Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/48—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
  • C08G77/50—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms by carbon linkages

Definitions

• This invention relates to organosiloxane copolymers containing halophenylsiloxane units and fluoroalkylsiloxane units which copolymers are particularly useful as lubricants and hydraulic fluids.
• hydrocarbon substituted organosiloxanes With the commercial advent of hydrocarbon substituted organosiloxanes it soon became apparent that these materials, particularly the methylsiloxanes, had many of the desirable properties required for lubricants operating over a wide range of temperature. These properties were: excellent high temperature stability, extremely low freezing point and a relatively slight change in viscosity with temperature.
• the hydrocarbon substituted siloxanes suffer from one serious defect; namely, that they were not satisfactory lubricants for sliding steel on steel bearing surfaces. Since steel is the primary metal employed in machinery the use of hydrocarbon substituted siloxanes as lubricants has been severely restricted.
• halophenylsiloxanes such as those described in U.S. Patent 2,599,984. It was found that by incorporating halophenylsiloxane units into hydrocarbon substituted siloxanes one could greatly improve the lubricating quality of siloxanes. However, the improvement was not sufficiently good tomake these materials generally satisfactory for the lubrication of steel sliding surfaces.
• fluoroalkyl'substituted siloxanes such as trifluoropropylmethylsiloxane.
• Homopolymers of these materials are excellent lubricants for sliding steel on steel bearing surfaces and in most respects they are equivalent to the best hydrocarbon oils.
• the fluoroalkylsiloxanes sulfer from the serious disadvantages that they have a relatively steep temperature viscosity slope and are not useable as lubricants at temperatures below 40 F. or as an aircraft hydraulic fluid below F.
• fluoroalkylsiloxane homopolymer fluids are not useable as lubricants in a wide variety of applications which require that the lubricant function at low temperatures.
• This invention relates to copolymers having (1) units of the group and R SiO on the ends of the molecules, the remaining units in said copolymer being substantially all (2) units of the group consisting of (a) R'SiO and
• ZSiO units in amount of from 0 to 10 inclusive mol percent, said units being interconnected through SiOSi linkages in which R is of the group methyl, phenyl, and
• Q is of the group hydrogen and C F CH CH n is an integer from 1 to 8 inclusive
• R and D are each of the group methyl and phenyl radicals, at least one R and D per silicon being on the average -a methyl radical,
• R' is of the group phenyl and methyl radicals
• Z is of the group phenyl, methyl and Q HCHrradicals
• X is of the group chlorine and bromine
• ' a is an integer from 1 to 4 inclusive
• b has a value from 0 to 2 inclusive.
• triorganosiloxy groups such as trifluoropropyl, penta- It should be understood that any combination of these groups can be attached to the silicon of the triorganosiloxy group (1).
• (1) can be any suit of the formula
• triorganosiloxy groups are trimethylsiloxy, triphenylsiloxy, phenyldimethylsiloxy, tribromophenyldimethylsiloxy, tetrachlor-ophenyldimethylsiloxy, monobromophenyldimethylsiloxy, trifluoropropyldimethylsiloxy, bistrifiuoropropylmethylsiloxy and a CF CHzCH2CHCH:-
• the substituents (2) can be entirely dihydrocarbonsiloxy groups (a) in which the substituents are phenyl and methyl radicals or (2) can be made up of up to 25 mol percent based on the amount of (a) of (b) silphenylene units of the formula in which D is phenyl or methyl.
• the total amount of silphenylene units should not exceed 15 mol percent of the total copolymer. In all cases there should be an average of at least one methyl group per silicon atom in the total number of (2) units.
• (2) can be made up entirely of dimethylsiloxy units or of phenylmethylsiloxy units or any combination of these or (2) can be made up of combinations of dimethylsiloxy units and diphenylsiloxy units,
• the copolymers can contain any combination of these fiuoroalkylsiloxane units.
• the copolymer can contain both trifluoropropylmethylsiloxane units and pentafluorobutylmethylsilonxane units or the copolymer can contain both trifluoropropylmethylsiloxane units and trifiuoropropylphenylsiloxane units.
• halophenylsiloxy groups are the halophenylsiloxy groups. These must be present in amount from 1 to 15 mol percent of the total copolymer. These groups can be of three types, namely,
• the latter type of unit is also an endblocking unit (1) and if such units are present in amount to give a total of at least one mol percent halophenylsiloxy units in the copolymers, no additional halophenyl units are needed.
• a combination of any two or all three types of halophenyl units can be present in the copolymer.
• the halophenyl units can be located solely on the ends of the molecules or they can be located along the molecular chain of the copolymer or they can be located in both positions in any particular copolymer.
• operative halophenylsiloxy units are chlorophenylsiloxy units, dibromophenylmethylsiloxy units, tetrachlorophenylmethylsiloxy units, chlorodibromophenylsiloxy units, and tetrabromophenylsiloxy units.
• the copolymers of this invention can also contain an optional ingredient (5) which is either monomethylsiloxane units, monophenylsiloxane units, or any CnFfinH Q nomsiom unit where Q and n are as defined above or any combination of these three types of units.
• (5) can be CF CH CH SiO C F CH CH SiO i CFaCHzCHgUHCHzSiOa/I and In any event, siloxane units (5) should not exceed a total of 10 mol percent of the copolymer.
