CA2028301A1 - Process for the preparation of a thermoplastically processable aromatic polyamide - Google Patents
Process for the preparation of a thermoplastically processable aromatic polyamideInfo
- Publication number
- CA2028301A1 CA2028301A1 CA 2028301 CA2028301A CA2028301A1 CA 2028301 A1 CA2028301 A1 CA 2028301A1 CA 2028301 CA2028301 CA 2028301 CA 2028301 A CA2028301 A CA 2028301A CA 2028301 A1 CA2028301 A1 CA 2028301A1
- Authority
- CA
- Canada
- Prior art keywords
- component
- preparation
- aromatic polyamide
- thermoplastically processable
- processable aromatic
- 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.)
- Abandoned
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
- C08G69/32—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from aromatic diamines and aromatic dicarboxylic acids with both amino and carboxylic groups aromatically bound
-
- 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
- C08G69/28—Preparatory processes
-
- 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
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyamides (AREA)
Abstract
Abstract A process for the preparation of thermoplastically processable aromatic polyamide by polycondensation of (A) HOOC-Ar-COOH and (B) H2N-Ar'-NH2, wherein Ar is, for example, 1,3-or 1,4-phenylene and Ar' is wherein X is -SO2- or -CO- and Y is -O- or -S-, in the melt at a temperature of from 200 to 400°C, in the presence of a catalyst and in a molar excess of component (A) relative to component (B).
The polyamides so obtained have an improved resistance to thermo-oxidation and hydrolysis and are useful in moulding compositions.
The polyamides so obtained have an improved resistance to thermo-oxidation and hydrolysis and are useful in moulding compositions.
Description
1 ~ 23443 428 HULS ARTIENGESELLSCHAFT O.Z- 4437 - PATENTABT~ILUNG -Proceqs for the preparation of a thermoDlastically processible aromatlc polyamide ~he invention relates to a process for the preparation of a thermoplastically proceqsible aromatic polyamide by polycondensation of the following starting monomers~
. HOOC - Ar - COOH
B. H2N - Ar' - NH2 in which the ~y~bol~ have the meaning~ which follow Ar: 1,3- or 1,4-Phenylene; 1,4-, 1,5-, 2,6- or 2,7-naphthylene, ~ Zn or ~Y~X~ ~
Ar':
~Y~X~Y~
X: -52-; -CO-;
y: -0-; -S-;
Z: -0-; -S-; -S02-; -C0-; -CR2-;
R: -H Cl - C4-Alkyl;
n: 0; 1;
in the melt in the pre~ence of a catslyst at temperatures in the range of from 200 to 400-C.
The preparation of polyamides of this type is known in prin-ciple(German Published Patent Application No. 3,609,011). How-ever, the melt viscosity of these aromatic polyamides is high.
Very high temperatures are therefore necessary in their preparation and processing - generally at least 350C. At these - 2 ~ i o.z. 4437 temperatures, damage to the product is often observed, recognizable from discolorations or a deterioration in the mechanical properties.
A further disadvantage of the polyamides which have been prepared in this manner is their sen~itivity to hydrolytic degradation, resulting from a hiqh water absorption. To prevent this, other measures are necessary during processing, for example dryinq.
The object of the invention is to provide moulding compositions based on aromatic polyamides, which do not have the described disadvantage~ of the prior art products.
This ob~ect is achieved by using the component A. in a molar excess relative to the component B..
The mole ratio of component A.: component B. i~ prefer-ably in the range of from 1.1 to 1.01:1.0 and in par-ticular 1.08 to 1.02:1Ø
Suitable aromatic dicarboxylic acids (component A.) are isophthalic acid, terephthalic acid, 1,4-, 1,5-, 2,6-, and 2,7-naphthalenedicarboxylic acid, 4,4~-diphenyl ether dicarboxylic acid or 4,4~-benzophenonedicarboxylic acid, 4,4'-diphenyl sulphone dicarboxylic acid, 2-phenoxy-terephthalic acid, 4,4'-biphenyldicarboxylic acid or mixtures thereof.
Preference i8 given to the use of isophthalic acid alone or a mixture of isophthalic acid and one of the other abovementioned acids, as component A.. Ultimately up to 45 mol % of isophthalic acid is replaced.
