GB1237844A - Reinforced polymer compositions - Google Patents
Reinforced polymer compositionsInfo
- Publication number
- GB1237844A GB1237844A GB0896/70A GB189670A GB1237844A GB 1237844 A GB1237844 A GB 1237844A GB 0896/70 A GB0896/70 A GB 0896/70A GB 189670 A GB189670 A GB 189670A GB 1237844 A GB1237844 A GB 1237844A
- Authority
- GB
- United Kingdom
- Prior art keywords
- caprolactam
- sic
- polyamide
- quartz
- moh
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
1,237,844. Polyamide compositions. MONSANTO CO. 14 Jan., 1970, No. 1896/70. Heading C3R. A reinforced polymer composition C comprises (a) a polymer matrix M and (b) 2-55% vol. of C of a substantially anhydrous particulate inorganic filler F treated with an organosilane coupling agent S. M has intrinsic viscosity #1À3 and contains #50% wt. of polyamide P, F has Moh's hardness #4 and particle size such that 100% of the particles #40 Ám and #95% wt. are #15 Ám. Silane S is where a #1; b is 0, 1, or 2; c # 1; n is 0 or 1; a+b + c = 4. X is a hydrolysable group capable of reacting with an OH gp.; Y is H or monovalent hydrocarbon gp.; Z is primary or secondary amino or amido, or epoxy; R is a C 1-20 divalent hydrocarbon gp. R may be, e.g., ethylene, propylene, isobutenylene, decylene, undecylene, octadecylene, phenyl, or toluyl. X may be halogen, OH, alkoxy, cycloalkoxy, aryloxy, e.g. #-methoxyethoxy, alkoxycarbonyl, alkylcarboxylate, or acyl carboxylate, with #8 C-atoms. Y may be H, CH 3 , C 2 H 5 , vinyl, isobutyl, phenyl, or other hydrocarbyl with #10 C-atoms. S may be a γ-aminopropyl trialkoxysilane where the alkoxy groups each have #8 C-atoms, e.g. methoxy or ethoxy. Examples of S are (EtO) 3 SiC 3 H 6 NH 2 , (MaO) 3 SiC 3 H 6 NH 2 , (MeO) 2 C 6 H 5 SiC 3 H 6 NH 2 , γ-glycidoxypropyltripropoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, NH 2 COC 2 H 4 Si(OEt) 3 , (MeO) 3 SiC 3 H 6 NHC 2 H 4 NH 2 , (MeO) 3 SiC 11 H 22 NH 2 . There may be 0À1-5% wt. of S based on F. P may be formed by polymerization in the presence of S-treated F; e.g. by adding S-F adduct to a solution of diamine salt of a dicarboxylic acid and polymerizing, or by including S-F adduct in a lactam polymerization system. S and F may be mixed in the presence of the monomer(s) yielding P; or F and S may be mixed with P; F and S may be first mixed, the treated F then being mixed with P, e.g. by melt-blending; or slurry of F and S in a solution of P may be formed, P then being precipitated on the particles, e.g. by cooling the solution to crystallize P. The solvent may be ethylene glycol. F may be treated by mixing with S in the presence or absence of a solvent V for S and drying the mixture to remove volatile reaction products and any V. V may be H 2 O, alcohol, dioxane, or benzene. The S-F adduct may be heated to 50-200% or more to increase the extent of bonding. Polyamide P has intrinsic viscosity of #1-3 to 10 or more, and viscosity average M.W. of 29,000 to 10<SP>7</SP> or more. P may be linear, or a cross-linked polyamide insoluble in m-cresol; the cross-linking agent may be polyethyleneimine, tetra-(3-aminopropoxymethyl)methane, S, di- or tri-isocyanates, polyisopropyl acrylamide or polymethyl methacrylate. P may be nylon 6 or 66; or a homo- or copolymer derived from: C 3-12 lactams, e.g. #- and other caprolactams, α-pyrrolidone, piperidone, valerolactam, methyl cyclohexanone isoximes, capryllactam, cyclodecanone isoxime, or laurolactam, or or polycarboxylic acids and polyamines, e.g. HOOC-(CH 2 ) k -COOH, where k is 4, 5, 6, 7, 8 or 10, or terephthalic acid; where m is 3, 4, 5, 6, 8, or 12, or bis-(tamino)cyclohexylmethane; or polyblends thereof. Or P may be a copolymer of a polyamide with polypropylene, ethylene, ethyleneimine, styrene, acrylonitrile, butadiene, styrene/acrylonitrile, acrylonitrile rubbers, or phenylene oxide; or M may be a blend of polyamide and the above polymers. P may be