CA1156784A - Siloxane modified novolaks, their production and their use for the production of friction linings - Google Patents
Siloxane modified novolaks, their production and their use for the production of friction liningsInfo
- Publication number
- CA1156784A CA1156784A CA000342940A CA342940A CA1156784A CA 1156784 A CA1156784 A CA 1156784A CA 000342940 A CA000342940 A CA 000342940A CA 342940 A CA342940 A CA 342940A CA 1156784 A CA1156784 A CA 1156784A
- Authority
- CA
- Canada
- Prior art keywords
- novolak
- production
- alkyl
- friction linings
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920003986 novolac Polymers 0.000 title claims abstract description 36
- 238000004519 manufacturing process Methods 0.000 title abstract description 13
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title abstract 2
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 22
- -1 polysiloxane Polymers 0.000 claims abstract description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 21
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012766 organic filler Substances 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229920005989 resin Polymers 0.000 abstract description 29
- 239000011347 resin Substances 0.000 abstract description 29
- 229920001568 phenolic resin Polymers 0.000 abstract description 11
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000005809 transesterification reaction Methods 0.000 abstract description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 2
- LMWMTSCFTPQVCJ-UHFFFAOYSA-N 2-methylphenol;phenol Chemical compound OC1=CC=CC=C1.CC1=CC=CC=C1O LMWMTSCFTPQVCJ-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 235000019256 formaldehyde Nutrition 0.000 description 4
- 229960004279 formaldehyde Drugs 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 229960004011 methenamine Drugs 0.000 description 4
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000006887 Ullmann reaction Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000005248 alkyl aryloxy group Chemical group 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- CXUXSVRYIFBRSZ-UHFFFAOYSA-N 2-cyclohexyl-1,3-benzothiazole Chemical compound C1CCCCC1C1=NC2=CC=CC=C2S1 CXUXSVRYIFBRSZ-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 101710095439 Erlin Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 125000002061 L-isoleucyl group Chemical group [H]N([H])[C@]([H])(C(=O)[*])[C@](C([H])([H])[H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 229920013648 Perbunan Polymers 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000546339 Trioxys Species 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- VOOLKNUJNPZAHE-UHFFFAOYSA-N formaldehyde;2-methylphenol Chemical compound O=C.CC1=CC=CC=C1O VOOLKNUJNPZAHE-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229940119177 germanium dioxide Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- NOKUWSXLHXMAOM-UHFFFAOYSA-N hydroxy(phenyl)silicon Chemical compound O[Si]C1=CC=CC=C1 NOKUWSXLHXMAOM-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000001034 iron oxide pigment Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000013365 molecular weight analysis method Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16D—COUPLINGS FOR TRANSMITTING ROTATION; CLUTCHES; BRAKES
- F16D69/00—Friction linings; Attachment thereof; Selection of coacting friction substances or surfaces
- F16D69/02—Composition of linings ; Methods of manufacturing
- F16D69/025—Compositions based on an organic binder
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Engineering & Computer Science (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Braking Arrangements (AREA)
- Silicon Polymers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Lubricants (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
SILOXANE MODIFIED NOVOLAKS, THEIR PRODUCTION
AND THEIR USE FOR THE PRODUCTION OF FRICTION
LININGS.
Abstract of the Disclosure A polysiloxane containing a novolak residue corresponding to the formula wherein each A is a novolak residue, a C1-C8 alkyl, C6-C12 aryl or C7-C12 alkyl aryl group, each R is a C1-C8 alkyl, C6-C18 cycloalkyl, C6-C12 aryl or C7-C12 alkyl aryl group, and n is a number of from 3 to 100 provided that at least one A is a novolak residue, can be produced by reacting a respective substituted polysiloxane with a phenol-formaldehyde and/or cresol-formaldehyd novolak resin in presence of an acid trans-esterification catalyst at temperatures of from 110 to 180°C. The described products can be used for the pro-duction of friction linings.
Le A 19 372
AND THEIR USE FOR THE PRODUCTION OF FRICTION
LININGS.
Abstract of the Disclosure A polysiloxane containing a novolak residue corresponding to the formula wherein each A is a novolak residue, a C1-C8 alkyl, C6-C12 aryl or C7-C12 alkyl aryl group, each R is a C1-C8 alkyl, C6-C18 cycloalkyl, C6-C12 aryl or C7-C12 alkyl aryl group, and n is a number of from 3 to 100 provided that at least one A is a novolak residue, can be produced by reacting a respective substituted polysiloxane with a phenol-formaldehyde and/or cresol-formaldehyd novolak resin in presence of an acid trans-esterification catalyst at temperatures of from 110 to 180°C. The described products can be used for the pro-duction of friction linings.
Le A 19 372
Description
~ 1567~
The present invention relates to the use of siloxane-modified novolaks for the production of friction linings.
The use of novolaks for the production of friction linings is known (cf. Gummi, Asbest, Kunststoffe 9, (1978), Vol. 31, pages 666 to 670). Resins of this type are used for glueing numerous fillers and additives, and they enable the moulding compositions to be subsequently hardened by heating.
High-temperature-resistant mouldings, such as friction linings which are preferably used for the production of clutch and brake linings, are required to have a very high decomposition temperature and a low evaporation rate of thermal decomposition products. In this context, high temperatures are generally understood to be temperatures in the range of from 250 to 800C.
The effectiveness of friction linings and their useful life is drastically reduced by the presence of a high proportion of volatile cracking products, such as mainly benzene, toluene, xylene, phenol and cresol, and by a lack of dimensional stability (breaking out of friction lining fragments) at high temperatures.
