 6 carbon atoms.

2. The mixture of polyalkylsiloxanes according to claim 1, wherein the amount of polyalkylhydrosiloxanes is at least 60% of the stoichiometric amount, but not more than the stoichiometric amount relative to the mixture of monounsaturated olefins.

3. The mixture of polyalkylsiloxanes according to claim 1, wherein the one or more polyalkylhydrosiloxanes includes polymethylhydrosiloxanes polymethylhydrosiloxanes.

4. The mixture of polyalkylsiloxanes according to claim 1, wherein at least 80 mol % of the mixture of monounsaturated olefins are selected from -olefins.

5. The mixture of polyalkylsiloxanes according to claim 1, wherein the temperature at which the mixture of monounsaturated olefins is reacted with the one or more polyalkylhydrosiloxanes is in a range of from 80 C. to 180 C. for a time sufficient to yield not more than 10 mol % SiH bonds in the mixture of polyalkylsiloxanes.

6. The mixture of polyalkylsiloxanes according to claim 1, wherein the hydrosilylation catalyst is a platinum catalyst.

7. The mixture of polyalkylsiloxanes according to claim 1, wherein an inert liquid vehicle that acts as a solvent for the one or more polyalkylhydrosiloxanes and/or the mixture of monounsaturated olefins is present in an amount of less than 20 wt.-%; and/or the mixture of polyalkylsiloxanes is an oil.

8. The mixture of polyalkylsiloxanes according to claim 7, wherein the inert liquid vehicle is present in an amount of less than 1 wt.-%; and/or the mixture of polyalkylsiloxanes is an oil.

9. The mixture of polyalkylsiloxanes according to claim 1, wherein the mixture of polyalkylsiloxanes is an oil.

10. The mixture of polyalkylsiloxanes according to claim 1, wherein at least 80 mol % of the repeating units of the one or more polyalkylhydrosiloxanes according to the general structure (I) have a residue R.sup.1 that is a methyl group.

11. A water-based metal casting mold release agent composition comprising: 1) 1-50 wt.-% of a mixture of polyalkylsiloxanes according to claim 1, 2) 1-15 wt.-% of a non-ionic surfactant having an HLB value of at least 8, and 3) less than 20 wt.-% of waxes.

12. A polyalkylsiloxane comprising repeating units according to general structure (II): ##STR00008## wherein n represents the number of repeating units comprised in the polyalkylsiloxane, and n is an integer of 5 to 10,000; wherein residue R.sup.1 is selected from the group consisting of linear or branched alkyl groups with less than 6 carbon atoms; and a) in 1-20% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 40 to 60 carbon atoms; b) in 1-20% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 16 to 30 carbon atoms; c) in 60-98% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 6 to 15 carbon atoms; and d) in 0-10% of the repeating units, R.sup.2 is H.

13. The polyalkylsiloxane according to claim 12, wherein in c), R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 10 to 14 carbon atoms.

14. The polyalkylsiloxane according to claim 12, wherein a) in 2-10% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 40 to 60 carbon atoms; b) in 2-15% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 16 to 30 carbon atoms, c) in 75-96% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 6 to 15 carbon atoms.

15. The polyalkylsiloxane according to claim 12, wherein the polyalkylsiloxane has a ratio of the repeating units according to a) to the repeating units according to b) in a range of from 2:3 to 3:2.

16. The polyalkylsiloxane according to claim 12, wherein the polyalkylsiloxane is an oil.

17. The polyalkylsiloxane according to claim 12, wherein R.sup.1 of each repeating unit according to general structure (II) is a methyl group.

18. A water-based metal casting mold release agent composition comprising: 1) 1-50 wt.-% of at least one polyalkylsiloxane according to claim 12, 2) 1-15 wt.-% of a non-ionic surfactant having an HLB value of at least 8, and 3) less than 20 wt.-% of waxes.

19. A metal casting process comprising: A.) applying a mold release agent to a metal-casting mold, the mold release agent comprising at least one polyalkylsiloxane selected from: i) a polyalkylsiloxane mixture obtained through a hydrosilylation reaction wherein a mixture of monounsaturated olefins consisting of 1-20 mol % of olefins with 40 to 60 carbon atoms, 1-20 mol % of olefins with 16 to 30 carbon atoms, and 60-98 mol % of olefins with 6 to 15 carbon atoms is reacted with an amount of one or more polyalkylhydrosiloxanes in the presence of a hydrosilylation catalyst, wherein each of the one or more polyalkylhydrosiloxanes comprises a repeating unit according to the general structure (I): ##STR00009## wherein n indicates the number of repeating units and ranges from 5 to 10,000; and wherein the residue R.sup.1 is selected from linear or branched alkyl groups with less than 6 carbon atoms; ii) a polyalkylsiloxane comprising repeating units according to general structure (II): ##STR00010## wherein n represents the number of repeating units comprised in the polyalkylsiloxane, and n is an integer of 5 to 10,000; wherein residue R.sup.1 is selected from the group consisting of linear or branched alkyl groups with less than 6 carbon atoms; a) in 1-20% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 40 to 60 carbon atoms; b) in 1-20% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 16 to 30 carbon atoms; c) in 60-98% of the repeating units, R.sup.2 is selected from the group consisting of linear or branched alkyl groups with 6 to 15 carbon atoms; and d) in 0-10% of the repeating units, R.sup.2 is H; iii) a polyalkylsiloxane comprise a repeating unit according to the following general structure (Ill): ##STR00011## wherein n indicates the number of repeating units being in a range of from 5 to 10,000; wherein for each repeating unit, the residue R.sup.1 is independently selected from linear alkyl groups with less than 6 carbon atoms; and wherein for each repeating unit, the residue R.sup.2 is independently selected from hydrogen, linear or branched alkyl groups having 6 to 15 carbon atoms, 16 to 30 carbon atoms or 40 to 60 carbon atoms, wherein, expressed as a fraction of 1, amount of repeating units with a residue R.sup.2 being hydrogen is less than 0.1, being a linear or branched alkyl group having 16 to 30 carbon atoms is in a range of from 0.01-0.2, being a linear or branched alkyl group having 40 to 60 carbon atoms is in a range of from 0.01-0.2, and being a linear or branched alkyl group having 6 to 15 carbon atoms is in a range of from 0.6-0.98; and mixtures thereof; B.) casting a metal in the metal-casting mold to form a casting; C.) releasing the casting from the metal-casting mold.