formed by anhydrous base-catalysed anionic polymerization of a lactam, e.g. with a monofunctional initiator. As catalyst may be NaH, EtMgBr, Na caprolactam, Mg caprolactam, or Ca lauryl. lactam; or Ca caprolactam chloride, Mg caprolactam bromide, or Ba valerolactam iodide. The polylactam composition may be leached with water or dil HCOOH or HC1. The initiator may be CO, phenyl isocyanate, 2,4- or 2,6- tolylene diisocyanate, di-(p-isocyanatophenyl) methane, or polyfunctional isocyanate; or acetyl caprolactam, diisopropyl carbodiimide, dycyclohexyl carbodiimide, N,N-diphenyl cyanamide, N - (2 - pyridyl) - # - caprolactam; N- (4 - pyridyl) : # - caprolactam; tris - N - 2,4,6- triazino - # - caprolactam; N - (2 - pyrazinyl). #-caprolactam or the initiator can be formed by the reaction in situ of a lactam with 2-chloropyridine, 4 - bromopyridine, 2 - bromopyrazine, 2-methoxypyridine, 2-methoxypyrazine, 2,4,6- trichloro-s-triazine, 2-bromo-4,6-dichloro-s-triazine, or 2,4 - dimethoxy - 6 - chloro - s - triazine. The mixture should be held <140‹ C., preferably <80‹ C., cast into a mould and polymerized at e.g. 140-295‹ C. Filler F particles may be granular, plate-like, tubular, oblong, or acicular, with l/d of from 1/15 up to 25. F particle size may have maximum 20 Ám; average size may be <5 Ám. F hardness may be Moh 4-9. F may be Al 2 O 3 , SiO 2 , calcined kaolinite, feldspar, mullite, kyanite, wollastonite, hercynite, amosite, mineral silicates, phosphates, aluminates, aluminosilicates, sulphates, sulphides, carbides; metals, e.g. Al, Sn, Fe, steel, Mg, Ti, Zr, V, Cr, Mn, Co, Cu, Ni, or Zn; oxides of Ca, Sr, Ba, Sn, Pb, Mg, Ti, Zr, V, Cr, Mn, Fe, Co, Cu, Ni, or Zn; or boron carbide, SiC, CaCO 3 , or C black. Preferred F are: corundum or α-Al 2 O 3 , e.g. from calcination of e.g. bauxite, laterite, diaspore, gibbsite, boehmite or manufactured hydrated Al 2 O 3 ; #-Al 2 O 3 ; or calcined kaolin, e.g. kaolinite, nacrite, dickite, livesite, halloysite, anauxite, allophane, ball clay; α-quartz, crystobalite, or tridymite. Additionally present may be fibres, e.g. of glass, cellulose, asbestos, metal, or ceramic. Also present may be surfactants, which may be anionic, cationic, and /or non-ionic, e.g. Zn stearate, dioctadecyl dimethyl ammonium chloride, or ethylene-oxide/stearic acid adducts. From less than 0À05 to 0À5% wt., based on C, of surfactant may be present. C may be formed into granules for injection-moulding; or it may be milled for compression-moulding or calendering. C may be moulded, e.g. at # the melt temperature of M. Comparative examples describe compositions containing ingredients outside the scope of the invention: (A) “ inch glass fibres; (B) mica, 50% >44 Ám; (C) talc, Moh hardness 1-1À5; (D) feldspar, 50% >44 Ám; (E) wollastonite, 95% >37 Ám; (F) kaolin, Moh hardness 2À5; (G) calcined slate, Moh hardness 3; (H) hydrated alumina (diaspore); (I) α-Al 2 O 3 , 50% >37 Ám; (J) quartz, 51À7% #15 Ám. In further comparative experiments, silanes outside the scope of the invention were used: (M) and (Q) vinyl methoxysilane, (N) and (R) methacryloxypropyl trimethoxy silane, (O) and (S) phenyl triethoxy silane, (P) and (T) #-cyano ethyl triethoxy silane. In contrasting example (U), (V) or matrix has intrinsic viscosity <1À2, (Z) nylon has intrinsic viscosity <1À1; (K) 70% quartz >44 Ám; (L) 95% quartz >44 Ám; (W) uncalcined kaolin clay, Moh hardness 2À5; (X) hydrated alumina; (Y) quartz 70% >744 Ám. Specification 1,069,752 is referred to.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR215647/69A BR6915647D0 (en) | 1968-12-30 | 1969-12-29 | REINFORCED POLYAMIDE COMPOSITION AND PROCESS FOR PREPARING THE SAME WELL AS REINFORCED POLYAMIDE ARTICLE |
CA071,042A CA943280A (en) | 1968-12-30 | 1969-12-29 | Filled reinforced polyamide compositions |
BE743839D BE743839A (en) | 1968-12-30 | 1969-12-30 | |
FR6945482A FR2032588A5 (en) | 1968-12-30 | 1969-12-30 | |