By the process described in German Offenlegungsschrift No. 2,306,463, in which phenol-formaldehyde resins and polysiloxanes are mixed in solution and the mouldings ,,~
~ , 2 1 1~678~
are subsequently hardened subsequent to removal of the solvent, it is possible to obtain high-temperature--res~
istant mouldings from which friction linings can be pro-duced.
l~owever, in comparison with friction linings produced on the basis of phenol novolaks, the friction linings obtained in this particular way show an increased break-out of fragments o~ the friction lining moulding at high temperatures. ~his would appear to be caused by an inad-cquate bond between the low molecular weignt components of the novolak, and the silicone resin in the moulded friction lining.
The object of the present invention is to reduce distinctly this decom~osition of high--temperature-stressed phenol-formaldehyde and/or cresol-formaldehyde resins by suitable chemical modification thereof, and to increase their dimensional stability at high temperatures by improv-ing their elasticity, tear propagation resistance and ten-sile strength.
It has now been found that phenol-formaldehyde and/or cresol-formaldehyde resins of the novolak type can be reacted with polysiloxanes containing terminal alkoxy, alkyl-aryloxy or aryloxy groups under acid-catalysed conditions with elimination of alcohol or phenol to form siloxane-modified novolaks which not only readily lend Le A 19 372 1 ~567~4 themselves to fabrication but also give high-temperature-resistant moulding compositions having improved elasticity, tear propagation resistance and tensile strength. The resins of the present invention may be processed into friction linings which, in addition to the akove mentioned properties, show considerably improved noise-damping properties and excellent dimensional stability at high temperatures.
Accordingly, the present invention provides a friction lining molded from a polysiloxane of the formula IR
A _O - Si - - O-A
wherein each A is a novolak residue, a Cl - C8 alkyl, a C6 - C12 aryl or a C7 - C12 alkaryl group; each R is a Cl - C8 alkyl, C - C cycloalkyl, C6 - C12 aryl or C7 C12 Y
n is from 3 to 100 with the proviso that at least one A is a novolak residue, reacted with a formaldehyde donor and containing an organic or inorganic filler.
The novolak-containing polysiloxane used in the production of the friction linings of the present invention may be a process which is characterised in that a polysiloxane containing Cl - C8 alkyloxy, C6 - C12 aryloxy and/or C7 - C12 ~ ~56~
alkyl aryloxy groups is reacted with a phenol-formaldehyde and/or cresol-formaldehyde resin of the novolak type in the presence of an acid tranesterification catalyst at a temperature in the range of from 110 to 180C, the polysiloxane being used in quantities of from 20 to 120 parts by weight, based on 100 parts by weight of novolak, and the volatile fractions formed are distilled off.
In the above formula A and P represent a Cl - C8 alkyl radical, wuch as for example methyl, ethyl, propyl, _-, i_ or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl and n-or i_octyl; a C6 - C12 aryl radical such as, for example, phenyl or ~ -naphthyl, a C7 - C12 alkyl aryl radical such as, for example, tolyl, ~-tert.-butyl phenyl or n- or i-hexyl phenyl;
and/or novolak residue. In addition, R may represent a C6 - C18 cycloalkyl group.
The novolak residue and the novolak resin used in the production process may be formed from phenol-formaldehyde and/or cresol-formaldehyde resins obtained in known manner by reacting phenols and/or cresols with, for example, aqueous formaldehyde solutions in a molar ratio 1 ~5~7~
of from 1:1.05 to 1:1.4 in the presence of an acid catalyst (cf. Ullmanns Encyclopadie der techn. Chemie, Vol.
13, page 459, Publishers: Urban & Schwarzenberg, Munich-Berlin, 1962).
The resin is preferably bound to the polysiloxane through a hydroxy methylene group from which a hydroqen atom is eliminated during the reaction. The phenol groups present in the resin are slow in reaction and, for this reason, only react towards the end of the reaction, if at all.
The polysiloxane used for the production of the polysiloxanes of the present invention correspond to the following formula:
R
B - - 0-Si -0-B
R n wherein each B is a Cl-C8 alkyl, C6-C12 aryl or C7-C12 alkyl aryl 20radical, each R represents a Cl-C8 alkyl, C6-C18 cycloalkyl, C6-C12 aryl, or C7-C12 alkyl aryl radical, and n represents numbers of from 3 to 100.
hese polysiloxane resins may be dissolved in a sol-vent, such as benzene, toluene or xylene, although they are Le A 19 372 1 ~67~
preferably used in solvent~free form. The solvent--free polysiloxanes are liquids and generally have a viscosity of from 40 to 20,000 c/Stokes (measured at 20C).
Polysiloxane resins such as these may be produced by processes known from the literature, for example by the controlled hydrolysis of silanes corresponding to the general formula (R2) Si(X)2, where R as hereinbefore defined and each X is for example, a chlorine atom or an O-alkyl group containing from 1 to 8 carbon atoms, optionally in the presence of organic solvents, such as toluene or xylene, and optionally in thc presence of an alkali or an acid and a suitable quantity of chain-terminating Cl-C8 hydroxy alkyls, C6-C12 hydroxy aryls or C7-C12 hydroxy alkyl aryls (cf. for example W. Noll, 'Chemie und Technologie der Silicone", Verlag Chemie GmbH, 1~einheim/Bergstra3e 1968, pages 162 - 171).
So far as the novolaks used are concerned, reference is made to the comments hereinabove.
The quantity in which the polysiloxane is used for the reaction preferably amounts to between 30 and 80 parts by weight, based on lOO parts by weight of the novolak.
