GB1565577A - Creation of Inventions and Patents with Artificial Intelligence

GB1565577A – Method for making polyeherimides
– Google Patents

GB1565577A – Method for making polyeherimides
– Google Patents
Method for making polyeherimides

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Publication number
GB1565577A

GB1565577A
GB15093/77A
GB1509377A
GB1565577A
GB 1565577 A
GB1565577 A
GB 1565577A
GB 15093/77 A
GB15093/77 A
GB 15093/77A
GB 1509377 A
GB1509377 A
GB 1509377A
GB 1565577 A
GB1565577 A
GB 1565577A
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GB
United Kingdom
Prior art keywords
radical
formula
bis
sodium chloride
polyetherimide
Prior art date
1976-04-16
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

Application number
GB15093/77A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

General Electric Co

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General Electric Co
Priority date (The priority date 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 date listed.)
1976-04-16
Filing date
1977-04-12
Publication date
1980-04-23

1977-04-12
Application filed by General Electric Co
filed
Critical
General Electric Co

1980-04-23
Publication of GB1565577A
publication
Critical
patent/GB1565577A/en

Status
Expired
legal-status
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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

C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 – C08G71/00

C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain

C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety

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

C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

C08G73/1003—Preparatory processes

C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines

C08G73/1021—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the catalyst used

