CA1317407C - Aromatic sulfideamide polymer and method for producing the same - Google Patents
Aromatic sulfideamide polymer and method for producing the sameInfo
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- CA1317407C CA1317407C CA000586908A CA586908A CA1317407C CA 1317407 C CA1317407 C CA 1317407C CA 000586908 A CA000586908 A CA 000586908A CA 586908 A CA586908 A CA 586908A CA 1317407 C CA1317407 C CA 1317407C
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/025—Preparatory processes
- C08G75/0254—Preparatory processes using metal sulfides
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- 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
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- 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
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/02—Polythioethers
- C08G75/0204—Polyarylenethioethers
- C08G75/0236—Polyarylenethioethers containing atoms other than carbon or sulfur in a linkage between arylene groups
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- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
A class of amide group-containing aromatic dihalide compounds are sulfidlzed to provide a novel class of aromatic sulfideamide polymers increased in crystalline melting point (Tm). The polymers exhibit excellent resis-tance to high temperatures, resistance to solvents, flame-retardant properties and improved mechanical properties.
A class of amide group-containing aromatic dihalide compounds are sulfidlzed to provide a novel class of aromatic sulfideamide polymers increased in crystalline melting point (Tm). The polymers exhibit excellent resis-tance to high temperatures, resistance to solvents, flame-retardant properties and improved mechanical properties.
Description
This invention relates to a novel aromatic sulfideamide polymer and a process for production of the novel polymer.
The polymers according to the invention have a chemical structure in which phenylene and alkylene qroups are alternately bonded via an amide group and a thioether group.
The polymers are useful as materials for producing articles exhibiting improved properties such as excellent resistance to high temperatures, flame-retardant properties, resistance to solvents, good mechanical properties, etc.
Polyphenylene sulfide which is a polymeric compound comprising phenylene groups linked to each other via a thioether group is well known in the art. This polymer has such properties as good flame-retardancy, low moisture absorption, high dimensional stability, etc. However, since this type of polymer exhibits a relatively low heat distor-tion temperature (HDT) of 260C (GF 40%; i.e. where contain-ing 40% by weight of glass fibers) and a crystalline melting point of 281C, its usefulness in applications where high resistance to heat is required is inevitably limited.
Consequently there has been a demand in the art for the development of polyphenylene sulfide materials having higher crystalline melting points.
A polymer substance containing thioether, phenylene and amide groups in the macromolecular backbone, i.e. a polymer of aromatic polythioether amide, and a process for production thereof are described in Japanese Patent Public Disclosure (KOKAI) No. 60-226528. This polymer substance presents some problems in practice because it has a rather low softening point, is soluble in organic solvents such as dimethyl sulfoxide or N-methyl-2-pyrrolidone and exhibits poor resistance to chemicals. Additionally the synthesis of thiol group-containing monomers to be used in the preparation of the polymer is so expensive that production of the polymer is not feasible from the economic viewpoint.
1 31 74n7 The present invention, provides a novel aromatic sulfideamide polymer substance comprising a co~mercially available, inexpensive aliphatic moiety in the repeating units and which is improved in terms of resistance to high - 5 temperatures, resistance to solvents and mechanical properties.
The present invention also provides a process for production of such a novel polymer substance.
According to one aspect of the present invention, there is provided a novel aromatic sulfideamide polymer compound or -- compounds which comprise(s) repeating structural units represented by the following formula (I) and/or (II):
Ar~(Rl)a-C-N-R~-N-C-Ar2(R2)b-S ] (I) o Rs R6 o [ Ar3(R3)c-C-N R8~ N-C-Ar~(R~)d-S ] (II) O O
wherein Arl, Ar2, Ar3 and Ar4 each represent an aromatic ring: Rl, R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of R5 and R6 optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; and R7, R8 and R9, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms, said polymer compound or compounds having a logarithmic viscosity ln~ of 0.02 to 2.00, as determined by measuring the relative viscosity of polymer dissolved in a concentrated sulfuric acid solvent (specific gravity of 1.84) at 30C and at a polymer concentration of 0.5 g/100 ml and computing the result in accordance with the equation:
` 1317407 [ 1 1 - (relative vlscoslty) Q = n (polymer concentratlon) -According to another aspect of the present invention, there is provided a process for production of an aromatic - 2a -sulfldeamide polymer compound or compounds comprising the above defined repeating units (I) and/or (II) lin which the ratio of units ~I) to units (II) ranges from 100:0 to 0:100]: said process comprising the step of sulfidizing one or more amide group-containing dihalide compounds havlng the following general formula (III) and/or (IV) wlth a sulfidiz-ing agent in an organic polar solvent;
X-Arl(Rl)a-C-N-R7-N--C-Ar2(R2)b-Y (III) o R5 R6 0 X-Ar3(R3)c-C-N''RR9 N-lCI-Ar4(R4)d-Y (IV) O O
wherein Arl, Ar2, Ar3 and Ar4 each represent an aromatic ring; Rl, R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of Rs and R~ optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; R7, R8 and R~, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms; and X and Y, which may be the same or different, each represent a halogen.
The accompanying Figs. 1 and 2 show an IR spectrum (wave length: 400 - 4000 cm~l) and an X-ray diffraction pattern (X-ray intensity: counts/angle: 10- - 40) of the polymer obtained in Example 1, respectively.
The invention will now be described in more detail.
Examples of groups Arl, Ar2, Ar3 and Ar4 in the amide group-containing dihalide compounds which may be used in the invention include:
~ ~ . ~ and ~ Z ~
where Z represents -0-, -S-, -S02-, -CO-, -CH2- or -C(CH3 )2-- The groups may be the same or different in one compound.
~ --4--Examples of particularly preferred dihalide compounds (III) and (IV) for use ln the present invention include:
Cl ~ C-N-CH2-N-C ~ Cl.