Examples of suitable aromatic diamines (component B.) are 4,4'-bis(4-amino-phenoxy)diphenyl sulphone, 4,4'-bis(3-aminophenoxy)diphenylsulphone~4r4~-bist4-aminophenoxy) benzophenone,4,4'-bis(3-aminophenoxy)benzophenone~4~4~-~ i 23443-428 - 3 - O.Z. 4437 bis(p-aminophenylmercapto)benzophenon0, 4,4'-b$s~p-amino-phenylmercapto)diphenyl ~ulphone or mixture~ thereof.
Preference i8 given to the u~e of 4,4'-bi3(4-amino-phenoxy)diphenyl sulphone.
The glass tran~ition temperature (T,) of the polyamides according to the invention i8 in the range of from 190 to 270-C and the visco~ity number~ (J value3) are approximately 30 to 100 cm3~g; preferably 6 to 80 cm3/q.
The preparation of the aromatic polyamides is known in principle. I~ i~ desc~ibsd in, amon~ other source~, German Published Patent Application No. 3,609,011.
The polycondensation i~ carried out in the pre~ence of catalysts. Suitable catalyst~ for this purpose are pho~phorus-containlng compounds ~uch as triphenyl phosphite or acids of the general formula H3P0~ in which m - 2 to 4. It ie also pos~ible to u~e, mixed with these substances, tin~II) compounda such a~, for example, tin(II) ~alts of organic carboxylic acida.
It is al~o known to addition~lly u~e co-catalysts such as, for ex~mple, dialkylam$nopyridine~.
~he catalysts are used in amount~ ~rom 0.05 to 4 mol ~, preferably 0.1 to 2 mol %, relAtive to the 8um of the components A. and B
~he reaction i8 carried out ~n the melt at temperatures in the range of from 200 to 400-C, preferably from 230 to 360-C.
It i8 normal to operate at atmo~pheric pressure under an inert ga~. However, it io ~180 poa~ible to employ elevated pre~ure or reduced pre~sure.
The molecular weight can be increased by sub~ecting the - 4 - ~ .Z. 4437 aromatic polyamides ~o solid phase post-conden~ation in an inert gas atmosphere.
The polyamides can be processed on conventional machines by in~ection moulding or extrusion to give moulding compositions.
The moulding compositions may additionally contain fillers such as talc or reinforcing agents ~uch as glas~
fibres, ARAMIDR fibres or carbon fibres and also other customary additives such as, for example, pigments or ~tabilizers.
The moulding compositions are processed by conventional processes such as in~ection moulding, extrusion and the liXe to give moulding~, fibres, films and 50 on. Equally, it is possible to use the said moulding compositions as coating compositions starting from powder (for example fluidized bed coating), from a liquid dispersion or from a solution.
Aromatic polyamides which have been prepared by the process according to the invention withstand unexpectedly high temperature~. The products can be processed at temperatures even in excess of 340C without diminution of the molecular weight or brown discoloration occurring.
Furthermore, moulding compositions obtained according to the invention have an excellent resistance to thermo-oxidation so that they can be used at significantlyhigher temperatures than the corresponding prior art composi~ions. These properties include good heat resi~tance, i.e. moulding compositions which are based on aromatic polyamides according to the invention can be exposed to high temperatures for long period-~ without a significant loss of mechanical properties. Furthermore, the said compositions have an unexpectedly high hydrolysis resistance.
The quantities mentioned in the description and in the - 5 ~ O.Z. 4437 examples were determined using the processes which are given below.
The glass transition temperature (T~) was determined by DSC using a heating rate of 10C/min.
The viscosity numbers (J) were determined from 0.5 %
strength by weight solutions of the polyamide~ in a phenol/o-dichlorobenzene mixture (1:1 by weight) at 25C
in accordance with DIN 53 728.
The heat ageing of the test pieces was carried out at 250C in a circulating-air oven with a fresh air supply of 10 %.
The examples designated by letters are not according to the invention.
Examples _xam~le 1:
21.62 g (O.OS mol) of 4,4'-bis(4-aminophenoxy)diphenyl sulphone and 8.64 g (0.052 mol) of isophthalic acid were melted with 155 mg (0.0005 mol) of triphenyl phosphite and 61.1 mg (0.005 mol) of 4-dimethylaminopyridine in a polycondensation reactor fitted with a stirrer, nitrogen feed and distillation arm at 250C. After 20 minute~, the temperature was increased to 300C. At the same time the viscosity of the melt increased steadily while the water liberated in the course of the reaction was distilled off. After 10 minutes at 300C, the reaction was terminated.