The reaction is preferably carried out in the presence of fromO.OOOlto 0.05% by weight of an acid transesterifi-cation catalyst (based on the total weight of the reaction mixture), such as for exam~le an organic or inorganic acid, such as oxalic acid, formic acid, acetic acid, trichloro--Le A 19 372 ~ J
~ 15~7~4 --8~-acetic or trifluoroacetic acid, benzene sulphonic acid, ~-toluene sulphonic acid, hydrochloric acid, sulphuric acid, phosphoric acid or a Lewis acid, such as aluminium chloride, iron (III) chloride, zinc chloride, antimony(III) chloride, 5 germanium dioxide or zinc oxide.
.he reaction temperature is preferably in the range of f~om 130 to 170C. The "B-radical" eliminated during the reaction may be distilled off under normal pressure, but is preferably distilled off under a vacuum of from 1 to 10 500 mbars.
me liquid viscous resin of the present invention is drained off from the reaction vessel and worked up, advantageously on a ~elletising belt or a cooling roller. It may then be ground.
me resins of the present invention thus obtained generally have a softening point of from 60 to 110C preferably of from 70 to 100C (as nieasured in accordance with DIN 53 180). They have a higher average molecular weight (as measured ~y osmometryi than the components used for the 20 reaction. For example, the reaction of a novolak having a molecular weight MoS of 530 with a polysiloxane containing terminal methoxy groups and having a molecular weight Mos of 510 gives an end product having a molecular weight MoS
of 760. The chemical reaction of the novolak with the 25 polysiloxane may readily be monitored and established through Le A 19 372 1 ~ 5 G 7~
--9.
this molecular weight analysis.
To obtain friction linings, the resins of the present invention are thoroughly ~ ed with inorganic and/or organic fillers, such as metals and/or metal oxides, fluorspar, asbestos, silica or butyl, nitrile and/or chloroprene rubber, in the presence of formaldehyde donors, such as hexamethylene tetramine or trioxy or tetraoxy methylene in standard mixing units, such as kneaders or internal mixers, at temperatures preferably in the range of from 60 to 150C. me form-aldehyde donors are added in quantities of from 4 to 16%
by weight and preferably in quantities of from 7 to 14%
by weight, based on 100 parts by weight of the resin of the present invention.
me muxtures thus obtained are generally moulded at 140 to 15 180C and more particularly at 140 to 160C, optionally under a pressure of from 150 to 250 bars, to form friction linings (cf. Vieweg/Becker "Kunststoffhandbuch", Vol.
10, Duroplaste, pages 93 to 95, Carl Hanser Verlag, Munich, 1968).
The thermal properties of the mouldings obtained are shown in Table 1 below which contains data on the weight loss of 2 resin samples as determined by thermogravimetry under nitrogen ~heating rate: 20C per minute).
Le A 19 372 l 15~7~4 Table 1: Thermogravimetric analysis ~1eight losses in % by weight Temp (C) Resin 1 (x) Resin 2 (xx) 100 4.0 0 5 150 4.5 0.7 200 5.0 1.1 250 5.5 1.3 300 6.0 1.7 350 6.6 2.0 400 7.5 2.4 450 11.0 2.8 500 15.5 3.5 550 22.4 6.0 600 28.o 8.5 650 33.2 12.6 700 37.0 14.0 750 40.1 16.1 800 42.4 17.2 x) Resin 1: phenol-formaldehyde resin (MoS = 530) mixed with 12~ by weight of hexamethylene te~ramine xx) Resin 2: siloxane-modified novolak prepared according to the procedures of Example 1 described hereinafter mixed with 12Po by weight Gf hex-amethylene tetramine.
The present invention is further illustrated by the following examples.
Le A 19 372 1 ~ 5~7g~
Example 1 A novolak produced in known manner from phenol andformaldehyde in a molar ratio of ~`1.08 in the presence of an acid catalyst, such as oxalic acid, an~ having a molecular weight Mos f 530 and an Ol~ number of 535 (cf.
Ullmanns Encyclopadie der technischen Chemie, Vol. 13, page 459, Publishers Urban Schwarzenberg, Munich-~erlin, 1962) is used in a quantity of 660 g.
This novolak is reacted with 330 g of a diphenyl-polysiloxane containing terminal methoxy groups and having the following characteristic data:
M = 510 os viscosity (DIN 53 015): llO c/Stokes ~ by weight of methoxy groups 14 to 16 The reaction is carried out at 160C in the presence of 0.002 % by weight p-toluene sulphonic acid (based on the total weight of the reaction mixture). After reaction under a nitrogen atmosphere for 1 hour with intensive stirring at 160C, 36.5 g of methanol is distilled off under a pressure 20 of 350 to lO mbars. At the same time, 3.0 g of phenol and water are removed by distillation.
me liquid viscous resin obtained is subsequently removed from the reaction vessel and ground after cooling. The product has the following characteristic data:
softening point (according to DI~ 54 180): 8gC
Le A 19 372 1 ~567~
os OH-number = 330 silicon content: 6.2%
The resin produced in accordance with the procedure of Example 1 was ground, mixed with 12~ by weight of hexamethylene tetramine and analysed by thermogravimetry (cf. resin 2 of Table 1).
At temperatures above 300~C, the friction linings produced from the resin of Example 1 are characterised not only by the considerably lower evaporation rate of low molecular weight compounds indicated by way of example in Table 1, but are also characterized by increased elasticity, tear propagation resistance and tensile strength and greater hardness than friction linings produced from a phenol-formaldehyde resin or from a mixture of polysiloxaneand phenolic resin (cf. Table 2).