DE19691965434 DE1965434A1 (en) | 1968-12-30 | 1969-12-30 | Reinforced polyamide preparations and processes for their manufacture |
GB0896/70A GB1237844A (en) | 1968-12-30 | 1970-01-14 | Reinforced polymer compositions |
GB1625974A GB1457815A (en) | 1968-12-30 | 1974-04-11 | Reinforced polyamide-containing compositions |
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US80633268A | 1968-12-30 | 1968-12-30 | |
US80633368A | 1968-12-30 | 1968-12-30 | |
US80633168A | 1968-12-30 | 1968-12-30 | |
FR6945482A FR2032588A5 (en) | 1968-12-30 | 1969-12-30 | |
GB0896/70A GB1237844A (en) | 1968-12-30 | 1970-01-14 | Reinforced polymer compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1237844A true GB1237844A (en) | 1971-06-30 |
Family
ID=27515345
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB0896/70A Expired GB1237844A (en) | 1968-12-30 | 1970-01-14 | Reinforced polymer compositions |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB1237844A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4542174A (en) * | 1984-03-14 | 1985-09-17 | Union Carbide Corporation | Organosilicon/oxirane additives for filled condensation polymer composites |
FR2719840A1 (en) * | 1990-12-18 | 1995-11-17 | Hoechst Celanese Corp | Injection moldable ceramic and metal compositions and process for their preparation |
RU2637962C1 (en) * | 2016-11-10 | 2017-12-08 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Powder polymer composition and method of its production |
CN112625381A (en) * | 2020-12-09 | 2021-04-09 | 安徽腾龙泵阀制造有限公司 | Preparation method of wear-resistant mud pump acid baffle plate |
US11059956B2 (en) * | 2017-03-27 | 2021-07-13 | Lg Chem, Ltd. | Organic-inorganic composite for rubber reinforcement, method for preparing the same, and rubber composition for tires comprising the same |
WO2022135250A1 (en) * | 2020-12-21 | 2022-06-30 | 金发科技股份有限公司 | Alloy material having ceramicized surface, preparation method therefor and application thereof |
CN117342807A (en) * | 2023-12-05 | 2024-01-05 | 山东崇正特种水泥有限公司 | Low-heat cement and production process thereof |
-
1970
- 1970-01-14 GB GB0896/70A patent/GB1237844A/en not_active Expired
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4542174A (en) * | 1984-03-14 | 1985-09-17 | Union Carbide Corporation | Organosilicon/oxirane additives for filled condensation polymer composites |
FR2719840A1 (en) * | 1990-12-18 | 1995-11-17 | Hoechst Celanese Corp | Injection moldable ceramic and metal compositions and process for their preparation |
GB2293826A (en) * | 1990-12-18 | 1996-04-10 | Hoechst Celanese Corp | Injection moldable ceramic and metallic compositions and method of preparing the same |
GB2293826B (en) * | 1990-12-18 | 1996-07-03 | Hoechst Celanese Corp | Injectable moldable ceramic and metallic compositions and method of preparing the same |
RU2637962C1 (en) * | 2016-11-10 | 2017-12-08 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") | Powder polymer composition and method of its production |
US11059956B2 (en) * | 2017-03-27 | 2021-07-13 | Lg Chem, Ltd. | Organic-inorganic composite for rubber reinforcement, method for preparing the same, and rubber composition for tires comprising the same |
CN112625381A (en) * | 2020-12-09 | 2021-04-09 | 安徽腾龙泵阀制造有限公司 | Preparation method of wear-resistant mud pump acid baffle plate |
CN112625381B (en) * | 2020-12-09 | 2023-05-26 | 安徽腾龙泵阀制造有限公司 | Preparation method of wear-resistant mud pump acid baffle |
WO2022135250A1 (en) * | 2020-12-21 | 2022-06-30 | 金发科技股份有限公司 | Alloy material having ceramicized surface, preparation method therefor and application thereof |
CN117342807A (en) * | 2023-12-05 | 2024-01-05 | 山东崇正特种水泥有限公司 | Low-heat cement and production process thereof |
CN117342807B (en) * | 2023-12-05 | 2024-01-30 | 山东崇正特种水泥有限公司 | Low-heat cement and production process thereof |
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