The viscosity number (J) was 24 cm3/g. Solid phase post-condensation at 250C and 0.5 mbar gave, after 24 h, a polyamide having J = 68 cm3/g .
. HOOC - Ar - COOH
B. H2N - Ar' - NH2 in which the ~y~bol~ have the meaning~ which follow Ar: 1,3- or 1,4-Phenylene; 1,4-, 1,5-, 2,6- or 2,7-naphthylene, ~ Zn or ~Y~X~ ~
Ar':
~Y~X~Y~
X: -52-; -CO-;
y: -0-; -S-;
Z: -0-; -S-; -S02-; -C0-; -CR2-;
R: -H Cl - C4-Alkyl;
n: 0; 1;
in the melt in the pre~ence of a catslyst at temperatures in the range of from 200 to 400-C.
The preparation of polyamides of this type is known in prin-ciple(German Published Patent Application No. 3,609,011). How-ever, the melt viscosity of these aromatic polyamides is high.
Very high temperatures are therefore necessary in their preparation and processing - generally at least 350C. At these - 2 ~ i o.z. 4437 temperatures, damage to the product is often observed, recognizable from discolorations or a deterioration in the mechanical properties.
A further disadvantage of the polyamides which have been prepared in this manner is their sen~itivity to hydrolytic degradation, resulting from a hiqh water absorption. To prevent this, other measures are necessary during processing, for example dryinq.
The object of the invention is to provide moulding compositions based on aromatic polyamides, which do not have the described disadvantage~ of the prior art products.
This ob~ect is achieved by using the component A. in a molar excess relative to the component B..
The mole ratio of component A.: component B. i~ prefer-ably in the range of from 1.1 to 1.01:1.0 and in par-ticular 1.08 to 1.02:1Ø
Suitable aromatic dicarboxylic acids (component A.) are isophthalic acid, terephthalic acid, 1,4-, 1,5-, 2,6-, and 2,7-naphthalenedicarboxylic acid, 4,4~-diphenyl ether dicarboxylic acid or 4,4~-benzophenonedicarboxylic acid, 4,4'-diphenyl sulphone dicarboxylic acid, 2-phenoxy-terephthalic acid, 4,4'-biphenyldicarboxylic acid or mixtures thereof.
Preference i8 given to the use of isophthalic acid alone or a mixture of isophthalic acid and one of the other abovementioned acids, as component A.. Ultimately up to 45 mol % of isophthalic acid is replaced.
Examples of suitable aromatic diamines (component B.) are 4,4'-bis(4-amino-phenoxy)diphenyl sulphone, 4,4'-bis(3-aminophenoxy)diphenylsulphone~4r4~-bist4-aminophenoxy) benzophenone,4,4'-bis(3-aminophenoxy)benzophenone~4~4~-~ i 23443-428 - 3 - O.Z. 4437 bis(p-aminophenylmercapto)benzophenon0, 4,4'-b$s~p-amino-phenylmercapto)diphenyl ~ulphone or mixture~ thereof.
Preference i8 given to the u~e of 4,4'-bi3(4-amino-phenoxy)diphenyl sulphone.
The glass tran~ition temperature (T,) of the polyamides according to the invention i8 in the range of from 190 to 270-C and the visco~ity number~ (J value3) are approximately 30 to 100 cm3~g; preferably 6 to 80 cm3/q.
The preparation of the aromatic polyamides is known in principle. I~ i~ desc~ibsd in, amon~ other source~, German Published Patent Application No. 3,609,011.
The polycondensation i~ carried out in the pre~ence of catalysts. Suitable catalyst~ for this purpose are pho~phorus-containlng compounds ~uch as triphenyl phosphite or acids of the general formula H3P0~ in which m - 2 to 4. It ie also pos~ible to u~e, mixed with these substances, tin~II) compounda such a~, for example, tin(II) ~alts of organic carboxylic acida.
It is al~o known to addition~lly u~e co-catalysts such as, for ex~mple, dialkylam$nopyridine~.
~he catalysts are used in amount~ ~rom 0.05 to 4 mol ~, preferably 0.1 to 2 mol %, relAtive to the 8um of the components A. and B
~he reaction i8 carried out ~n the melt at temperatures in the range of from 200 to 400-C, preferably from 230 to 360-C.
It i8 normal to operate at atmo~pheric pressure under an inert ga~. However, it io ~180 poa~ible to employ elevated pre~ure or reduced pre~sure.