Table 2 compares th~ properties of friction lining mixtures produced A) from a mixture of acrylonitrile/butadiene copclymer and a phenol-formaldehyde novolak having an average mole-cular weight Mos of 530 and an OH number of 535, B) from a mixture of acrylonitrile/butadiene copolymer and a siloxane-modified novolak of the present invention corresponding to the resin produced in Example 1, and C) from a mixture of an acrylonitrile/butadiene copolymer Le A 19 372 I ~$~7~
and a phenol novolak/silicone resin mixture corresponding to resins4 of German Offenlegungsschrift No. 2,306,463.
The mixture of phenol novolak and silicone resin corresponding to resins4 of German Offenlegungsschrift No. 2,306,463 is produced as follows:
33% by weight (based on solids content) of a methyl silicone resin containing 3 mole percent of phenyl siloxane, in the form of a 51% solution in xylene which has a viscos-ity of from 40 to 60 cSt tas measured at 20CC) is mixed with 60% by weight of a phenol novolak having a molecular weight MoS of 530 and an OH number of 535.
This mixture is thoroughly mixed with the above-mentioned-acrylonitr.ile/butadiene copolymer and with the other components of the friction lining mixture, _he xylene being removed at 80C and 100 mbars pressure.
The friction lining mixtures (A), (B) and (C) are hardened by moulding for 30 minutes at 150C under a pressure of 200 kp/cm2. 4 mm thick plates ~ere produced and made up into standard test bars.
Table 2 (I) Production of the friction lining mixtures:
(A) (B) (C~
Perbunan N 3307 NS 59.1 59.1 59.1 Phenol-formaldehyde resin (=resin 1 of Table 1) 50.0 ~ -Le A 19 372 ~ f~-~De ,~
1 1567~
Table 2 Contd:
(A) (B) (C) Siloxane-modified novclak acc-ording to ~xample 1 (= resin 2 of Table 1) - 50.0 Resin 4 according to German Offenlegungsschrift No. 2306463 page 5 - - 50.0 Stearic acid 2.43 2.43 2.43 Styrene/butadiene resin cont-aining 60% by weight of styrene 27.3 27.3 27.3 Colophony 10.9 10.9 10.9 Kaolin 118.0 118.0 118.0 Calcium silicate 18.2 18.2 18.2 Active zinc oxide 9.1 9.1 9.1 Iron oxide pigment 9.1 9.1 9.1 Sulphur 3.64 3.64 3.64 Cyclohexyl benzthiazole sul-phenamide 1.69 1.69 1.69 Hexamethylene tetramine granulate - 4.0 4.0 -Mooney viscosity (ML -4 at 76 53 51 100 C) .
(II) Mechanical values, as measured on standard test bars after vulcanisation for 30 minutes at 150C
-Mixtures (A) F ¦ D HD¦ E WRF
14.3 40 67 1 22 49.1 , HL 120C/ 1 day: 18.0 27 74 1 25 29;2 Le A 19 372 1 ~5~7~
Mixtures (A) F D ¦ HD E WRF I
HL 120C/ 3 days: l9.I 20 ¦ 7S 25 28.4 ¦
HL 12_C/ 5_da~s._ _ _ 19.8 20 l 75 _25 _ 22 . 9 !
(B) F D HDE WRF
15.9 20 70 _ 28 52.6 HL 120C/ 1 day: 20.7 10 78 30 31.6 HL 120CC/ 3 days: 21.710 78 31 31.1 HL 120C/ 5 days: 20.6 10 79 _ 31 29.1 (C) F D HD E WRF
12.6 57 6422 45.6 HL 120C/ 1 day: 16.4 30 70 24 31.9 I~L 120C/ 3 days: ~ 18.8 20 74 26 28.6 HL 120C/ 5 days: 20.2 17 74 26 23.8 ~:
F = tensile strength (MPa) D = elongation at break (~) HD = hardness (~hore D) E = shock elasticity (~) WRF = tear propagation resistance (N/mm) HL-120C = hot-air ageing at 120C
Le A 19 372 ~5~J8~
Friction linings produced from the siloxane-modified novolaks of the present invention are distinguished by lower mixing viscosities and hence by more favourable prGcessing behaviour in comparison with friction linings 5 containing phenol novalaks (cf. the ~ooney viscosity values in Table 2). In addition, tensile strength (F), elasticity (E) and tear propagation resistance (WRF), which are measures of the dimensional stability of the ~riction lining, are distinctly improved in comparison 10 with a friction lining based on a phenol novolak/silicone r~sin mixture (cf. mixtures (B) and (C) in Table 2, II).
The hardening effect of the resins of the present invention in friction lining mixtures is also greater than that of a pure phenol novolak/silicone resin mixture (cf. HD
15 values in Table 2, II for mixtures (A), (B) and (C)).
Le A 19 372
The present invention relates to the use of siloxane-modified novolaks for the production of friction linings.
The use of novolaks for the production of friction linings is known (cf. Gummi, Asbest, Kunststoffe 9, (1978), Vol. 31, pages 666 to 670). Resins of this type are used for glueing numerous fillers and additives, and they enable the moulding compositions to be subsequently hardened by heating.
High-temperature-resistant mouldings, such as friction linings which are preferably used for the production of clutch and brake linings, are required to have a very high decomposition temperature and a low evaporation rate of thermal decomposition products. In this context, high temperatures are generally understood to be temperatures in the range of from 250 to 800C.