20. The metal casting process of claim 19, further comprising step D.) painting or plating the casting, wherein after step C.) and prior to step D.), the casting is not cleaned; and wherein the mold release agent is wax-free.

Description

EXAMPLES

Example 1

(1) Preparation of Modified Polysiloxane

(2) To a mixture of polymethylhydrosiloxane with the average formula (CH.sub.3).sub.3SiO(CH.sub.3HSiO).sub.25 Si(CH.sub.3).sub.3 (40 g, 602.5 mmol free SiH), 1-dodecene (4.76 g, 28.3 mmol) and -olefin with the average formula CH.sub.3(CH.sub.2).sub.40CHCH.sub.2 (16.32 g, 27.1 mmol, AlphaPlus C30+HA) was added 4 ppm of a H.sub.2PtCl.sub.6 solution in isopropanol (73 L, 17.1 mg/mL). The mixture was heated to 80 C. resulting in an exotherm heating the mixture to 140 C. A mixture of 1-dodecene (74.64 g, 443.4 mmol) and -olefin with the average formula CH.sub.3(CH.sub.2).sub.19CHCH.sub.2 (12.17 g, 43.4 mmol) was added at such a rate to keep the temperature at 140-150 C. After complete addition, the mixture was heated at 150 C. for 2 hours: FTIR analysis showed 5.0% remaining SiH groups. The viscosity of the product was 6300 mPa.Math.s.

(3) Preparation of Die Casting Release Agent

(4) The abovementioned modified polymethylsiloxane (30.5 g) was added to an emulsifier mixture (14.3 g). Under vigorous stirring, water was added to create the inversion point (7.0 g). Additional modified polymethylsiloxane (59.1 g) was added slowly under vigorous stirring. After 10 minutes water (89.1 g) was added slowly followed by addition of Acticide MV14 (Thor Chemie, 0.02 g). 76 gram of this emulsion was added to a mixture of Mayco base RP8765 (Dover Chemical Corporation, 2.6 g) and water (120.5 gram). To this mixture was added SAG 10E (Momentive, 0.1 gram) and Acticide MBS (Thor Chemie 0.8 g).

(5) Pressure Die Casting Tests

(6) The pressure die casting emulsion was tested against the wax-containing lubricant Deltacast CP-579 (23% solids, 0.8% dilution in water) which gives lubricant build-up during its use. The new lubricant (17% solids, 1.0% dilution in water) gave good release and afforded good clean castings without observable lubricant build-up on the die or spray nozzles.

Example 2

(7) Preparation of Modified Polysiloxane

(8) Preparation similar to Example 1 with a mixture of polymethylhydrosiloxane with the average formula (CH.sub.3).sub.3SiO(CH.sub.3HSiO).sub.25Si(CH.sub.3).sub.3 (40 g, 602.5 mmol free SiH), 1-dodecene (4.65 g, 27.7 mmol) and -olefin with the average formula CH.sub.3(CH.sub.2).sub.40CHCH.sub.2 (19.59 g, 32.5 mmol). Addition of a mixture of 1-dodecene (72.93 g, 433.3 mmol) and -olefin with the average formula CH.sub.3(CH.sub.2).sub.19CHCH.sub.2 (13.69 g, 48.8 mmol). FTIR analysis showed 4.7% remaining SiH groups. The viscosity of the product was 14000 mPa.Math.s.

(9) Preparation of die casting release agent was performed similar to Example 1.

Example 3

(10) Preparation of Modified Polysiloxane

(11) Preparation similar to Example 1 with a mixture of polymethylhydrosiloxane with the average formula (CH.sub.3).sub.3SiO(CH.sub.3HSiO).sub.25Si(CH.sub.3).sub.3 (60 g, 903.8 mmol free SiH), 1-dodecene (10.27 g, 61.0 mmol), -olefin with the average formula CH.sub.3(CH.sub.2).sub.19CHCH.sub.2 (3.76 g, 12.2 mmol) and -olefin with the average formula CH.sub.3(CH.sub.2).sub.30CHCH.sub.2 (3.42 g, 8.1 mmol). Addition of a mixture of 1-dodecene (92.4 g, 549.0 mmol), -olefin with the average formula CH.sub.3(CH.sub.2).sub.19CHCH.sub.2 (33.88 g, 109.8 mmol) and -olefin with the average formula CH.sub.3(CH.sub.2).sub.30CHCH.sub.2 (3.42 g, 8.1 mmol). FTIR analysis showed 5.5% remaining SiH groups. The viscosity of the product was 9100 mPa.Math.s.

(12) Preparation of die casting release agent was performed similar to Example 1.