O H H O
5Cl ~ C-IN-C2H4-N-C ~ Cl, Cl ~ C-N-C2H4-N-ICl ~ Cl' O H H O
Cl ~ C-N-C2H4-N - C ~ Cl, Cl ~ C-N-CH-CH2-N-C ~ Cl, OH
15Cl ~ C-N-CH2-CH-CH2-N-IC ~ Cl, O H H o Cl- ~ C-N-t-CH2)4 Nl-C ~ Cl, 20Cl ~ ~ CH2)6 1 ~C, ~ Cl, Cl~ lC~ -Nl ( CH2 ) 6 ~N- IC~ ~2Cl ~
Cl ~ ICI-N ~ CH2)6 Nl-lCl ~ Cl, CHa H O
25Cl ~ C-N-t--CH2) N-C ~ Cl, O H ~ O
Cl- ~ C-N-t-CH2)12 IN- lCI ~ Cl, O H ~ H O
Cl- ~ C-IN-CH2 ~ CH2-N-C ~ Cl, O H H O
Cl ~ C-N-CH2 ~ CH2-N-C ~ Cl, O H H O
(cis or trans) Cl ~ g-N-CH2- ~ CH2-N-C ~ Cl, (cis or trans) Cl ~ C-N-CH2 ~ N-C ~ Cl, O H ~ O
(cis or trans) Cl ~ C-N ~ N-C ~ Cl, (cis or trans) Cl ~ C-N ~ N-C ~ Cl, O H H O
Cl ~ C-N N-C ~ Cl and Cl~~ ~Cl-O O
It is preferred that the amide group-containing dihalide compounds contain bonds at the Para positions if it is mainly desired to improve the thermal resistance prop-erties of the product polymers. On the other hand, if it is desired to improve the solubility and molding properties of the sulfideamide polymer products, the dihalide compounds may contain bonds at the metha positions and/or at the ortho positions, or may be branched.
The amide group-containing dihalide compounds may be synthesized by the conventional amide linkage formation technique. A typical example of synthesis is a process in which a corresponding halogen-containing aromatic carbonyl chloride is reacted with a corresponding aliphatic diamine.
The organic polar solvents used in the process of the present invention are preferably aprotic ones and ones which are stable in the presence of alkalis at elevated tempera-tures. Examples of the preferred solvents include N,N-dimethyl acetamide ~DJ~), N-ethyl-2-pyrrolidone, hexamethyl phosphoric triamide (HMPA), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (l~MP), 1,3-dimethyl imidazolidinone.
The sulfidizing agents which may be used in the process include alkali metal sulfides, combinations of hydrogen sulfide with alkali metal bases, and combinations of alkali metal hydrosulfides with alkali metal basis.
The alkali metal sulfides and hydrosulfides may be used as hydrates (from 0.5 to lO molar equivalents). The sulfldizlng agents may be prepared in situ prior to introductlon of the dihalide compound of the general formula (III) and/or (IV) into the reaction system. Of course, the sulfidizing agent may be prepared outside the reaction system and then introduced to the system. It ls preferred that, before the sulfidizing agent is introduced for commencement of the polymerization in the reaction system, the content of water in the system should be reduced to a level of less than 2.5 molar equivalents per equivalent of the sulfidizing agent to be introduced.
Among the available sulfidizing agents, sodium sulfide, sodium hydrosulfide in con~unction with sodium hydroxide, and hydrogen sulfide in con~unction with sodium hydroxide are preferred.
In the polymerization, a phase transfer catalyst such as a crown-ether compound, phosphor salt or an ammonium salt compound as well as an assistant such as an alkali metal carboxylate may be used to effectively increase the molecu-lar weight of the resulting polymer.
The polymerization is effected at a temperature of about 150 - 300C, preferably 180 - 280C, for a period of about 0.5 - 24 hours, preferably 1 - 12 hours.
The preferred molar ratio of the dihalide compound (III) and/or (IV) to the sulfidizing agent used in the present process ranges from 0.9:1.0 to 1.1:1Ø
The quantity of solvent used in the process may be such that the reaction system will contain 7 - 50%, prefer-ably 10 - 40%, by weight of the product polymer upon completion of the polymerization.
The product polymer may be recovered by conventional methods, such as vacuum distillation, flash-off, and re-precipitation with organic solvents or water. The isolated product polymer may be washed with any suitable organic solvent or water and then dried.
Generally, the aromatic sulfideamide polymers according to the present invention have a logarithmic viscosity in the range of 0.02 to 2.00, as measured at a concentration of 0.5 g/100 ml in concentrated sulfuric acid . --7--at a temperature of 30C. Polymers having viscosities of 0.05 to 2.00 are preferred.
The aromatic polysulfideamide polymers of the invention may be advantageously chain-extended and/or cross-linked and/or branched by heating in an oxidative atmos-phere, such as air or oxygen-enriched alr.
Where the polymers are molded or otherwise shaped, they may contain various filler materials. Examples of suitable filler materials include (a) fiber fillers, such as glass fibers, carbon fibers, boron fibers, aramid fibers, alumina fibers, etc. and (b) inorganic fillers, such as mica, talc, clay, graphite, carbon black, silica, asbestos, molybdenum disulfide, magnesium oxide, calcium oxide, etc.
As shown in the following Examples, the polymers of the present invention exhibit, on IR analysis, absorptions around 1090 cm~l (caused by thioether linkages), around 1640 cm~' (caused by carbonyl groups in amide linkages) and around 3320 cm~l and 1540 cm~l (both caused by amino groups in amide linkages). These IR data confirm that the present polymers have the structural repeating units (I) and/or (II).
The invention is illustrated in detail but not limited by the following Examples.
