US3383368A - Novel copolymaides of phenylindan carboxylic acid - Google Patents
Novel copolymaides of phenylindan carboxylic acid Download PDFInfo
- Publication number
- US3383368A US3383368A US457828A US45782865A US3383368A US 3383368 A US3383368 A US 3383368A US 457828 A US457828 A US 457828A US 45782865 A US45782865 A US 45782865A US 3383368 A US3383368 A US 3383368A
- Authority
- US
- United States
- Prior art keywords
- copolyamide
- carboxylic acid
- mole percent
- phenylindan
- novel
- 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 - Lifetime
Links
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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
-
- 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
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
- C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
Definitions
- ABSTRACT UP THE DISCLGSURE Copolyamides having high boiling water shrinkage are composed of hexamethylene adipamide and hexamethylene 3-(4-carboxyphenyl)1,1,3-trimethyl-5-indan carboxylamide. These copolyamides are useful in the production of yarns, fabrics, films, textile fibers and reinforcing cords.
- Polyamides such as polyhexamethylene adipamide (nylon 66) and polycaproamide (nylon 6) are Well known in the art and have found significant commercial success both as textile fibers and as reinforcing fibers, such as tire cord.
- nylon 66 polyhexamethylene adipamide
- nylon 6 polycaproamide
- these previously known polyamides all possess a relatively low shrinkage value, that is, the amount of shrinkage that occurs in fibers made from these polyamides when they are treated with boiling Water is relatively small.
- conjugate fibers that is, a fiber having two or more components
- I t is a further object of this invention to provide a novel synthetic linear fiber-forming copolyamide which has increased boiling water shrinkage characteristics.
- copolyamides of the present invention are useful in the production of shaped articles by extrusion, rnolding or casting in the nature of yarns, fabrics, films, pellicles, bearings, ornaments or the like. They are particularly useful in the production of textile fibers and as reinforcin cords produced therefrom.
- the present invention provides a novel linear fiberforming copolyamide composed of (A) 1 to 99 mole percent, based on the molecular weight of the copolyamide, of units represented by the structure -L I(OHZ)GI I-( ;(CHQ)4 (B) 1 to 99 mole percent, based on the molecular weight of the copolyamide, of units represented by the structure wherein R is a divalent hydrocarbon radical selected from the group consisting of tetramethylene and 1,4-Cyclohexylene and R is a member of the group consisting of hydrogen and alkyl groups containing 1 to 3 carbon atoms.
- the copolyamide is formed by interpolymerizing (A) substantially equimolecular proportions of adipic acid and hexamethylene diamine, (B) substantiaily equimolecular proportions of a phenylindan dicarboxylic acid and a diamine selected from the group consisting of hexamethylene diamine and 1,4-cyclohexanbis-(methylamine), wherein component (A) is present in an amount sutficient to provide 1 to 99, preferably 50 to mole percent of the final copolymer and component (B) is present in an amount sufiicient to provide 1 to 99, preferably 10 to 50 mole percent of the final copolymer.
- component (A) is present in an amount sutficient to provide 1 to 99, preferably 50 to mole percent of the final copolymer and component (B) is present in an amount sufiicient to provide 1 to 99, preferably 10 to 50 mole percent of the final copolymer.
- component (A) is present
- the copolyamides of this invention are prepared by procedures well known in the art and commonly employed in the manufacture of simple polyamides. That is, the reactants are heated at a temperature of from C. to 300 C. and preferably from 200 C. to 295 C. until the product has a sufiiciently high molecular weight to exhibit fiber-forming properties, which properties are reached when the copolyamide has an intrinsic viscosity of at least 0.4.
- the reaction can be conducted at super atmospheric, atmospheric, or subatmospheric pressure. Often it is desirable, especially in the last stage of the reaction, to employ conditions, e.g. reduced pressure, which will aid in the removal of the reaction by-products. Preferably the reaction is carried out in the absence of oxygen, for example, in an atmosphere of nitrogen.
- Intrinsic viscosity as employed herein is defined as in which N is the relative viscosity of a dilute solution of the polymer in rn-cresol in the same units at the same temperature and C is the concentration of grams of polymer per 100 cc. of solution.
- the amount of component (A) present in the copolymers of the present invention ranges from 1 to 99, preferably 90 to 50 mole percent based on the molecular weight of the copolymer and component (B) is present in the copolymer in an amount of from 1 to 99, preferably 10 to 50 mole percent based on the weight of the copolymer. It has been found that the copolymer compositions thus prepared have a substantially increased boiling water shrinkage and show a great decrease in their tendency to fiatspot when they are used as reinforcing fibers for vehicle tires.
- phenylindan carboxylic acids which are employed in the preparation of the copolymers of the present invention may be represented by the formula:
- R is as defined above.