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

C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain

C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon

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

C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule

C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain

C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur

Description

PATENT SPECIFICATION (“) 1 565 577
t ( 21) Application No 15093/77 ( 22) Filed 12 April 1977 k ( 31) Convention Application No 677773 1 l ( 32) Filed 16 April 1976 in l ( 33) United States of America (US)
( 44) Complete Specification published 23 April 1980
4 M ( 51) INT CL 3 C 08 G 73/06 ( 52) Index at acceptance C 3 R 7 N 5 A 7 PX ( 72) Inventors FRANK JARVIS WILLIAMS III and HOWARD JOHN KLOPFER ( 54) METHOD FOR MAKING POLYETHERIMIDES ( 71) We, GENERAL ELECTRIC COMPANY, a corporation organized and existing under the laws of the State of New York, United States of America, of 1 River Road, Schenectady 12305, State of New York, United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and 5 by the following statement:-
The present invention relates to a method for making polyetherimides by effecting reaction between an aromatic bis (ether anhydride) and an organic diamine under melt polymerization conditions More particularly, the present invention relates to the use of catalytic amounts of sodium chloride or ferric sulfate to enhance the rate of 10 formation of polyetherimides.
In U S Patent Specification No 3,803,085 there is described a method for making polyetherimides by melt polymerizing a mixture of certain aromatic bis(ether anhydrides) and organic diamines For example, an aromatic bis(ether anhydride) of the formula 15 o o oc c II fl o O and organic diamine of the formula ( 2) HNR 1 NH, is melt polymerized at temperatures up to 350 C, where R is a divalent aromatic organic radical having from 6-30 carbon atoms, R’ is a divalent organic radical and 20 is as defined by R, an alkylene radical having from 2-20 carbon atoms, a cycloalkylene radical, or a C( 28) alkylene terminated polydiorganosiloxane radical.
Radicals included by R are, for example, aromatic hydrocarbon radicals and halogenated aromatic hydrocarbon radicals, for example, phenylene, tolylene, chlorophenylene, and naphthalene, and radicals included by the formula 25 -R 92-(Q) 7-R 2 _where R 2 is a divalent aromatic radical having from 6-13 carbon atoms, a hydrocarbon radical or a halogenated hydrocarbon radical, and Q is a divalent organo radical of the formula O O R ii ji -Cy H 2,y-, -C, -S-, -S-, -0 O or -Si 30 O 11 1 O R where a is 0 or 1, y is an integer having a value of from 1-5 inclusive, and R’ is a monovalent hydrocarbon radical, which is for example methyl or phenyl.
Radicals included by RI are, for example, t-Qo Q O -CH 2 & cv -KD 2 (o Jj H 3 i:2 e H 3 alkylene radicals for example hexamethylene, and cyclohexylene and R 3 3 (CH 2)n 51 i lOS i 0fi 3 i where R is as defined above, m is equal to 6 to 100 inclusive and N is 28 inclusive.
The above described melt polymerization method is a valuable procedure for making a variety of polyetherimides Methods are constantly being sought, however, for accelerating the rate of melt polymerization of the mixture of aromatic bis(ether anhydride) and organic diamine while maintaining the valuable injection molding 10 characteristics of the resulting polyetherimide.
The present invention is based on the discovery that catalytic amounts of either sodium chloride, or ferric sulfate, can be used in a melt polymerization mixture of the aromatic bis(ether anhydride) of formula ( 1) and organic diamine of formula ( 2) to enhance substantially the rate of polyetherimide formation from the resulting melt 15 polymerization mixture without substantially imparing desirable characteristics of the resulting polyetherimide.
There is provided by the present invention a method for making polyetherimides consisting essentially of chemically combined units of the formula o o II II -crc N-R-N O-R O 20 Ic/c 0 o where R and RI are as previously defined, which comprises effecting the reaction under melt polymerization conditions between an aromatic bis(ether anhydride) of formula ( 1) and an organic diamine of formula ( 2) in the presence of a sodium chloride or a ferric sulfate catalyst.
Included by the aromatic bis(ether anhydride) of formula ( 1) which can be used 25 in the practice of the invention and, for example, 0 o c c ( 3) O-R-0 o If If o o o o O C C ( 4) O O o O-R O 1,565,577 1,565,577 3 o o O ( 5) o$ 9 c> 0 0-R-O O where R is as defined above.
Dianhydrides included by formula ( 3) are, for example, 2,2 ‘-bisl 4-( 2,3-dicarboxyphenoxy)phenyll-propane dianhydride; 4,4 ‘-bis( 2,2-dicarboxyphenoxy)diphenyl ether dianhydride; 1,3-bis( 2,3-dicarboxyphenoxy)-benzene dianhydride; 5 4,4 ‘-bis-( 2,3-dicarboxyphenoxy)-diphenyl sulfide dianhydride; 1,4-bis( 2,3-dicarboxyphenoxy)-benzene dianhydride; and 4,4 ‘-bis-( 2,3-dicarboxyphenoxy)-diphenyl sulfone dianhydride.
Dianhydrides included by formulae ( 4) and ( 5) are, for example, 2,2-hisl 4-( 3,4-dicarboxyphenoxy)-phenyll-propane dianhydride; 10 ( 3,4-dicarboxyphenoxy)-diphenyl ether dianhydride; 4,4 ‘-bis( 3,4-dicarboxyphenoxy)-diphenylsulfone dianhydride; 1,3-bis( 3,4-dicarboxyphenoxy)-benzene dianhydride; 1,4-bis( 3,4-dicarboxyphenoxy)-benzene dianhydride; 4,42-bis( 3,4-dicarboxyphenoxy)-diphenylsulfone dianhydride; and 15 4-( 2,3-dicarboxyphenoxy)-4 ‘-( 3,4-dicarboxyphenoxy)-2,2-diphenyl propane dianhydride.
Included by the organic diamines of formula ( 2) are, for example, m-phenylenediamine; p-phenylenediamine; 20 4,4 ‘-diaminodiphenylpropane; 4,4-diaminodiphenylmethane; benzidine; 4,4 ‘-diaminodiphenyl sulfide; 4,4 ‘-diaminodiphenyl sulfone; 25 4,4 ‘-diaminodiphenyl ether; 1,5-diaminonaphthalene; 3,3 ‘-dimethylbenzidine; 3,3 ‘-dimethoxybenzidine; 2,4-bis(-amino-t-butyl)toluene; 30 bis(p-,,-amino-t-butylphenyl)ether; bis(p-j-methyl-o-aminopentyl)benzene; 1,3-diamino 4-isopropylbenzene; 1,2-bis( 3-aminopropoxy)ethane; m-xylylenediamine; 35 p-xylylenediamine; 2,4-diaminotoluene; 2,6-diaminotoluene; bis( 4-aminocyclohexyl)methane; 3-methylheptamethylenediamine; 40 4,4-dimethylheptamethylenediamine; 2,11-dodecanediamine; 2,2 -dimethylpropylenediamnine; octamethylenediamine; 3-methoxyhexamethylenediamine; 2,5-dimethylhexamethylenediamine; 2,5-dimethylheptamethylenediamfine; 3-methylheptamethylenediamine; 5-methylnonamethylenediamine; 1,4-cyclohexanediamine; so 1 50 1,12-octadecanediamine; bis( 3-aminopropyl)sulfide; N-methyl-bis( 3-aminopropyl) amine; hexamethylenediamine; We make no claim to the use of benzidine in contravention of the Carcinogenic 55 Substances Regulations 1967 1,565,577 3 A heptamethylenediamine; 4 nonheptamethylenediamine; nonamethylenediamine; decamethylenediamine; bis-( 3-aminopropyl)tetramethyldisiloxane; and bis-( 4-aminobutyl)tetramethyldisiloxane 5 In the practice of the invention, the aromatic bis(ether anhydride) and the organic diamine are blended thoroughly together with the metal salt catalyst which hereinafter will signify either sodium chloride, or ferric sulfate In addition, aqueous solutions or suspensions of the catalyst can be used to insure that the catalyst is evenly distributed throughout the mixture of monomers If desired, a chain stopper, for example phthalic 10 anhydride, also can be used.