Since most of the polymers according to the invention are only soluble in some special solvents such as concen-trated sulfuric acid or an N-methyl-2-pyrrolidone/lithium chloride (95/S by weight) mixture, and are only sparingly soluble or insoluble in common organic solvents, it is not readily possible to determine the average molecular weight of the present pol~ers by a conventional method. Hence, the logarithmic viscosity value [n ] of a polymer is herein employed as a measure of the molecular weight of that polymer. The logarithmic viscosity value [~] is obtained by measuring the relative viscosity of polymer dissolved in a concentrated sulfuric acid solvent at 30~C and at a polymer concentration of 0.5 g/100 ml and calculating the result in accordance with the equation:
-8- ' 1317407 - 1 trelative viscosity) [n ~ - n (polymer concentration) ExamPle A 500 ml autoclave was charged with Na2S-2.7H20 (0.04 moles) and N-methyl-2-pyrrolidone (NlVlP) 150 ml and 5 heated to a temperature of 200 C with stlrring so as to dehydrate the mixture. By this dehydration, 1.26 g of water containing 4.31% of NMP was distilled off. After cooling the reaction system down to 100 C, a dichloride Cl~ g-Nff~H2) N-C~Cl (0.04 moles) was added together with an additional S0 ml of NMP. The system was shielded and heated to 250C. At this temperature, the polymerization was allowed to proceed for 6 hours.
At the end of the polymerization period, the system was cooled and methanol was added to precipitate out the product polymer. The mixture was filtered. The filter cake was repeatedly washed with warm water and filtered and then washed with methanol and dried to give a light gray powdery 20 polymer product (10 g; corresponding to a yield of 70.6%).
The polymer had a logarithmic viscosity of 0.16 (as measured in H2 S04 at a concentration of 0.5 g/100 ml at 30-C). The polymer as such was not melt-moldable, but was soluble in, for example, concentrated sulfuric acid or 25 NMP/LiCl mixture (such a solution could be used in casting to give a film).
The infra-red absorption spectrum of the polymer showed absorptions at 1090 cm~' (thioether linkage) and 3350, 1640 and 1544 cm~l (amide linkage, respectively) (see 30 Fig. 1).
Results of the elemental analysis are listed below:
Found (wt%): C 66.9, H 5.8, N 7.7, S 8.6 Theoretical (wt%): C 67.8, H 6.2, N 7.9, S 9.0 X-ray diffraction confirmed that the product sulfide-35 amide polymer was crystalline in nature (see Fig. 2).
The polymer showed a decomposition temperature of425C but did not show a definite melting point.
ExamPles ~ - 7 The apparatus and procedure of Example 1 was used to polymerize various dihalide compounds. The polymers obtained in all the cases were crystalline.
ExamPle 2 The following dihalide compound was employed:
Cl ~ C-IN ( CH2t--Nl-C ~ Cl Yield: 11.4 g (87.3%) Logarithmic viscosity: 0.11 (measured with a 0.5 g/100 ml solution in H2 S04 at 30C) IR: 1090 cm~' (thioether linkage), 3320; 1617; 1541 cm~
(amide linkage) Elemental analysis:
Found (wt%): C 65.5, H 5.4, N 8.3, S 8.8 Theoretical (wt%): C 66.2, H 5.5, N 8.6, S 9.8 Decomposition temperature: 413-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, NMP, etc.
ExamPle 3 The following dihalide compound was employed:
Cl ~ ICl-lN ( CH2 ~ ~-ICI ~ Cl Yield: 9.7 g (81.3%) Logarithmic viscosity: 0.08 (measured with a 0.5 g/100 ml solution in H2S04 at 30C) IR: 1070 cm~' (thioether linkage), 3320; 1642; 1552 cm~
(amide linkage) Elemental analysis:
Found (wt%): C 64.0, H 4.6, N 9.2, S 8.9 Theoretical (wt%): C 64.4, H 4.7, N 9.4, S 10.7 Decomposition temperature: 351C
(with no definite melting point) -lo- 1 31 7407 Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, etc.
ExamPle 4 The following dihalide compound was employed:
Cl ~ C-N N-C- ~ Cl Yield: 10.4 g (80.1%) Logarithmic viscosity: 0.10 (measured with a 0.5 g/100 ml solution in H2S04 at 30~C) IR: 1075 cm~l (thioether linkage), 1642 cm~~ (carbonyl group) Elemental analysis:
Found (wt%): C 65.0, H 4.9, N 8.5, S 8.1 Theoretical (wt%): C 66.7, H 5.0, N 8.6, S 9.9 Decomposition temperature: 432-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, etc.
ExamDle 5 The following dihalide compound was employed:
Cl ~ ICI-IN-CH2 ~ CH2-NI-lCl ~ Cl Yield: 14.6 g (97.9%) Logarithmic viscosity: 0.09 (measured with a 0.5 g/100 ml solution in H2S0~ at 30C) IR: 1090 cm~1 (thioether linkage), 3320; 1642; 1542 cm~' (amide linkage) Elemental analysis:
Found (wt%): C 68.9, H 4.8, N 7.3, S 7.7 Theoretical (wt%): C 70.1, H 4.8, N 7.5, S 8.5 5 Decomposition temperature: 384-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, etc.
Example 6 The following dihalide compound was employed:
Cl ~ IC-lN-CH2 ~ CH2-Nt-~C~ ~ Cl Yield: 14.9 g (99.0~) Logarithmic viscosity: 0.09 (measured with a 0.5 g/100 ml solution in H2S04 at 30~C) IR: 1080 cm~l (thioetner linkage), 3300; 1640; 1542 cm~
(amide linkage) Elemental analysis:
Found (wt%): C 69.6, H 4.7, N 7.3, S 8.0 Theoretical (wt%): C 70.1, H 4.8, N 7.5, S 8.5 15 Decomposition temperature: 387-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, NMP, DMS0, DMA, etc.
Insoluble in methanol, m-cresol, pyridine, etc.