The effectiveness of friction linings and their useful life is drastically reduced by the presence of a high proportion of volatile cracking products, such as mainly benzene, toluene, xylene, phenol and cresol, and by a lack of dimensional stability (breaking out of friction lining fragments) at high temperatures.
By the process described in German Offenlegungsschrift No. 2,306,463, in which phenol-formaldehyde resins and polysiloxanes are mixed in solution and the mouldings ,,~
~ , 2 1 1~678~
are subsequently hardened subsequent to removal of the solvent, it is possible to obtain high-temperature--res~
istant mouldings from which friction linings can be pro-duced.
l~owever, in comparison with friction linings produced on the basis of phenol novolaks, the friction linings obtained in this particular way show an increased break-out of fragments o~ the friction lining moulding at high temperatures. ~his would appear to be caused by an inad-cquate bond between the low molecular weignt components of the novolak, and the silicone resin in the moulded friction lining.
The object of the present invention is to reduce distinctly this decom~osition of high--temperature-stressed phenol-formaldehyde and/or cresol-formaldehyde resins by suitable chemical modification thereof, and to increase their dimensional stability at high temperatures by improv-ing their elasticity, tear propagation resistance and ten-sile strength.
It has now been found that phenol-formaldehyde and/or cresol-formaldehyde resins of the novolak type can be reacted with polysiloxanes containing terminal alkoxy, alkyl-aryloxy or aryloxy groups under acid-catalysed conditions with elimination of alcohol or phenol to form siloxane-modified novolaks which not only readily lend Le A 19 372 1 ~567~4 themselves to fabrication but also give high-temperature-resistant moulding compositions having improved elasticity, tear propagation resistance and tensile strength. The resins of the present invention may be processed into friction linings which, in addition to the akove mentioned properties, show considerably improved noise-damping properties and excellent dimensional stability at high temperatures.
Accordingly, the present invention provides a friction lining molded from a polysiloxane of the formula IR
A _O - Si - - O-A
wherein each A is a novolak residue, a Cl - C8 alkyl, a C6 - C12 aryl or a C7 - C12 alkaryl group; each R is a Cl - C8 alkyl, C - C cycloalkyl, C6 - C12 aryl or C7 C12 Y
n is from 3 to 100 with the proviso that at least one A is a novolak residue, reacted with a formaldehyde donor and containing an organic or inorganic filler.
The novolak-containing polysiloxane used in the production of the friction linings of the present invention may be a process which is characterised in that a polysiloxane containing Cl - C8 alkyloxy, C6 - C12 aryloxy and/or C7 - C12 ~ ~56~
alkyl aryloxy groups is reacted with a phenol-formaldehyde and/or cresol-formaldehyde resin of the novolak type in the presence of an acid tranesterification catalyst at a temperature in the range of from 110 to 180C, the polysiloxane being used in quantities of from 20 to 120 parts by weight, based on 100 parts by weight of novolak, and the volatile fractions formed are distilled off.
In the above formula A and P represent a Cl - C8 alkyl radical, wuch as for example methyl, ethyl, propyl, _-, i_ or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl and n-or i_octyl; a C6 - C12 aryl radical such as, for example, phenyl or ~ -naphthyl, a C7 - C12 alkyl aryl radical such as, for example, tolyl, ~-tert.-butyl phenyl or n- or i-hexyl phenyl;
and/or novolak residue. In addition, R may represent a C6 - C18 cycloalkyl group.
The novolak residue and the novolak resin used in the production process may be formed from phenol-formaldehyde and/or cresol-formaldehyde resins obtained in known manner by reacting phenols and/or cresols with, for example, aqueous formaldehyde solutions in a molar ratio 1 ~5~7~
of from 1:1.05 to 1:1.4 in the presence of an acid catalyst (cf. Ullmanns Encyclopadie der techn. Chemie, Vol.
13, page 459, Publishers: Urban & Schwarzenberg, Munich-Berlin, 1962).
The resin is preferably bound to the polysiloxane through a hydroxy methylene group from which a hydroqen atom is eliminated during the reaction. The phenol groups present in the resin are slow in reaction and, for this reason, only react towards the end of the reaction, if at all.
The polysiloxane used for the production of the polysiloxanes of the present invention correspond to the following formula:
R
B - - 0-Si -0-B
R n wherein each B is a Cl-C8 alkyl, C6-C12 aryl or C7-C12 alkyl aryl 20radical, each R represents a Cl-C8 alkyl, C6-C18 cycloalkyl, C6-C12 aryl, or C7-C12 alkyl aryl radical, and n represents numbers of from 3 to 100.
hese polysiloxane resins may be dissolved in a sol-vent, such as benzene, toluene or xylene, although they are Le A 19 372 1 ~67~
preferably used in solvent~free form. The solvent--free polysiloxanes are liquids and generally have a viscosity of from 40 to 20,000 c/Stokes (measured at 20C).
Polysiloxane resins such as these may be produced by processes known from the literature, for example by the controlled hydrolysis of silanes corresponding to the general formula (R2) Si(X)2, where R as hereinbefore defined and each X is for example, a chlorine atom or an O-alkyl group containing from 1 to 8 carbon atoms, optionally in the presence of organic solvents, such as toluene or xylene, and optionally in thc presence of an alkali or an acid and a suitable quantity of chain-terminating Cl-C8 hydroxy alkyls, C6-C12 hydroxy aryls or C7-C12 hydroxy alkyl aryls (cf. for example W. Noll, 'Chemie und Technologie der Silicone", Verlag Chemie GmbH, 1~einheim/Bergstra3e 1968, pages 162 - 171).
