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GB826979A - Improvements in or relating to polymeric materials - Google Patents

Improvements in or relating to polymeric materials

Info

Publication number
GB826979A
GB826979A GB25144/56A GB2514456A GB826979A GB 826979 A GB826979 A GB 826979A GB 25144/56 A GB25144/56 A GB 25144/56A GB 2514456 A GB2514456 A GB 2514456A GB 826979 A GB826979 A GB 826979A
Authority
GB
United Kingdom
Prior art keywords
cyclobutene
methyl
chloride
dicarboxylic acid
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB25144/56A
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.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and 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.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of GB826979A publication Critical patent/GB826979A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • C08G63/54Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67Unsaturated compounds having active hydrogen
    • C08G18/675Low-molecular-weight compounds
    • C08G18/676Low-molecular-weight compounds containing the unsaturation at least partially in a non-aromatic carbocyclic ring
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66Polyesters containing oxygen in the form of ether groups
    • C08G63/668Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/676Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/08Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00General processes for preparing compounds provided for in this subclass

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

The Specification describes the preparation of the following compounds containing a cyclobutene ring for use as intermediates in the manufacture of condensation polymers (see Group IV (a)): (a) 1-methyl-1-cyclobutene-2 : 3-dicarbonyl chloride is prepared from 1-methylenecyclobutene - 2 : 3 - dicarboxylic anhydride (the adduct of allene and maleic anhydride) by hydrolysing and isomerizing it with aqueous alkali and then acidifying with HCl to form the free cyclobutene dicarboxylic acid which is then treated with thionyl chloride; (b) 1-cyano-1-cyclobutene-3 : 4-dicarboxylic acid anhydride is prepared from 3-methylenecyclobutane-1 : 2-dicarboxylic acid anhydride (the adduct of allene and maleic anhydride) by treating it with ozone to convert the methylene group into the O= group, treating this compound with hydrogen cyanide and ammonia to give 3-amino-3-cyanocyclobutane-1 : 2-dicarboxylic anhydride, forming the trimethylammonium iodide salt of this compound and heating it with aqueous alkali; (c) 3-hydroxymethyl-1-carboxy-1-cyclobutene is made from 3-methylenecyclobutene-1-carbonitrile (the adduct of allene and acrylonitrile) by adding bromine to the double bond, hydrolysing with aqueous NaOH and neutralizing with HCl; (d) 1-methyl-3 : 3-dicarboethoxy-1-cyclobutene is made by adding isobutylene dibromide to diethyl malonate to form 1 - methylene - 3 : 3 - dicarboethoxycyclobutane, treating this compound with HI to give 1 - iodo - 1 - methyl - 3 : 3 - dicarboethoxycyclobutane and dehydrohalogenating the latter with triethylamine; (e) 1 : 1-di-(aminomethyl)-2-cyclobutene is made by reacting 1-bromo-3-chloropropane with dicyanomethane to form 1 : 1-dicyanocyclobutane, treating this compound with chlorine to give 2- and 3-chloro-1 : 1-dicyanocyclobutane, treating the mixture of isomers with triethylamine to give 1 : 1-dicyano-2-cyclobutene and reducing the latter with lithium aluminium hydride; (f) 3-(aminomethyl) - 1 - carbomethoxy - 1 - cyclobutene is made by the peroxide catalysed addition of hydrogen bromide to 3-methylene-1-cyclobutane-1-carbonitrile which is then reacted with ammonia to form 3-aminocyclobutane-1-carbonitrile, the free amino group of which is acetylated and the compound brominated in the position alphato the nitrile group. The resulting bromo compound is then hydrolysed with aqueous NaOH to the sodium salt of 3-(aminomethyl) - 1 - carboxy - 1 - cyclobutene which is converted to the ester by neutralization with HCl followed by esterification with methanol; (g) the N-carboanhydride of 1-amino-1-carboxy-2-cyclobutene is made by treating 1-methylene - 3 - cyclobutyltrimethylammonium iodide with ozone to convert the methylene group to the =O group and reacting the resulting compound with hydrogen cyanide and p ammonium chloride to form the 1-amino-1-cyano derivative. This compound is hydrolysed with HCl to form the hydrochloride of 1 - amino - 1 - carboxy - 3 - cyclobutyltrimethylammonium chloride, the quaternary ammonium radical of which is removed by heating with aqueous NaOH. After neutralization, the resulting 1-amino-1-carboxy-2-cyclobutene is converted to the N-carboanhydride by treatment with phosgene; (h) 1 : 2-di-(aminomethyl)-1-cyclobutene is made by treating the corresponding chloromethyl compound with ammonia. Specification 805,664 is referred to.ALSO:A cross-linkable condensation polyester, polyamide, polyurethane or polyurea has a chain structure containing recurring cyclobutene rings intralineal with the chain. Cross-linking, due to opening of the cyclobutene ring, is effected by heating the polymer at 100-325 DEG C. The cross-linking may be applied to the polymer when in the form of a shaped article, a fibre, a coating on a surface, an adhesive between lamin or as printed matter. The following polymers are exemplified:- Polyesters obtained from (a) dimethyl-1-cyclobutene-1:2-dicarboxylate and diphenylol propane, N,N-diethanol-aniline or ethylene-, triethylene-, trimethylene-, tetramethylene-, hexamethylene- or decamethylene-glycol; (b) the dimethyl ester of 3-methyl-1-cyclobutene-1:2-dicarboxylic acid, the dimethyl ester of 3:3-diethyl-1-cyclobutene-1:2-dicarboxylic acid or the dimethyl ester of 3:4-dimethyl-1-cyclobutene-1:2-dicarboxylic acid and hexamethylene glycol; (c) 1-methyl-1-cyclobutene-2:3-dicarbonyl chloride, sebacyl chloride and diphenylol propane; (d) 1-methyl-1-cyclobutene-2:3-dicarbonyl chloride and ethylene glycol; (e) 1 - methyl - 1 - cyclobutene - 2:3 - dicarbonyl chloride, terephthaloyl chloride and ethylene glycol; (f) 1-methyl-1-cyclobutene-2:3-dicarboxylic acid and ethylene glycol; (g) 1 - cyano - 1 - cyclobutene - 3:4 - dicarboxylic anhydride and ethylene glycol; (h) 1:2-di-(hydroxymethyl) - 1 - cyclobutene and malonic, succinic, maleic, adipic, suberic, terephthalic, p-phenylene diacetic or thioldibutyric acid or ester-forming derivatives thereof; (i) a hydroxyethylated 1:2-dihydroxymethyl-1-cyclobutene and adipic acid; (j) 3-hydroxymethyl-1-carboxy-1-cyclobutene. Polyamides obtained from (a) dimethyl-1-cyclobutene-1:2-dicarboxylate and ethylene-, hexamethylene-, 3 - methylhexamethylene-, decamethylene- or m-phenylene-diamine; (h) 1 - methyl - 1 - cyclobutene - 2:3 - dicarbonyl chloride, sebacyl chloride and 2-methoxymethyl-5 - methylhexamethylenediamine; (c) 1-methyl-1 - cyclobutene - 2:3 - dicarboxylic acid, 3:3-diethyl - 1 - cyclobutene - 1:2 - dicarboxylic acid or 3:4 - dimethyl - 1 - cyclobutene - 1:2 - dicarboxylic acid (or amide-forming derivatives thereof) and hexamethylene diamine; (d) 1-methyl - 3:3 - dicarboethoxy - 1 - cyclobutene and ethylene diamine; (e) 1:1-di(aminomethyl)-2-cyclobutene and adipyl chloride; (f) 3 - (aminomethyl) - 1 - carbomethoxy - 1 - cyclobutene; (g) the N-carboanhydride of 1-amino - 1 - carboxy - 2 - cyclobutene. Polyurethanes obtained from (a) 1:2-di-(hydroxymethyl) - 1 - cyclobutene and hexamethylene diisocyanate; (b) 3-methyl-2-cyclobutene-1,2-bis-methanol and hexamethylene diisocyanate; (c) 3-methyl-2-cyclobutene-1.2-bis-methanol, ethylene glycol and 3-methyl-2-cyclobutene-1,2-bismethanol; (d) a diisocyanate having a cyclobutene ring and a glycol (both unspecified). Polyureas obtained from 1:2-di-(aminomethyl) - 1 - cyclobutene and hexamethylene diisocyanate. Specification 805,664 is referred to.
GB25144/56A 1955-08-16 1956-08-16 Improvements in or relating to polymeric materials Expired GB826979A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US826979XA 1955-08-16 1955-08-16

Publications (1)

Publication Number Publication Date
GB826979A true GB826979A (en) 1960-01-27

Family

ID=22172831

Family Applications (1)

Application Number Title Priority Date Filing Date
GB25144/56A Expired GB826979A (en) 1955-08-16 1956-08-16 Improvements in or relating to polymeric materials

Country Status (1)

Country Link
GB (1) GB826979A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2267438A (en) * 1992-05-28 1993-12-08 British Tech Group Alicyclic diamine plant fungicides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2267438A (en) * 1992-05-28 1993-12-08 British Tech Group Alicyclic diamine plant fungicides
GB2267438B (en) * 1992-05-28 1995-04-19 British Tech Group Alicyclic diamine fungicides
US5464873A (en) * 1992-05-28 1995-11-07 British Technology Group Limited Alicyclic diamine fungicides
US5583261A (en) * 1992-05-28 1996-12-10 British Technology Group Ltd. Alicyclic diamine fungicides

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