Exam~le 7 The following dihalide compounds were employed in admixture:
Cl ~ tCI-Nt-t-CH2) 6 Nl-IC ~ Cl (0.02 moles) and Cl ~ C-N N-C ~ Cl O O
(0.02 moles) 30 Yield:11.2 g ~82.3%) Logarithmic viscosity: 0.11 (measured with a 0.5 g/100 ml solution in H2S04 at 30~C) IR: 1080 cm~~ (thioether linkage), 3350; 1642; 1545 cm~' (amide linkage) Elemental analysis:
Found (wt%): C 66.9, H 5.5, N 8.3, S 9.1 Theoretical (wt%): C 67.2, H 5.6, N 8.3, S 9.5 1 31 74~7 Decomposi~ion temperature: 427-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, etc.
From the above description, it will be appreoiated that the present invention provides a novel class of aromatic sulfideamide polymers which may be synthesi~ed from commercially available materials by a simple process. It is 10 expected that the polymers will find a wide range of appli-tions as engineering plastics because of their excellent heat resistance properties and processability.
The polymers according to the invention have a chemical structure in which phenylene and alkylene qroups are alternately bonded via an amide group and a thioether group.
The polymers are useful as materials for producing articles exhibiting improved properties such as excellent resistance to high temperatures, flame-retardant properties, resistance to solvents, good mechanical properties, etc.
Polyphenylene sulfide which is a polymeric compound comprising phenylene groups linked to each other via a thioether group is well known in the art. This polymer has such properties as good flame-retardancy, low moisture absorption, high dimensional stability, etc. However, since this type of polymer exhibits a relatively low heat distor-tion temperature (HDT) of 260C (GF 40%; i.e. where contain-ing 40% by weight of glass fibers) and a crystalline melting point of 281C, its usefulness in applications where high resistance to heat is required is inevitably limited.
Consequently there has been a demand in the art for the development of polyphenylene sulfide materials having higher crystalline melting points.
A polymer substance containing thioether, phenylene and amide groups in the macromolecular backbone, i.e. a polymer of aromatic polythioether amide, and a process for production thereof are described in Japanese Patent Public Disclosure (KOKAI) No. 60-226528. This polymer substance presents some problems in practice because it has a rather low softening point, is soluble in organic solvents such as dimethyl sulfoxide or N-methyl-2-pyrrolidone and exhibits poor resistance to chemicals. Additionally the synthesis of thiol group-containing monomers to be used in the preparation of the polymer is so expensive that production of the polymer is not feasible from the economic viewpoint.
1 31 74n7 The present invention, provides a novel aromatic sulfideamide polymer substance comprising a co~mercially available, inexpensive aliphatic moiety in the repeating units and which is improved in terms of resistance to high - 5 temperatures, resistance to solvents and mechanical properties.
The present invention also provides a process for production of such a novel polymer substance.
According to one aspect of the present invention, there is provided a novel aromatic sulfideamide polymer compound or -- compounds which comprise(s) repeating structural units represented by the following formula (I) and/or (II):
Ar~(Rl)a-C-N-R~-N-C-Ar2(R2)b-S ] (I) o Rs R6 o [ Ar3(R3)c-C-N R8~ N-C-Ar~(R~)d-S ] (II) O O
wherein Arl, Ar2, Ar3 and Ar4 each represent an aromatic ring: Rl, R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of R5 and R6 optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; and R7, R8 and R9, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms, said polymer compound or compounds having a logarithmic viscosity ln~ of 0.02 to 2.00, as determined by measuring the relative viscosity of polymer dissolved in a concentrated sulfuric acid solvent (specific gravity of 1.84) at 30C and at a polymer concentration of 0.5 g/100 ml and computing the result in accordance with the equation:
` 1317407 [ 1 1 - (relative vlscoslty) Q = n (polymer concentratlon) -According to another aspect of the present invention, there is provided a process for production of an aromatic - 2a -sulfldeamide polymer compound or compounds comprising the above defined repeating units (I) and/or (II) lin which the ratio of units ~I) to units (II) ranges from 100:0 to 0:100]: said process comprising the step of sulfidizing one or more amide group-containing dihalide compounds havlng the following general formula (III) and/or (IV) wlth a sulfidiz-ing agent in an organic polar solvent;
X-Arl(Rl)a-C-N-R7-N--C-Ar2(R2)b-Y (III) o R5 R6 0 X-Ar3(R3)c-C-N''RR9 N-lCI-Ar4(R4)d-Y (IV) O O
wherein Arl, Ar2, Ar3 and Ar4 each represent an aromatic ring; Rl, R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of Rs and R~ optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; R7, R8 and R~, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms; and X and Y, which may be the same or different, each represent a halogen.
The accompanying Figs. 1 and 2 show an IR spectrum (wave length: 400 - 4000 cm~l) and an X-ray diffraction pattern (X-ray intensity: counts/angle: 10- - 40) of the polymer obtained in Example 1, respectively.
The invention will now be described in more detail.
Examples of groups Arl, Ar2, Ar3 and Ar4 in the amide group-containing dihalide compounds which may be used in the invention include:
~ ~ . ~ and ~ Z ~
where Z represents -0-, -S-, -S02-, -CO-, -CH2- or -C(CH3 )2-- The groups may be the same or different in one compound.
~ --4--Examples of particularly preferred dihalide compounds (III) and (IV) for use ln the present invention include:
Cl ~ C-N-CH2-N-C ~ Cl.