So far as the novolaks used are concerned, reference is made to the comments hereinabove.
The quantity in which the polysiloxane is used for the reaction preferably amounts to between 30 and 80 parts by weight, based on lOO parts by weight of the novolak.
The reaction is preferably carried out in the presence of fromO.OOOlto 0.05% by weight of an acid transesterifi-cation catalyst (based on the total weight of the reaction mixture), such as for exam~le an organic or inorganic acid, such as oxalic acid, formic acid, acetic acid, trichloro--Le A 19 372 ~ J
~ 15~7~4 --8~-acetic or trifluoroacetic acid, benzene sulphonic acid, ~-toluene sulphonic acid, hydrochloric acid, sulphuric acid, phosphoric acid or a Lewis acid, such as aluminium chloride, iron (III) chloride, zinc chloride, antimony(III) chloride, 5 germanium dioxide or zinc oxide.
.he reaction temperature is preferably in the range of f~om 130 to 170C. The "B-radical" eliminated during the reaction may be distilled off under normal pressure, but is preferably distilled off under a vacuum of from 1 to 10 500 mbars.
me liquid viscous resin of the present invention is drained off from the reaction vessel and worked up, advantageously on a ~elletising belt or a cooling roller. It may then be ground.
me resins of the present invention thus obtained generally have a softening point of from 60 to 110C preferably of from 70 to 100C (as nieasured in accordance with DIN 53 180). They have a higher average molecular weight (as measured ~y osmometryi than the components used for the 20 reaction. For example, the reaction of a novolak having a molecular weight MoS of 530 with a polysiloxane containing terminal methoxy groups and having a molecular weight Mos of 510 gives an end product having a molecular weight MoS
of 760. The chemical reaction of the novolak with the 25 polysiloxane may readily be monitored and established through Le A 19 372 1 ~ 5 G 7~
--9.
this molecular weight analysis.
To obtain friction linings, the resins of the present invention are thoroughly ~ ed with inorganic and/or organic fillers, such as metals and/or metal oxides, fluorspar, asbestos, silica or butyl, nitrile and/or chloroprene rubber, in the presence of formaldehyde donors, such as hexamethylene tetramine or trioxy or tetraoxy methylene in standard mixing units, such as kneaders or internal mixers, at temperatures preferably in the range of from 60 to 150C. me form-aldehyde donors are added in quantities of from 4 to 16%
by weight and preferably in quantities of from 7 to 14%
by weight, based on 100 parts by weight of the resin of the present invention.
me muxtures thus obtained are generally moulded at 140 to 15 180C and more particularly at 140 to 160C, optionally under a pressure of from 150 to 250 bars, to form friction linings (cf. Vieweg/Becker "Kunststoffhandbuch", Vol.
10, Duroplaste, pages 93 to 95, Carl Hanser Verlag, Munich, 1968).
The thermal properties of the mouldings obtained are shown in Table 1 below which contains data on the weight loss of 2 resin samples as determined by thermogravimetry under nitrogen ~heating rate: 20C per minute).
Le A 19 372 l 15~7~4 Table 1: Thermogravimetric analysis ~1eight losses in % by weight Temp (C) Resin 1 (x) Resin 2 (xx) 100 4.0 0 5 150 4.5 0.7 200 5.0 1.1 250 5.5 1.3 300 6.0 1.7 350 6.6 2.0 400 7.5 2.4 450 11.0 2.8 500 15.5 3.5 550 22.4 6.0 600 28.o 8.5 650 33.2 12.6 700 37.0 14.0 750 40.1 16.1 800 42.4 17.2 x) Resin 1: phenol-formaldehyde resin (MoS = 530) mixed with 12~ by weight of hexamethylene te~ramine xx) Resin 2: siloxane-modified novolak prepared according to the procedures of Example 1 described hereinafter mixed with 12Po by weight Gf hex-amethylene tetramine.
The present invention is further illustrated by the following examples.
Le A 19 372 1 ~ 5~7g~
Example 1 A novolak produced in known manner from phenol andformaldehyde in a molar ratio of ~`1.08 in the presence of an acid catalyst, such as oxalic acid, an~ having a molecular weight Mos f 530 and an Ol~ number of 535 (cf.
Ullmanns Encyclopadie der technischen Chemie, Vol. 13, page 459, Publishers Urban Schwarzenberg, Munich-~erlin, 1962) is used in a quantity of 660 g.
This novolak is reacted with 330 g of a diphenyl-polysiloxane containing terminal methoxy groups and having the following characteristic data:
M = 510 os viscosity (DIN 53 015): llO c/Stokes ~ by weight of methoxy groups 14 to 16 The reaction is carried out at 160C in the presence of 0.002 % by weight p-toluene sulphonic acid (based on the total weight of the reaction mixture). After reaction under a nitrogen atmosphere for 1 hour with intensive stirring at 160C, 36.5 g of methanol is distilled off under a pressure 20 of 350 to lO mbars. At the same time, 3.0 g of phenol and water are removed by distillation.
me liquid viscous resin obtained is subsequently removed from the reaction vessel and ground after cooling. The product has the following characteristic data:
softening point (according to DI~ 54 180): 8gC
Le A 19 372 1 ~567~
os OH-number = 330 silicon content: 6.2%
The resin produced in accordance with the procedure of Example 1 was ground, mixed with 12~ by weight of hexamethylene tetramine and analysed by thermogravimetry (cf. resin 2 of Table 1).