The molecular weight can be increased by sub~ecting the - 4 - ~ .Z. 4437 aromatic polyamides ~o solid phase post-conden~ation in an inert gas atmosphere.
The polyamides can be processed on conventional machines by in~ection moulding or extrusion to give moulding compositions.
The moulding compositions may additionally contain fillers such as talc or reinforcing agents ~uch as glas~
fibres, ARAMIDR fibres or carbon fibres and also other customary additives such as, for example, pigments or ~tabilizers.
The moulding compositions are processed by conventional processes such as in~ection moulding, extrusion and the liXe to give moulding~, fibres, films and 50 on. Equally, it is possible to use the said moulding compositions as coating compositions starting from powder (for example fluidized bed coating), from a liquid dispersion or from a solution.
Aromatic polyamides which have been prepared by the process according to the invention withstand unexpectedly high temperature~. The products can be processed at temperatures even in excess of 340C without diminution of the molecular weight or brown discoloration occurring.
Furthermore, moulding compositions obtained according to the invention have an excellent resistance to thermo-oxidation so that they can be used at significantlyhigher temperatures than the corresponding prior art composi~ions. These properties include good heat resi~tance, i.e. moulding compositions which are based on aromatic polyamides according to the invention can be exposed to high temperatures for long period-~ without a significant loss of mechanical properties. Furthermore, the said compositions have an unexpectedly high hydrolysis resistance.
The quantities mentioned in the description and in the - 5 ~ O.Z. 4437 examples were determined using the processes which are given below.
The glass transition temperature (T~) was determined by DSC using a heating rate of 10C/min.
The viscosity numbers (J) were determined from 0.5 %
strength by weight solutions of the polyamide~ in a phenol/o-dichlorobenzene mixture (1:1 by weight) at 25C
in accordance with DIN 53 728.
The heat ageing of the test pieces was carried out at 250C in a circulating-air oven with a fresh air supply of 10 %.
The examples designated by letters are not according to the invention.
Examples _xam~le 1:
21.62 g (O.OS mol) of 4,4'-bis(4-aminophenoxy)diphenyl sulphone and 8.64 g (0.052 mol) of isophthalic acid were melted with 155 mg (0.0005 mol) of triphenyl phosphite and 61.1 mg (0.005 mol) of 4-dimethylaminopyridine in a polycondensation reactor fitted with a stirrer, nitrogen feed and distillation arm at 250C. After 20 minute~, the temperature was increased to 300C. At the same time the viscosity of the melt increased steadily while the water liberated in the course of the reaction was distilled off. After 10 minutes at 300C, the reaction was terminated.
The viscosity number (J) was 24 cm3/g. Solid phase post-condensation at 250C and 0.5 mbar gave, after 24 h, a polyamide having J = 68 cm3/g .
- 6 ~ 3~ ~ 0.2. 4437 ExamDles 2 - 6 and Exam~les A and B
The Examples 2 - 6 and also Examples A and B were poly-condensed similarly to Example 1, but the excess of dicarboxylic acid and the catalyst components were varied S in accordance with the following table.
Heat aaeina The polyamides prepared in Examples 1 to 6 and also in A
and B were press-moulded at 310C and a pressure of lO0 bar to sheetY of 1 mm thickness and aged for 2 hours in an circulating-air oven. The polyamides prepared in Examples A and B were dark brown in colour while the polyamides prepared according to Examples 1 to 6 showed virtually no discoloration.
r~ .L
~ 7 .
.~ ~ = 3 ~1 ~ ~ ~ r~ O ~
b co ~
. .
~3 , o~ C~, ~ , ,, ~ ~ ~ ~ ~ ~ ~ ~ ~
__ dP
o U~
. ~ , o ~ o o o ~ ~.
~ _ ~
dP ~o ~ o U~ )~
_ ~_ ~ ~-~ O ~ ~
_ _ _ ~ _ _ .
N _I It~ U~ U') Ul ISl ~r) 11~ In ~ ~
~ ~ o. o. o o o o o o. . 5. ~ o ~ _~ O O O O O O O O '~5 ~ ~ ~
. ~ ~- ~
u~ T;~
o o o o o o o o .~9 ~ i__~
~ ~ ~
.al ~ ~i ~
E~ ~ ~ ~ ~ u~ C m _ _ _ _ _ _ _
The Examples 2 - 6 and also Examples A and B were poly-condensed similarly to Example 1, but the excess of dicarboxylic acid and the catalyst components were varied S in accordance with the following table.