- Typical suitable compounds falling within this formula are: 3-(4-carboxyphenyl) indan carboxylic acid; 3 (3 carboxyphenyl) 5 indan carboxylic acid; 3 (4 carboxyphenyl) 1,1,3 trimethyl 5 indan carboxylic acid;
- Example I A solution containing 125.8 parts (90 mole percent) of hexamethylenediammonium adipate and 23.45 parts (10 mole percent) of the hexamethylenediamine salt of 3-(4- carboxyphenyl) 1,1,3 trimethyl 5 indan carboxylic acid, dissolved in 80 parts of water, was placed in a stainless-steel, high pressure autoclave which had been previously purged with purified nitrogen. The temperature and pressure within the autoclave were slowly raised until values of 220 C. and 250 p.s.i.g., respectively, were reached. The temperature was then further increased to 243 C. while the pressure was maintained at 250 p.s.i.g. by removal of steam as condensate. When this point was reached, the pressure within the autoclave was gradually reduced to atmospheric over a -minute period. During this period the temperature was allowed to level out at 280 C. at which point the polymer melt was allowed to equilibrate for minutes.
- the resultant polymer thus obtained, was nearly transparent and had a melting point of approximately 247 C.
- This molten polymer was melt spun directly from the bottom of the autoclave through a single-hole spinneret to yield a mono-filament yarn having good textile properties.
- Example 11 A solution of 104.2 parts (80 mole percent) of hexamethylenediammonium adipate and 43.9 parts (20 mole percent) of the hexamethylenediamine salt of 3-(4-carboxyphenyl)-l,1,3-trimethyl-5-indan carboxylic acid, dissolved in 80 parts of water, was added to a stainless-steel high-pressure autoclave. Polymerization of this mixture was brought about by the steps and procedures as set forth in Example I. The resulting, transparent polymer melting point was measured to be approximately 236 C.
- This finished polymer was melt spun directly from the autoclave through a single-hole spinneret to yield a monofilainent yarn having good textile properties.
- Example III A solution of 81.5 parts mole percent) of hexamethylenediammonium adipate and 61.6 parts (30 mole percent) of the hexamethylenediamine salt of 3-(4-carboxyphenyD-l,1,3-trirnethyl-5-indan carboxylic acid, dissolved in parts of water, was added to a stainless-steel high-pressure autoclave. The solution was polymerized in accordance with the conditions and procedures as set forth in Example I. The transparent polymer thus obtained had a melting point of about 222 C. This finished polymer was melt extruded directly from the bottom of the autoclave through a single-hole spinneret yielding a mono-filament yarn of good textile properties.
- Example IV A solution was prepared by introducing a mixture of 36.7 parts of hexamethylene diamine and 49.9 parts adipic acid (70 mole percent) and a mixture of 20.8 parts of cyclohexanbis-(methylamine) and 47.5 parts of 3-(4- carboxyphenyl)-1,1,3-trimethyl-5-indan carboxylic acid (30 mole percent) into 80 parts of water. This solution was added to a stainless-steel high pressure autoclave and polymerization was carried out as in Example I. The resulting transparent polymer had a melting point of 229 C. and was spun into a mono-filament yarn having good textile properties.
- the yarns prepared from the copolyamides obtained in accordance with the present invention exhibit a significant increase in boiling water shrinkage when compared to a yarn prepared from a conventional polyamide.
- Yarns made from the copolyamides of the present invention were formed into cords and used to reinforce rubber vehicle tires.
- the tires thus formed were tested for fiatspot severity and were found to have a significant reduction in the amount of fiatspot when compared to conventional polyhexaniethylene adipamide reinforced tires. This reduction in fiatspot was maintained over a variety of conditions of temperature and humidity, thus eliminating the need for any additional additive to counteract the effect of atmospheric changes.
- a linear fiber-forming copolyamide composed of (A) 1 to 99 mole percent based on the molecular weight of the copolyamide of units represented by the structure H HO 0 III I] and (B) 1 to 99 mole percent based .on the molecular weight of the copolyamide of units represented by the structure wherein R is a divalent hydrocarbon radical selected from the group consisting of tetramethylene and 1,4-cyclohexylene and R is a member of the group consisting of hydrogen and alkyl groups containing 1-3 carbon atoms.
- a linear fiber-forming copolyamide composed of (A) 90 to 50 mole percent, based on the molecular weight of the copolyamide of units represented by the structure weight of the copolyamide of units represented by the structure wherein R is a divalent hydrocarbon radical selected from the group consisting of tetramethylene and 1,4-cyclohexylene and R is a member of the group consisting of hydrogen and alkyl groups containing 1 to 3 carbon atoms. 7.
- R is tetramethylene and R is methyl.
- R is 1,4-cyclohexylene and R is methyl.
- a textile fiber composed of the copolyamide as defined in claim 1.