At temperatures above 300~C, the friction linings produced from the resin of Example 1 are characterised not only by the considerably lower evaporation rate of low molecular weight compounds indicated by way of example in Table 1, but are also characterized by increased elasticity, tear propagation resistance and tensile strength and greater hardness than friction linings produced from a phenol-formaldehyde resin or from a mixture of polysiloxaneand phenolic resin (cf. Table 2).
Table 2 compares th~ properties of friction lining mixtures produced A) from a mixture of acrylonitrile/butadiene copclymer and a phenol-formaldehyde novolak having an average mole-cular weight Mos of 530 and an OH number of 535, B) from a mixture of acrylonitrile/butadiene copolymer and a siloxane-modified novolak of the present invention corresponding to the resin produced in Example 1, and C) from a mixture of an acrylonitrile/butadiene copolymer Le A 19 372 I ~$~7~
and a phenol novolak/silicone resin mixture corresponding to resins4 of German Offenlegungsschrift No. 2,306,463.
The mixture of phenol novolak and silicone resin corresponding to resins4 of German Offenlegungsschrift No. 2,306,463 is produced as follows:
33% by weight (based on solids content) of a methyl silicone resin containing 3 mole percent of phenyl siloxane, in the form of a 51% solution in xylene which has a viscos-ity of from 40 to 60 cSt tas measured at 20CC) is mixed with 60% by weight of a phenol novolak having a molecular weight MoS of 530 and an OH number of 535.
This mixture is thoroughly mixed with the above-mentioned-acrylonitr.ile/butadiene copolymer and with the other components of the friction lining mixture, _he xylene being removed at 80C and 100 mbars pressure.
The friction lining mixtures (A), (B) and (C) are hardened by moulding for 30 minutes at 150C under a pressure of 200 kp/cm2. 4 mm thick plates ~ere produced and made up into standard test bars.
Table 2 (I) Production of the friction lining mixtures:
(A) (B) (C~
Perbunan N 3307 NS 59.1 59.1 59.1 Phenol-formaldehyde resin (=resin 1 of Table 1) 50.0 ~ -Le A 19 372 ~ f~-~De ,~
1 1567~
Table 2 Contd:
(A) (B) (C) Siloxane-modified novclak acc-ording to ~xample 1 (= resin 2 of Table 1) - 50.0 Resin 4 according to German Offenlegungsschrift No. 2306463 page 5 - - 50.0 Stearic acid 2.43 2.43 2.43 Styrene/butadiene resin cont-aining 60% by weight of styrene 27.3 27.3 27.3 Colophony 10.9 10.9 10.9 Kaolin 118.0 118.0 118.0 Calcium silicate 18.2 18.2 18.2 Active zinc oxide 9.1 9.1 9.1 Iron oxide pigment 9.1 9.1 9.1 Sulphur 3.64 3.64 3.64 Cyclohexyl benzthiazole sul-phenamide 1.69 1.69 1.69 Hexamethylene tetramine granulate - 4.0 4.0 -Mooney viscosity (ML -4 at 76 53 51 100 C) .
(II) Mechanical values, as measured on standard test bars after vulcanisation for 30 minutes at 150C
-Mixtures (A) F ¦ D HD¦ E WRF
14.3 40 67 1 22 49.1 , HL 120C/ 1 day: 18.0 27 74 1 25 29;2 Le A 19 372 1 ~5~7~
Mixtures (A) F D ¦ HD E WRF I
HL 120C/ 3 days: l9.I 20 ¦ 7S 25 28.4 ¦
HL 12_C/ 5_da~s._ _ _ 19.8 20 l 75 _25 _ 22 . 9 !
(B) F D HDE WRF
15.9 20 70 _ 28 52.6 HL 120C/ 1 day: 20.7 10 78 30 31.6 HL 120CC/ 3 days: 21.710 78 31 31.1 HL 120C/ 5 days: 20.6 10 79 _ 31 29.1 (C) F D HD E WRF
12.6 57 6422 45.6 HL 120C/ 1 day: 16.4 30 70 24 31.9 I~L 120C/ 3 days: ~ 18.8 20 74 26 28.6 HL 120C/ 5 days: 20.2 17 74 26 23.8 ~:
F = tensile strength (MPa) D = elongation at break (~) HD = hardness (~hore D) E = shock elasticity (~) WRF = tear propagation resistance (N/mm) HL-120C = hot-air ageing at 120C
Le A 19 372 ~5~J8~
Friction linings produced from the siloxane-modified novolaks of the present invention are distinguished by lower mixing viscosities and hence by more favourable prGcessing behaviour in comparison with friction linings 5 containing phenol novalaks (cf. the ~ooney viscosity values in Table 2). In addition, tensile strength (F), elasticity (E) and tear propagation resistance (WRF), which are measures of the dimensional stability of the ~riction lining, are distinctly improved in comparison 10 with a friction lining based on a phenol novolak/silicone r~sin mixture (cf. mixtures (B) and (C) in Table 2, II).
The hardening effect of the resins of the present invention in friction lining mixtures is also greater than that of a pure phenol novolak/silicone resin mixture (cf. HD
15 values in Table 2, II for mixtures (A), (B) and (C)).
Le A 19 372
Claims (2)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A friction lining molded from a polysiloxane of the formula wherein each A is a novolak residue, a C1 - C8 alkyl, a C6 - C12 aryl or a C7 - C12 alkaryl group; each R is a C1 - C8 alkyl, C6 - C18 cycloalkyl, C6 - C12 aryl or C7 - C12 aralkyl group and n is from 3 to 100 with the proviso that at least one A is a novolak residue, reacted with a formaldehyde donor and containing an organic or inorganic filler.