O H H O
5Cl ~ C-IN-C2H4-N-C ~ Cl, Cl ~ C-N-C2H4-N-ICl ~ Cl' O H H O
Cl ~ C-N-C2H4-N - C ~ Cl, Cl ~ C-N-CH-CH2-N-C ~ Cl, OH
15Cl ~ C-N-CH2-CH-CH2-N-IC ~ Cl, O H H o Cl- ~ C-N-t-CH2)4 Nl-C ~ Cl, 20Cl ~ ~ CH2)6 1 ~C, ~ Cl, Cl~ lC~ -Nl ( CH2 ) 6 ~N- IC~ ~2Cl ~
Cl ~ ICI-N ~ CH2)6 Nl-lCl ~ Cl, CHa H O
25Cl ~ C-N-t--CH2) N-C ~ Cl, O H ~ O
Cl- ~ C-N-t-CH2)12 IN- lCI ~ Cl, O H ~ H O
Cl- ~ C-IN-CH2 ~ CH2-N-C ~ Cl, O H H O
Cl ~ C-N-CH2 ~ CH2-N-C ~ Cl, O H H O
(cis or trans) Cl ~ g-N-CH2- ~ CH2-N-C ~ Cl, (cis or trans) Cl ~ C-N-CH2 ~ N-C ~ Cl, O H ~ O
(cis or trans) Cl ~ C-N ~ N-C ~ Cl, (cis or trans) Cl ~ C-N ~ N-C ~ Cl, O H H O
Cl ~ C-N N-C ~ Cl and Cl~~ ~Cl-O O
It is preferred that the amide group-containing dihalide compounds contain bonds at the Para positions if it is mainly desired to improve the thermal resistance prop-erties of the product polymers. On the other hand, if it is desired to improve the solubility and molding properties of the sulfideamide polymer products, the dihalide compounds may contain bonds at the metha positions and/or at the ortho positions, or may be branched.
The amide group-containing dihalide compounds may be synthesized by the conventional amide linkage formation technique. A typical example of synthesis is a process in which a corresponding halogen-containing aromatic carbonyl chloride is reacted with a corresponding aliphatic diamine.
The organic polar solvents used in the process of the present invention are preferably aprotic ones and ones which are stable in the presence of alkalis at elevated tempera-tures. Examples of the preferred solvents include N,N-dimethyl acetamide ~DJ~), N-ethyl-2-pyrrolidone, hexamethyl phosphoric triamide (HMPA), dimethyl sulfoxide (DMSO), N-methyl-2-pyrrolidone (l~MP), 1,3-dimethyl imidazolidinone.
The sulfidizing agents which may be used in the process include alkali metal sulfides, combinations of hydrogen sulfide with alkali metal bases, and combinations of alkali metal hydrosulfides with alkali metal basis.
The alkali metal sulfides and hydrosulfides may be used as hydrates (from 0.5 to lO molar equivalents). The sulfldizlng agents may be prepared in situ prior to introductlon of the dihalide compound of the general formula (III) and/or (IV) into the reaction system. Of course, the sulfidizing agent may be prepared outside the reaction system and then introduced to the system. It ls preferred that, before the sulfidizing agent is introduced for commencement of the polymerization in the reaction system, the content of water in the system should be reduced to a level of less than 2.5 molar equivalents per equivalent of the sulfidizing agent to be introduced.
Among the available sulfidizing agents, sodium sulfide, sodium hydrosulfide in con~unction with sodium hydroxide, and hydrogen sulfide in con~unction with sodium hydroxide are preferred.
In the polymerization, a phase transfer catalyst such as a crown-ether compound, phosphor salt or an ammonium salt compound as well as an assistant such as an alkali metal carboxylate may be used to effectively increase the molecu-lar weight of the resulting polymer.
The polymerization is effected at a temperature of about 150 - 300C, preferably 180 - 280C, for a period of about 0.5 - 24 hours, preferably 1 - 12 hours.
The preferred molar ratio of the dihalide compound (III) and/or (IV) to the sulfidizing agent used in the present process ranges from 0.9:1.0 to 1.1:1Ø
The quantity of solvent used in the process may be such that the reaction system will contain 7 - 50%, prefer-ably 10 - 40%, by weight of the product polymer upon completion of the polymerization.
The product polymer may be recovered by conventional methods, such as vacuum distillation, flash-off, and re-precipitation with organic solvents or water. The isolated product polymer may be washed with any suitable organic solvent or water and then dried.
Generally, the aromatic sulfideamide polymers according to the present invention have a logarithmic viscosity in the range of 0.02 to 2.00, as measured at a concentration of 0.5 g/100 ml in concentrated sulfuric acid . --7--at a temperature of 30C. Polymers having viscosities of 0.05 to 2.00 are preferred.
The aromatic polysulfideamide polymers of the invention may be advantageously chain-extended and/or cross-linked and/or branched by heating in an oxidative atmos-phere, such as air or oxygen-enriched alr.
Where the polymers are molded or otherwise shaped, they may contain various filler materials. Examples of suitable filler materials include (a) fiber fillers, such as glass fibers, carbon fibers, boron fibers, aramid fibers, alumina fibers, etc. and (b) inorganic fillers, such as mica, talc, clay, graphite, carbon black, silica, asbestos, molybdenum disulfide, magnesium oxide, calcium oxide, etc.
As shown in the following Examples, the polymers of the present invention exhibit, on IR analysis, absorptions around 1090 cm~l (caused by thioether linkages), around 1640 cm~' (caused by carbonyl groups in amide linkages) and around 3320 cm~l and 1540 cm~l (both caused by amino groups in amide linkages). These IR data confirm that the present polymers have the structural repeating units (I) and/or (II).
The invention is illustrated in detail but not limited by the following Examples.