The blend can be heated to a temperature of from 200 C to 400 C in a suitable agitator under an inert atmosphere to effect the formation of polyetherimide under melt polymerizing conditions A nitrogen atmosphere can be employed Suitable reactors for a batch process include, for example a Helicon mixer or a Brabender mixer, 15 while extruders can be used for a continuous process.
It has been found that if sodium chloride is used at a level of, for example, from 0.1 to 0 5 % of the total weight of monomer used, or that ferric sulfate is used at a level of, for example, from 0 01 to 0 05 %, based on total monomer weight, that the rate of polyetherimide formation is from two to four times faster than if no catalyst is 20 used This rate enhancement is seen in both continuous and batch melt polymerizations The properties of the polyetherimides from the catalyzed reaction are substantially equal to those of polyetherimides prepared in uncatalyzed reactions.
Substantially equal molar amounts of aromatic bis(ether anhydride) and organic diamine can be used Chain-stoppers, for example, phthalic anhydride, can be used, 25 for example from 1 mole percent to 5 mole percent, based on the total moles of aromatic bis(ether anhydride) used in the melt polymerization mixture.
In order that those skilled in the art will be better able to practice the invention, the following examples are given by way of illustration and not by way of limitation.
All parts are by weight 30 Example 1
A mixture of 81 19 parts of 2,2-bisl 4-( 2,3-dicarboxyphenoxy)pheny Il propane dianhydride (BPA-dianhydride), 17 38 parts of metaphenylene diamine and 1 43 part of phthalic anhydride was added to an argon-blanketed Helicone mixer bowl The mixture was converted to a melt at 500 F The mixture was heated for a period of up 35 to 60 minutes and samples were removed at 5 minute intervals starting after 10 minutes to determine the change, if any, of the I V in chloroform (CH Cl,) In addition, GPC scans were obtained at the 30 minute and 40 minute interval points to determine the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) 40 The above procedure was repeated except that there was employed 01 part of sodium chloride as a solution in 1 5 part of water which was added to the mixture prior to converting the mixture to a melt as described above Again the intrinsic viscosity of the mixture was measured periodically.
Another melt polymerization was effected following the same procedure as above 45 except that there was employed in the mixture prior to melt polymerization 0 025 to 0.5 part of sodium chloride in an aqueous solution.
The change in intrinsic viscosities “IV” over a period up to 60 minutes is shown below in Table I, where % Gel was determined in the polymer at the termination of the reaction by a procedure defined below 50 TABLE I
Sodium Chloride (WT%) Change in I V Over Time (Minutes) % Gel 10 15 20 25 35 40 45 55 60 55 0 31 35 40 44 49 0 0.01 45 46 46 45 45 47 45 0.025 44 43 44:41 43 43 47 0 5 0.05 46 46 44 43 45 44 44 0 1 41 46 46 48 0 60 0.5 42 45 46 45 47 1 6 Percent Gel in the polyetherimide was determined by heating 250 mg samples in a circulating air oven for 3 hours at 300 C The samples were then weighed and 1,565,577 1,565,577 5 placed in refluxing chloroform for 16 hours The weight percent gel was then determined by weighing the residue It also was found that although enhancement in polymerization rates in terms of I V over time was experienced with other sodium salts, for example sodium fluoride, sodium bromide, at equivalent weight percents, the increase in weight percent gel, such as 12 % with sodium fluoride, eliminated such 5 salts as potential catalysts Although sodium sulfate did not result in excess gel formation, it failed to show any significant rate enhancement.
Example 2
The above procedure was repeated, except that in place of sodium chloride there was used an aqueous suspension of ferric sulfate over a weight range of 01 %, 025 % 10 and 0 05 %, based on the weight of melt polymerization ingredients As described in Example 1, the change in intrinsic viscosity and Gel % was measured over a period of minutes, 15 minutes, 20 minutes, 25 minutes, etc The results of the melt polymerization is shown below in Table II:
TABLE II 15
Ferric Sulfate (WT%) Change in I V Over Time (Minutes) % Gel 15 20 25 30 35 40 45 60 0 33 43 46 48 20 0.01 27 33 36 37 41 0 0.025 32 41 45 46 48 0 7 39 43 47 48 3 Example 3
A mixture of substantially equal molar amounts of 2,2-bisl 4-( 2,3dicarboxyphen 25 oxy)phenyllpropane dianhydride and meta phenylene diamine and 2 5 mole percent of phthalic anhydride, based on the total moles of reactants in the mixture, were charged to a Werner Pfleiderer ZDS-K 28 twin screw extruder After the mixture had been thoroughly blended, the mixture was continuously extruded at 350 C There was obtained a polyetherimide having an intrinic viscosity of about 0 44 with 9 % by 30 weight of ge L The above procedure was repeated, except that there was utilized 0 1 % by weight of sodium chloride in the mixture which was incorporated by means of an aqueous solution of the salt Following the same conditions as previously described for the mixture free of sodium chloride, there was obtained a polyetherimide having 35 an intrinsic viscosity of 0 55 with 4 2 % by weight gel.
The above results demonstrate that, by using a metal salt catalyst in accordance with the method of the present invention under continuous polymerization conditions, higher molecular weight polyetherimide can be made in less time than if the polymerization is conducted in the absence of such catalyst 40 Although the above examples are limited to only a few of the very many variables which can be employed in the practice of the method of the present invention, it should be understood that the method of the present invention is broadly directed to making polyetherimide by a melt polymerization technique utilizing aromatic bis(ether anhydride) of formula ( 1) and organic diamine of formula ( 2) under melt 45 polymerization conditions in the presence of a metal salt catalyst as previously defined.

Claims (8)

WHAT WE CLAIM IS:-

1 A method for making polyetherimides consisting essentially of chemically combined units of the formula o O I l I c c N-R-No O O-R-0 50 cjc 0 o C) where R is a divalent aromatic organic radical having from 6-30 carbon atoms, R’ is a divalent organic radical and is as defined by R, an alkylene radical having from 2-20 carbon atoms, a cycloalkylene radical, or a C( 2,) alkylene terminated polydiorganosiloxane radical, which comprises effecting the reaction under melt polymerization conditions between an aromatic bis(ether anhydride) of the formula:
o o tl fl c c N 0 O -R O O fl II 0 o O and an organic diamine of the formula W H NR 1 i NHR 5 in the presence of a sodium chloride or a ferric sulfate catalyst.

2 A method in accordance with claim 1, where the aromatic bis(ether anhydride) is 2,2-bisl 4-( 2,3-dicarboxyphenoxy)phenyllpropane dianhydride.

3 A method as claimed in claim 1 or claim 2, where the organic diamine is meta phenylene diamine 10

4 A method as claimed in any one of the preceding claims, utilizing a phthalic anhydride as a chain stopper.

A method as claimed in any one of the preceding claims, where the metal salt is sodium chloride.

6 A method as claimed in any one of claims 1 to 4 where the metal salt is ferric 15 sulfate.

7 A method as claimed in any one of the preceding claims where the reaction is effected in a continuous manner in an extruder.

8 A method as claimed in claim 1, for making a polyetherimide substantially as hereinbefore described in any one of the Examples 20 9 A polyetherimide when produced by a method as claimed in any one of the preceding claims.
P M TURNER, Agent for the Applicants, Chartered Patent Agent, European Patent Attorney, 9, Staple Inn, London, WC 1 V 7 QM.
Printed for Her Majesty’s Stationery Office, by the Courier Press, Leamington Spa 1980 Published by The Patent Office, 25 Southampton Buildings, London, WC 2 A l AY, from which copies may be obtained.
1,565,577

GB15093/77A
1976-04-16
1977-04-12
Method for making polyeherimides

Expired

GB1565577A
(en)

Applications Claiming Priority (1)

Application Number
Priority Date
Filing Date
Title

US05/677,773

US3998840A
(en)

1976-04-16
1976-04-16
Method for making polyetherimides using a sodium chloride or ferric sulfate catalyst

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GB1565577A
true

GB1565577A
(en)

1980-04-23

Family
ID=24720066
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Application Number
Title
Priority Date
Filing Date

GB15093/77A
Expired

GB1565577A
(en)

1976-04-16
1977-04-12
Method for making polyeherimides

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US
(1)

US3998840A
(en)

BE
(1)

BE853623A
(en)

DE
(1)

DE2716444A1
(en)

FR
(1)

FR2348237A1
(en)

GB
(1)

GB1565577A
(en)

NL
(1)

NL7704121A
(en)

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US4073773A
(en)

1976-12-30
1978-02-14
General Electric Company
Melt polymerization method for making polyetherimides

GB2069513B
(en)

1980-01-30
1983-07-27
Gen Electric
Copolymers of etherimides and amides

US4324883A
(en)

1980-09-19
1982-04-13
General Electric Company
Method for making polyetherimide using a phenolic or carboxylic acid catalyst

USRE31805E
(en)

1980-09-19
1985-01-15
General Electric Company
Method for making polyimides

US4324882A
(en)

1980-09-19
1982-04-13
General Electric Company
Method for making polyimides

US4330666A
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1980-09-19
1982-05-18
General Electric Company
Method for making polyetherimides

US4324885A
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1982-04-13
General Electric Company
Quaternary Group VA salt catalyzed method for making polyetherimide

US4324884A
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1982-04-13
General Electric Company
Organic amine catalyzed method for making polyetherimide

US4417044A
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1982-05-25
1983-11-22
General Electric Company
Process for making polyetherimides

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Simro AG, Meilen

Spectacle frames and parts thereof

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1986-12-31
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General Electric Company
Process for preparing polyimides

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1986-12-31
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Peters Edward N
Novel poly(imide-siloxane) block copolymers and process for their preparation

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1986-12-31
1989-06-06
General Electric Company
Process for making polyimides

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SPECIAL POLYIMIDES AS THERMOPLASTICS

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Very high heat thermoplastic polyetherimides containing aromatic structure

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AROMATIC ETHERIMIDES

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2003-08-26
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Method of separating a polymer from a solvent

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Norberto Silvi
Method of separating a polymer from a solvent

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2003-10-10
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General Electric Company
Method for preparing polyimide and polyimide prepared thereby

US9127127B2
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2012-10-03
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Sabic Global Technologies B.V.
Polyetherimide compositions, methods of manufacture, and articles formed therefrom

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Polyetherimides with improved melt stability

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Shpp Global Technologies B.V.
Polyetherimide compositions, methods of manufacture, and articles prepared therefrom

CN106279085B
(en)

2016-08-17
2018-07-10
万华化学集团股份有限公司
A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride

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US3803085A
(en)

1972-12-29
1974-04-09
Gen Electric
Method for making polyetherimides

US3948941A
(en)

1973-10-26
1976-04-06
Exxon Research And Engineering Company
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1976

1976-04-16
US
US05/677,773
patent/US3998840A/en
not_active
Expired – Lifetime

1977

1977-04-08
FR
FR7710770A
patent/FR2348237A1/en
active
Granted

1977-04-12
GB
GB15093/77A
patent/GB1565577A/en
not_active
Expired

1977-04-14
DE
DE19772716444
patent/DE2716444A1/en
not_active
Withdrawn

1977-04-14
BE
BE176742A
patent/BE853623A/en
not_active
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1977-04-14
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FR2348237B1
(en)

1983-09-30

US3998840A
(en)

1976-12-21

BE853623A
(en)

1977-08-01

DE2716444A1
(en)

1977-10-27

NL7704121A
(en)

1977-10-18

FR2348237A1
(en)

1977-11-10

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