2. The friction lining of claim 1 which is produced by mixing said polysiloxane with a formaldehyde donor, heating the resulting mixture at a temperature of from 140 - 180°C and molding at a pressure of 150 to 250 bars.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19792900185 DE2900185A1 (en) | 1979-01-04 | 1979-01-04 | SILOXANE-MODIFIED NOVOLAKES, THE PRODUCTION AND USE THEREOF FOR THE PRODUCTION OF FRICTION COATINGS |
DEP2900185.2 | 1979-01-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1156784A true CA1156784A (en) | 1983-11-08 |
Family
ID=6060032
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA000342940A Expired CA1156784A (en) | 1979-01-04 | 1980-01-02 | Siloxane modified novolaks, their production and their use for the production of friction linings |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0013402B1 (en) |
JP (1) | JPS5592738A (en) |
AT (1) | ATE882T1 (en) |
BR (1) | BR8000013A (en) |
CA (1) | CA1156784A (en) |
DE (2) | DE2900185A1 (en) |
ES (1) | ES487426A1 (en) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4395527A (en) * | 1978-05-17 | 1983-07-26 | M & T Chemicals Inc. | Siloxane-containing polymers |
DE3008138A1 (en) * | 1980-03-04 | 1981-09-10 | Wacker-Chemie GmbH, 8000 München | METHOD FOR PRODUCING SILICONE MODIFIED RESINS |
DE3237000A1 (en) * | 1982-10-06 | 1984-04-12 | Hüttenes-Albertus Chemische Werke GmbH, 4000 Düsseldorf | UNDER POLYURETHANIZATION, COLD-HARDENING MOLD BINDERS, THEIR PRODUCTION AND THEIR USE |
FR2611730B1 (en) * | 1987-02-24 | 1989-06-16 | Rhone Poulenc Chimie | DIORGANOPOLYSILOXANE WITH ALPHA-MERCAPTOESTER FUNCTION USEFUL AS STABILIZER OF POLYVINYL CHLORIDE POLYMERS |
JPH0386716A (en) * | 1989-08-31 | 1991-04-11 | Toray Dow Corning Silicone Co Ltd | Production of phenolic resin modified with silicone resin |
JP3066700B2 (en) * | 1993-12-28 | 2000-07-17 | エヌエスケー・ワーナー株式会社 | Wet friction material |
CA2162027A1 (en) * | 1994-03-03 | 1995-09-08 | Hiroya Kakegawa | Binder composition for friction materials, and friction material |
GB9524361D0 (en) * | 1995-11-29 | 1996-01-31 | Bp Chem Int Ltd | Phenolic resins |
US6220405B1 (en) * | 1997-07-02 | 2001-04-24 | Alliedsignal Inc. | Friction material for drum-in-hat disc brake assembly |
JP3962146B2 (en) | 1998-03-03 | 2007-08-22 | Nskワーナー株式会社 | Wet friction material and manufacturing method thereof |
EP1086972B1 (en) * | 1999-01-29 | 2005-03-30 | Arakawa Chemical Industries, Ltd. | Hardener for epoxy resin, epoxy resin composition, and process for producing silane-modified phenolic resin |
DE102008055042A1 (en) | 2008-12-19 | 2010-06-24 | Hüttenes-Albertus Chemische Werke GmbH | Modified phenolic resins |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB766623A (en) * | 1954-03-08 | 1957-01-23 | Dow Chemical Co | Phenol-aldehyde organosilicon resinous compositions |
DE1006619B (en) * | 1954-05-25 | 1957-04-18 | Union Carbide & Carbon Corp | Process for the preparation of modified polysiloxanes |
US2920058A (en) * | 1955-01-14 | 1960-01-05 | Dow Corning | Compositicn consisting essentially of the resinous reaction product of an esterified phenol-aldehyde resin and a silicone resin |
SU439169A1 (en) * | 1972-03-20 | 1976-11-25 | Ордена Ленина Институт Элементоорганических Соединений Ан Ссср | Antifriction material |
SU507250A3 (en) * | 1973-02-09 | 1976-03-15 | Байер Аг (Фирма) | Press position |
DE2538818C3 (en) * | 1975-09-01 | 1980-04-30 | Wacker-Chemie Gmbh, 8000 Muenchen | Process for promoting condensation and / or equilibration reactions of organosilicon compounds |
-
1979
- 1979-01-04 DE DE19792900185 patent/DE2900185A1/en not_active Withdrawn
- 1979-12-21 DE DE7979105301T patent/DE2962598D1/en not_active Expired
- 1979-12-21 EP EP79105301A patent/EP0013402B1/en not_active Expired
- 1979-12-21 AT AT79105301T patent/ATE882T1/en active
- 1979-12-26 JP JP16847079A patent/JPS5592738A/en active Pending
-
1980
- 1980-01-02 CA CA000342940A patent/CA1156784A/en not_active Expired
- 1980-01-03 BR BR8000013A patent/BR8000013A/en unknown
- 1980-01-03 ES ES487426A patent/ES487426A1/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
DE2900185A1 (en) | 1980-07-17 |
DE2962598D1 (en) | 1982-06-03 |
ATE882T1 (en) | 1982-05-15 |
JPS5592738A (en) | 1980-07-14 |
ES487426A1 (en) | 1980-06-16 |
EP0013402A1 (en) | 1980-07-23 |
BR8000013A (en) | 1980-10-07 |
EP0013402B1 (en) | 1982-04-21 |
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