- a textile fiber composed of the copolyamide as defined in claim 6.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
- Artificial Filaments (AREA)
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US457828A US3383368A (en) | 1965-05-21 | 1965-05-21 | Novel copolymaides of phenylindan carboxylic acid |
GB21404/66A GB1099576A (en) | 1965-05-21 | 1966-05-13 | Novel copolyamides and process |
DE19661620993 DE1620993A1 (de) | 1965-05-21 | 1966-05-17 | Lineare faserbildende Mischpolyamide und Verfahren zu deren Herstellung |
LU51130A LU51130A1 (ja) | 1965-05-21 | 1966-05-17 | |
NL6606953A NL127438C (ja) | 1965-05-21 | 1966-05-20 | |
BE681322D BE681322A (ja) | 1965-05-21 | 1966-05-20 | |
FR62368A FR1480689A (fr) | 1965-05-21 | 1966-05-20 | Copolyamides |
CH739966A CH466572A (fr) | 1965-05-21 | 1966-05-23 | Procédé de fabrication de copolyamides |
US602121A US3376270A (en) | 1965-05-21 | 1966-12-16 | Polyamides from xylylene diamines and phenylindan dicarboxylic acids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US457828A US3383368A (en) | 1965-05-21 | 1965-05-21 | Novel copolymaides of phenylindan carboxylic acid |
Publications (1)
Publication Number | Publication Date |
---|---|
US3383368A true US3383368A (en) | 1968-05-14 |
Family
ID=23818222
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US457828A Expired - Lifetime US3383368A (en) | 1965-05-21 | 1965-05-21 | Novel copolymaides of phenylindan carboxylic acid |
Country Status (7)
Country | Link |
---|---|
US (1) | US3383368A (ja) |
BE (1) | BE681322A (ja) |
CH (1) | CH466572A (ja) |
DE (1) | DE1620993A1 (ja) |
GB (1) | GB1099576A (ja) |
LU (1) | LU51130A1 (ja) |
NL (1) | NL127438C (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3535286A (en) * | 1968-04-10 | 1970-10-20 | Goodyear Tire & Rubber | Terephthalic acid-phenyl indane dicarboxylic acid copolyester resin |
US3621002A (en) * | 1968-11-29 | 1971-11-16 | Monsanto Co | Transparent fiber-forming copolyamides |
US3936426A (en) * | 1971-12-21 | 1976-02-03 | Phillips Petroleum Company | Amorphous, optically clear polyamide from a bis(4-aminocyclohexyl)methane and a phenylindan dicarboxylic acid |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2990568B2 (ja) * | 1993-12-13 | 1999-12-13 | 花王株式会社 | 銅含有水素化触媒の調製法およびアルコールの製造法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2913433A (en) * | 1955-12-28 | 1959-11-17 | Du Pont | Polyamides from hydrocarbon substituted piperazines and carboxyclic dicarboxylic acid |
US2918454A (en) * | 1954-08-16 | 1959-12-22 | Ethyl Corp | Condensation polymers |
US3145193A (en) * | 1959-10-29 | 1964-08-18 | Grace W R & Co | Polyamides from a mixture of isophthalic acid, terephthalic acid and branched chain aliphatic diamine |
-
1965
- 1965-05-21 US US457828A patent/US3383368A/en not_active Expired - Lifetime
-
1966
- 1966-05-13 GB GB21404/66A patent/GB1099576A/en not_active Expired
- 1966-05-17 DE DE19661620993 patent/DE1620993A1/de active Pending
- 1966-05-17 LU LU51130A patent/LU51130A1/xx unknown
- 1966-05-20 NL NL6606953A patent/NL127438C/nl active
- 1966-05-20 BE BE681322D patent/BE681322A/xx unknown
- 1966-05-23 CH CH739966A patent/CH466572A/fr unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2918454A (en) * | 1954-08-16 | 1959-12-22 | Ethyl Corp | Condensation polymers |
US2913433A (en) * | 1955-12-28 | 1959-11-17 | Du Pont | Polyamides from hydrocarbon substituted piperazines and carboxyclic dicarboxylic acid |
US3145193A (en) * | 1959-10-29 | 1964-08-18 | Grace W R & Co | Polyamides from a mixture of isophthalic acid, terephthalic acid and branched chain aliphatic diamine |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3535286A (en) * | 1968-04-10 | 1970-10-20 | Goodyear Tire & Rubber | Terephthalic acid-phenyl indane dicarboxylic acid copolyester resin |
US3621002A (en) * | 1968-11-29 | 1971-11-16 | Monsanto Co | Transparent fiber-forming copolyamides |
US3936426A (en) * | 1971-12-21 | 1976-02-03 | Phillips Petroleum Company | Amorphous, optically clear polyamide from a bis(4-aminocyclohexyl)methane and a phenylindan dicarboxylic acid |
Also Published As
Publication number | Publication date |
---|---|
LU51130A1 (ja) | 1966-11-17 |
CH466572A (fr) | 1968-12-15 |
NL6606953A (ja) | 1966-11-22 |
NL127438C (ja) | 1969-10-15 |
GB1099576A (en) | 1968-01-17 |
BE681322A (ja) | 1966-11-21 |
DE1620993A1 (de) | 1970-05-14 |
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