Since most of the polymers according to the invention are only soluble in some special solvents such as concen-trated sulfuric acid or an N-methyl-2-pyrrolidone/lithium chloride (95/S by weight) mixture, and are only sparingly soluble or insoluble in common organic solvents, it is not readily possible to determine the average molecular weight of the present pol~ers by a conventional method. Hence, the logarithmic viscosity value [n ] of a polymer is herein employed as a measure of the molecular weight of that polymer. The logarithmic viscosity value [~] is obtained by measuring the relative viscosity of polymer dissolved in a concentrated sulfuric acid solvent at 30~C and at a polymer concentration of 0.5 g/100 ml and calculating the result in accordance with the equation:
-8- ' 1317407 - 1 trelative viscosity) [n ~ - n (polymer concentration) ExamPle A 500 ml autoclave was charged with Na2S-2.7H20 (0.04 moles) and N-methyl-2-pyrrolidone (NlVlP) 150 ml and 5 heated to a temperature of 200 C with stlrring so as to dehydrate the mixture. By this dehydration, 1.26 g of water containing 4.31% of NMP was distilled off. After cooling the reaction system down to 100 C, a dichloride Cl~ g-Nff~H2) N-C~Cl (0.04 moles) was added together with an additional S0 ml of NMP. The system was shielded and heated to 250C. At this temperature, the polymerization was allowed to proceed for 6 hours.
At the end of the polymerization period, the system was cooled and methanol was added to precipitate out the product polymer. The mixture was filtered. The filter cake was repeatedly washed with warm water and filtered and then washed with methanol and dried to give a light gray powdery 20 polymer product (10 g; corresponding to a yield of 70.6%).
The polymer had a logarithmic viscosity of 0.16 (as measured in H2 S04 at a concentration of 0.5 g/100 ml at 30-C). The polymer as such was not melt-moldable, but was soluble in, for example, concentrated sulfuric acid or 25 NMP/LiCl mixture (such a solution could be used in casting to give a film).
The infra-red absorption spectrum of the polymer showed absorptions at 1090 cm~' (thioether linkage) and 3350, 1640 and 1544 cm~l (amide linkage, respectively) (see 30 Fig. 1).
Results of the elemental analysis are listed below:
Found (wt%): C 66.9, H 5.8, N 7.7, S 8.6 Theoretical (wt%): C 67.8, H 6.2, N 7.9, S 9.0 X-ray diffraction confirmed that the product sulfide-35 amide polymer was crystalline in nature (see Fig. 2).
The polymer showed a decomposition temperature of425C but did not show a definite melting point.
ExamPles ~ - 7 The apparatus and procedure of Example 1 was used to polymerize various dihalide compounds. The polymers obtained in all the cases were crystalline.
ExamPle 2 The following dihalide compound was employed:
Cl ~ C-IN ( CH2t--Nl-C ~ Cl Yield: 11.4 g (87.3%) Logarithmic viscosity: 0.11 (measured with a 0.5 g/100 ml solution in H2 S04 at 30C) IR: 1090 cm~' (thioether linkage), 3320; 1617; 1541 cm~
(amide linkage) Elemental analysis:
Found (wt%): C 65.5, H 5.4, N 8.3, S 8.8 Theoretical (wt%): C 66.2, H 5.5, N 8.6, S 9.8 Decomposition temperature: 413-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, NMP, etc.
ExamPle 3 The following dihalide compound was employed:
Cl ~ ICl-lN ( CH2 ~ ~-ICI ~ Cl Yield: 9.7 g (81.3%) Logarithmic viscosity: 0.08 (measured with a 0.5 g/100 ml solution in H2S04 at 30C) IR: 1070 cm~' (thioether linkage), 3320; 1642; 1552 cm~
(amide linkage) Elemental analysis:
Found (wt%): C 64.0, H 4.6, N 9.2, S 8.9 Theoretical (wt%): C 64.4, H 4.7, N 9.4, S 10.7 Decomposition temperature: 351C
(with no definite melting point) -lo- 1 31 7407 Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, etc.
ExamPle 4 The following dihalide compound was employed:
Cl ~ C-N N-C- ~ Cl Yield: 10.4 g (80.1%) Logarithmic viscosity: 0.10 (measured with a 0.5 g/100 ml solution in H2S04 at 30~C) IR: 1075 cm~l (thioether linkage), 1642 cm~~ (carbonyl group) Elemental analysis:
Found (wt%): C 65.0, H 4.9, N 8.5, S 8.1 Theoretical (wt%): C 66.7, H 5.0, N 8.6, S 9.9 Decomposition temperature: 432-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, etc.
ExamDle 5 The following dihalide compound was employed:
Cl ~ ICI-IN-CH2 ~ CH2-NI-lCl ~ Cl Yield: 14.6 g (97.9%) Logarithmic viscosity: 0.09 (measured with a 0.5 g/100 ml solution in H2S0~ at 30C) IR: 1090 cm~1 (thioether linkage), 3320; 1642; 1542 cm~' (amide linkage) Elemental analysis:
Found (wt%): C 68.9, H 4.8, N 7.3, S 7.7 Theoretical (wt%): C 70.1, H 4.8, N 7.5, S 8.5 5 Decomposition temperature: 384-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, DMS0, etc.
Example 6 The following dihalide compound was employed:
Cl ~ IC-lN-CH2 ~ CH2-Nt-~C~ ~ Cl Yield: 14.9 g (99.0~) Logarithmic viscosity: 0.09 (measured with a 0.5 g/100 ml solution in H2S04 at 30~C) IR: 1080 cm~l (thioetner linkage), 3300; 1640; 1542 cm~
(amide linkage) Elemental analysis:
Found (wt%): C 69.6, H 4.7, N 7.3, S 8.0 Theoretical (wt%): C 70.1, H 4.8, N 7.5, S 8.5 15 Decomposition temperature: 387-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, NMP, DMS0, DMA, etc.
Insoluble in methanol, m-cresol, pyridine, etc.
Exam~le 7 The following dihalide compounds were employed in admixture:
Cl ~ tCI-Nt-t-CH2) 6 Nl-IC ~ Cl (0.02 moles) and Cl ~ C-N N-C ~ Cl O O
(0.02 moles) 30 Yield:11.2 g ~82.3%) Logarithmic viscosity: 0.11 (measured with a 0.5 g/100 ml solution in H2S04 at 30~C) IR: 1080 cm~~ (thioether linkage), 3350; 1642; 1545 cm~' (amide linkage) Elemental analysis:
Found (wt%): C 66.9, H 5.5, N 8.3, S 9.1 Theoretical (wt%): C 67.2, H 5.6, N 8.3, S 9.5 1 31 74~7 Decomposi~ion temperature: 427-C
(with no definite melting point) Soluble in concentrated sulfuric acid, NMP/LiCl mixture, etc.
Insoluble in methanol, DMF, etc.
From the above description, it will be appreoiated that the present invention provides a novel class of aromatic sulfideamide polymers which may be synthesi~ed from commercially available materials by a simple process. It is 10 expected that the polymers will find a wide range of appli-tions as engineering plastics because of their excellent heat resistance properties and processability.
Claims (20)
1. A novel aromatic sulfideamide polymer compound or compounds which comprise(s) repeating structural units represented by the following formula (I) and/or (II):
(I) ( II) wherein Ar1, Ar2, Ar3 and Ar4 each represent an aromatic ring; R1,R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of R5 and R6 optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; and R7, R8 and R9, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms, said polymer compound or compounds having a logarithmic viscosity ? of 0.02 to 2.00, as determined by measuring the relative viscosity of polymer dissolved in a concentrated sulfuric acid solvent at 30 C
and at a polymer concentration of 0.5 g/100 ml and computing the result in accordance with the equation:
? = ln-
(I) ( II) wherein Ar1, Ar2, Ar3 and Ar4 each represent an aromatic ring; R1,R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of R5 and R6 optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; and R7, R8 and R9, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms, said polymer compound or compounds having a logarithmic viscosity ? of 0.02 to 2.00, as determined by measuring the relative viscosity of polymer dissolved in a concentrated sulfuric acid solvent at 30 C
and at a polymer concentration of 0.5 g/100 ml and computing the result in accordance with the equation:
? = ln-
2. A polymer compound or compounds as claimed in Claim 1 in which groups Ar1, Ar2, Ar3 and Ar4 are each selected from , or where Z represents -0-, -S-, -S02-, -C0-, -CH2- or -C(CH3)2-.
3. A polymer compound or compounds as claimed in Claim 1 in which the logarithmic viscosity is in the range of 0.05 to 2.00.
4. A polymer compound or compounds as claimed in Claim 1 which is heated under an oxidative atmosphere in a controlled manner so as to cause chain extension and/or cross-linking and/or branching and/or any other structural change to occur to an intended or predetermined extent.
5. A process for production of an aromatic polymer compound or compounds comprising repeating units represented by the following formula (I) and/or (II):
(I) ( II) said process comprising the step of sulfidizing one or more amide group-containing dihalide compounds having the follow-lowing general formula (III) and/or (IV) with a sulfidizing agent in an organic polar solvent:
(III) ( IV) wherein Ar1, Ar2, Ar3 and Ar4 each represent an aromatic ring; R1, R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of R5 and R6 optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; R7, R8 and R9, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms; and X and Y, which may be the same or different, each represent a halogen.
(I) ( II) said process comprising the step of sulfidizing one or more amide group-containing dihalide compounds having the follow-lowing general formula (III) and/or (IV) with a sulfidizing agent in an organic polar solvent:
(III) ( IV) wherein Ar1, Ar2, Ar3 and Ar4 each represent an aromatic ring; R1, R2, R3, R4, R5 and R6, which may be the same or different, each represent an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an acyl group having 2 to 20 carbon atoms or an arylalkyl group having 7 to 20 carbon atoms, each of R5 and R6 optionally being hydrogen; a, b, c and d, which may be the same or different, each represent an integer of from 0 to 4; R7, R8 and R9, which may be the same or different, each represent an alkylene group having 1 to 20 carbon atoms; and X and Y, which may be the same or different, each represent a halogen.
6. A process as claimed in Claim 5 in which groups Ar1, Ar2, Ar3 and Ar4 are each selected from . . or where Z represents -O-, -S-, -S02-, -CO-, -CH2- or -C(CH3)2-.
7. A process as claimed in Claim 5 in which the amide group-containing dihalide compound employed is selected from the group consisting of:
(cis or trans) (cis or trans) (cis or trans) ?~ cis or trans) , and mixtures thereof.
(cis or trans) (cis or trans) (cis or trans) ?~ cis or trans) , and mixtures thereof.
8. A process as claimed in Claim 5 in which the organic solvent is aprotic.
9. A process as claimed in Claim 8 in which the solvent is selected from the group consisting of N,N-dimethyl acetamide, N-ethyl-2-pyrrolidone, hexamethyl phosphoric triamide, dimethyl-sulfoxide, N-methyl-2-pyrrolidone, and 1,3-dimethyl imidazoline.
10. A process as claimed in Claim 5 in which the sulfidizing agent is selected from the group consisting of sodium sulfide, a combination of sodium hydrosulfide and sodium hydroxide, and a combination of hydrogen sulfide and sodium hydroxide.
11. A process as claimed in Claim 5 in which a phase transfer catalyst and/or an assistant is present in the reaction mixture.
12. A process as claimed in Claim 11 in which the phase transfer catslyst is selected from the group consisting of crown ether compounds, phosphor salt and ammonium salt compounds.
13. A process as claimed in Claim 11 in which the assistant is an alkali metal carboxylate.
14. A process as claimed in Claim 5 in which the polymerization is effected at a temperature of about 150 -300 C for a period of about 0.5 - 24 hours.
15. A process as claimed in Claim 14, wherein the temperature is from 180 to 280 C, and the period is from one to 12 hours.
16. A process as claimed in Claim 5 in which the molar ratio of the dihalide compound of formula (III) and/or (IV) to the sulfidizing agent is in the range of from about 0.9:1.0 to about 1.1:1Ø
17. A process as claimed in Claim 5 in which the solvent is employed in such an amount that the reaction mixture will contain the product polymer in a proportion of about 7 - 50% by weight, preferably 10 - 40% by weight, after the polymerization reaction.
18. A process as claimed in Claim 5 which further comprises a step of recovering the product polymer.
19. A process as claimed in Claim 18 which further comprises a step of thermally treating the recovered product polymer in an oxidative atmosphere so as to structurally modify the polymer and hence to improve the physical and chemical properties.
20. A composition comprising an aromatic polymer as claimed in Claim 1 or produced by the process claimed in Claim 5 and one or more conventional additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP325277/1987 | 1987-12-24 | ||
| JP62325277A JPH0784524B2 (en) | 1987-12-24 | 1987-12-24 | Method for producing aromatic sulfide amide polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1317407C true CA1317407C (en) | 1993-05-04 |
Family
ID=18175015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000586908A Expired - Fee Related CA1317407C (en) | 1987-12-24 | 1988-12-22 | Aromatic sulfideamide polymer and method for producing the same |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4981947A (en) |
| EP (1) | EP0323176B1 (en) |
| JP (1) | JPH0784524B2 (en) |
| KR (1) | KR890010033A (en) |
| CA (1) | CA1317407C (en) |
| DE (1) | DE3888658T2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6951572B1 (en) * | 1997-02-20 | 2005-10-04 | Endologix, Inc. | Bifurcated vascular graft and method and apparatus for deploying same |
| US8034100B2 (en) * | 1999-03-11 | 2011-10-11 | Endologix, Inc. | Graft deployment system |
| US6261316B1 (en) | 1999-03-11 | 2001-07-17 | Endologix, Inc. | Single puncture bifurcation graft deployment system |
| JP4196673B2 (en) * | 2000-11-15 | 2008-12-17 | エンドロジックス、インク | Tubular wire support |
| US20080071343A1 (en) * | 2006-09-15 | 2008-03-20 | Kevin John Mayberry | Multi-segmented graft deployment system |
| US8523931B2 (en) * | 2007-01-12 | 2013-09-03 | Endologix, Inc. | Dual concentric guidewire and methods of bifurcated graft deployment |
| WO2009055615A1 (en) * | 2007-10-23 | 2009-04-30 | Endologix, Inc. | Stent |
| WO2009105699A1 (en) | 2008-02-22 | 2009-08-27 | Endologix, Inc. | Design and method of placement of a graft or graft system |
| US8236040B2 (en) * | 2008-04-11 | 2012-08-07 | Endologix, Inc. | Bifurcated graft deployment systems and methods |
| EP2293838B1 (en) | 2008-07-01 | 2012-08-08 | Endologix, Inc. | Catheter system |
| EP2429452B1 (en) | 2009-04-28 | 2020-01-15 | Endologix, Inc. | Endoluminal prosthesis system |
| EP2424447A2 (en) * | 2009-05-01 | 2012-03-07 | Endologix, Inc. | Percutaneous method and device to treat dissections |
| US10772717B2 (en) | 2009-05-01 | 2020-09-15 | Endologix, Inc. | Percutaneous method and device to treat dissections |
| US8491646B2 (en) | 2009-07-15 | 2013-07-23 | Endologix, Inc. | Stent graft |
| JP5588511B2 (en) | 2009-07-27 | 2014-09-10 | エンドロジックス、インク | Stent graft |
| CN101921396B (en) * | 2010-07-29 | 2012-03-21 | 四川大学 | Semi-aryl poly (phenylene sulfide amide) and preparation method thereof |
| EP2635241B1 (en) | 2010-11-02 | 2019-02-20 | Endologix, Inc. | Apparatus for placement of a graft or graft system |
| US9393100B2 (en) | 2010-11-17 | 2016-07-19 | Endologix, Inc. | Devices and methods to treat vascular dissections |
| WO2012118901A1 (en) | 2011-03-01 | 2012-09-07 | Endologix, Inc. | Catheter system and methods of using same |
| WO2017004265A1 (en) | 2015-06-30 | 2017-01-05 | Endologix, Inc. | Locking assembly for coupling guidewire to delivery system |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60226528A (en) * | 1984-04-25 | 1985-11-11 | Mitsubishi Petrochem Co Ltd | Aromatic polythioether amide polymer and its production |
| JPH0689133B2 (en) * | 1985-05-08 | 1994-11-09 | 三菱化成株式会社 | Method for producing polyester, polyesteramide and polyamide |
| JPH0689134B2 (en) * | 1985-05-09 | 1994-11-09 | 三菱化成株式会社 | Method for producing polyester, polyesteramide and polyamide |
| JPS6383135A (en) * | 1986-09-26 | 1988-04-13 | Tosoh Corp | Aromatic sulfideamide polymer and its production |
-
1987
- 1987-12-24 JP JP62325277A patent/JPH0784524B2/en not_active Expired - Fee Related
-
1988
- 1988-12-21 KR KR1019880017107A patent/KR890010033A/en not_active Application Discontinuation
- 1988-12-22 US US07/288,342 patent/US4981947A/en not_active Expired - Fee Related
- 1988-12-22 DE DE3888658T patent/DE3888658T2/en not_active Expired - Fee Related
- 1988-12-22 CA CA000586908A patent/CA1317407C/en not_active Expired - Fee Related
- 1988-12-22 EP EP88312269A patent/EP0323176B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3888658D1 (en) | 1994-04-28 |
| JPH01167333A (en) | 1989-07-03 |
| DE3888658T2 (en) | 1994-10-20 |
| EP0323176A3 (en) | 1990-06-13 |
| EP0323176A2 (en) | 1989-07-05 |
| JPH0784524B2 (en) | 1995-09-13 |
| US4981947A (en) | 1991-01-01 |
| EP0323176B1 (en) | 1994-03-23 |
| KR890010033A (en) | 1989-08-05 |
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