• the copolymers of this invention are best prepared by cohydrolyzing the corresponding chlorosilanes followed by equilibration of the cohydrolyzate with alkali metal hydroxide catalysts or catalysts comprising the alkali metal salts of silanols. During the equilibration it is often desirable to remove water as it is formed and to maintain the equilibrating system in an anhydrous condition. This is particularly true where the halophenyl substituents contain more than two halogen atoms. Thus, it can be seen that the copolymers of this invention are prepared by conventional techniques for copolymerizing siloxanes.
• silphenylene units When silphenylene units are to be incorporated into the copolymer it is best to add the corresponding diol of the formula to the acid free hydrolyzate containing the remaining ingredients and to equilibrate the mixture with the alkaline catalysts supra.
• the starting halosilanes and diols from which the copolymers of this invention are prepared are all wellknown materials.
• the molecular size of the copolymers of this invention is not critical since they are all excellent lubricants regardless of polymer size. However, in many applications it is preferred that the viscosity of the copolymer be in the range for from 25 to 10,000 cs. at 77 F.
• the copolymers of this invention are particularly desirable for use as hydraulic fluids and for this use a particularly desirable form has a viscosity from 50 to cs. at 77 F. It is obvious that the viscosity of the copolymer will be determined by the mol ratio of triorganosiloxy groups to the other siloxy groups. Thus, the viscosity can be varied at will by increasing or decreasing the mol percent of triorganisiloxy groups in the system.
• Example 1 CF CH CH SL0 M01 per 651 16 1000 g. of a copolymer of 6.2 mol percent dichlorocgg f, 2 phenylsiloxane, 75.3 mol percent dimethylsiloxane, 13.5 M61810 65 mol percent trimethylsiloxane and 5 mol percent phenyland methylsiloxane was mixed with 200 g. of Me omonroms io 2n (oFioHwHsioh The copolymer was a fluid having good low temperaalld 10 of KOH and the mixture Was Stirred and healed ture stability and excellent lubricity for steel on steel for 18 hours at 160 to 170 C. The resulting fluid was bearing surfaces.
• Example 4 copolymer had the average composition: 5.6 mol percent E l i th procedure of E l 2, a copolymer dichlofophellyl 3/2 11101 p M62510, was obtained having the following composition. mol percent Me SiO 4.9 mol percent C H (Me)S1O M01 per cent and 9.7 mol percent CF CH CH (Me)SiO. Me Si0 4 10
• This copolymer had the following propertlesz i gg giasiom 2 Temperature, F.: Viscosity, cs. and
• the copolymer was a fluid having good low tempera-- ture ro erties and was an excellent lubricant for steel.
• the fluid was tested on the Shell 4-bal1 wear tester p p and gave a scar diameter of .16 mm. after 2 hours at Example 5 v 1200 -P- at K under a load of 4 65
• a copolymer was obtained having a viscosity of 70.1 cs. at 77 F. and Example 2 having the composition
• a series of fluids were made and tested as shown in the M01 per cent table below.
• the fluid was cooled and neutralized with Me SiCl, filtered and stripped to 290 C. at 1.5 mm.
• the resulting fluid copolymer had the composition 10 mol percent Me SiO 5 mol percent C12 Sloan 55 mol percent Me SiO, 15 mol percent Me CF CHgCHiS iO and 15 mol percent It gave a scar diameter of .333 mm. when tested on the Shell 4-ball wear tester at 167 F. for 2 hours at 10 kg.
• Q is selected from the group consisting of hydrogen and C F2 +1CH2CH2,
• n is an integer from 1 to 8 inclusive
• R and D are each independently selected from the group consisting of phenyl and methyl radicals, at least one R and D group per silicon being on the average a methyl radical,
• R is selected from the group consisting of methyl and phenyl radicals
• Z is selected from the group consisting of phenyl
• X is selected from the group consisting of chlorine and bromine
• a is an integer from 1 to 4 inclusive
• b has a value from 0 to 2 inclusive.
• composition in accordance with claim 4 having a viscosity of from 25 to 10,000 cs. at 77 F.
• composition in accordance with claim 4 having a viscosity of from 50 to 150 cs. at 77 F.
• Mei Mei and R SiO on the ends of the molecules, the remaining units in said copolymer being substantially all (2) units of the group consisting of (a) R' SiO and the total units (2) being present in amount of at least 24 mol percent of the total copolymer and any units (b) being present in amount of from 0 to 25 mol percent of the amount of units (a), and from 0 to 15 mol percent of the total copolymer,
• xii-Q3103 and :dQsro 1 1 units in amount such that the total number of units of the formula in said copolymer is from 1 to 15 mol percent of the total copolymer and (5) ZSiO units in amount of from to 10 inclusive mol percent of the total copolymer, said units being interconnected through SiOSi linkages, in which R is selected from the group phenyl, methyl and radicals,
• Q is selected from the group consisting of hydrogen and C F CH CH n is an integer from 1 to 8 inclusive,
• R and D are each independently selected from the group consisting of phenyl and methyl radicals, at least one R and D group per silicon being on the average a methyl radical,
• R' is selected from the group consisting of methyl and phenyl radicals
• Q is selected from the group consisting of phenyl
• a method of lubricating moving metallic parts which comprises maintaining therebetween a copolymer having (1) trimethylsiloxy units on the ends of the molecules,

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
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• Silicon Polymers (AREA)
• Laminated Bodies (AREA)

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Citations (7)

• 1963
  • 1963-06-10 US US286491A patent/US3334120A/en not_active Expired - Lifetime
• 1964
  • 1964-04-07 FR FR970011A patent/FR1387724A/fr not_active Expired
  • 1964-04-23 GB GB16912/64A patent/GB1006789A/en not_active Expired
  • 1964-05-13 DE DED44424A patent/DE1258998B/de active Pending
  • 1964-05-15 BE BE647975D patent/BE647975A/xx unknown
  • 1964-05-15 AT AT427664A patent/AT263979B/de active

Patent Citations (7)

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