Heat aaeina The polyamides prepared in Examples 1 to 6 and also in A
and B were press-moulded at 310C and a pressure of lO0 bar to sheetY of 1 mm thickness and aged for 2 hours in an circulating-air oven. The polyamides prepared in Examples A and B were dark brown in colour while the polyamides prepared according to Examples 1 to 6 showed virtually no discoloration.
r~ .L
~ 7 .
.~ ~ = 3 ~1 ~ ~ ~ r~ O ~
b co ~
. .
~3 , o~ C~, ~ , ,, ~ ~ ~ ~ ~ ~ ~ ~ ~
__ dP
o U~
. ~ , o ~ o o o ~ ~.
~ _ ~
dP ~o ~ o U~ )~
_ ~_ ~ ~-~ O ~ ~
_ _ _ ~ _ _ .
N _I It~ U~ U') Ul ISl ~r) 11~ In ~ ~
~ ~ o. o. o o o o o o. . 5. ~ o ~ _~ O O O O O O O O '~5 ~ ~ ~
. ~ ~- ~
u~ T;~
o o o o o o o o .~9 ~ i__~
~ ~ ~
.al ~ ~i ~
E~ ~ ~ ~ ~ u~ C m _ _ _ _ _ _ _
Claims (4)
1. A process for the preparation of a thermoplastically processable aromatic polyamide by polycondensation of the follow-ing starting monomers:
(A). HOOC - Ar - COOH and (B). H2N - Ar' - NH2 wherein Ar is 1,3- or 1,4-phenylene; 1,4- 1,5- 2,6- or 2,7-naphthylene, or ;
Ar' is wherein X is -SO2- or -CO-;
Y is -O- or -S-;
Z is -O-, -S-, -SO2-, -CO- or -CR2-;
R is -H or C1- C4-alkyl; and n is 0 or 1;
in the melt in the presence of a catalyst at a temperature of from 200 to 400°C, wherein the component (A). is used in a molar excess relative to the component (B).
(A). HOOC - Ar - COOH and (B). H2N - Ar' - NH2 wherein Ar is 1,3- or 1,4-phenylene; 1,4- 1,5- 2,6- or 2,7-naphthylene, or ;
Ar' is wherein X is -SO2- or -CO-;
Y is -O- or -S-;
Z is -O-, -S-, -SO2-, -CO- or -CR2-;
R is -H or C1- C4-alkyl; and n is 0 or 1;
in the melt in the presence of a catalyst at a temperature of from 200 to 400°C, wherein the component (A). is used in a molar excess relative to the component (B).
2. A process according to claim 1, wherein the mole ratio of component (A). to component (B). is in the range of from (1.1 to 1.01) to 1Ø
3. A process according to claim 1, characterized in that the mole ratio of component (Al. to component (B). is in the range of from (1.08 to 1.02) to 1Ø
4. A moulding composition comprising a thermoplastically processable aromatic polyamide prepared according to claim 1, 2 or 3.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3935467.9 | 1989-10-25 | ||
| DE19893935467 DE3935467A1 (en) | 1989-10-25 | 1989-10-25 | METHOD FOR PRODUCING A THERMOPLASTICALLY PROCESSABLE, AROMATIC POLYAMIDE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2028301A1 true CA2028301A1 (en) | 1991-04-26 |
Family
ID=6392139
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2028301 Abandoned CA2028301A1 (en) | 1989-10-25 | 1990-10-23 | Process for the preparation of a thermoplastically processable aromatic polyamide |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0424639A1 (en) |
| JP (1) | JPH03153735A (en) |
| CA (1) | CA2028301A1 (en) |
| DE (1) | DE3935467A1 (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3609011A1 (en) * | 1986-03-18 | 1987-09-24 | Huels Chemische Werke Ag | METHOD FOR PRODUCING THERMOPLASTICALLY PROCESSABLE AROMATIC POLYAMIDES |
-
1989
- 1989-10-25 DE DE19893935467 patent/DE3935467A1/en not_active Withdrawn
-
1990
- 1990-08-30 EP EP90116611A patent/EP0424639A1/en not_active Withdrawn
- 1990-10-23 CA CA 2028301 patent/CA2028301A1/en not_active Abandoned
- 1990-10-24 JP JP28452390A patent/JPH03153735A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| DE3935467A1 (en) | 1991-05-02 |
| EP0424639A1 (en) | 1991-05-02 |
| JPH03153735A (en) | 1991-07-01 |
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| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |