GB573965A - Manufacture of new rubber-like polymeric materials - Google Patents

Manufacture of new rubber-like polymeric materials

Info

Publication number
GB573965A
GB573965A GB1211243A GB1211243A GB573965A GB 573965 A GB573965 A GB 573965A GB 1211243 A GB1211243 A GB 1211243A GB 1211243 A GB1211243 A GB 1211243A GB 573965 A GB573965 A GB 573965A
Authority
GB
United Kingdom
Prior art keywords
maleate
methyl
sodium
acids
fumarate
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
GB1211243A
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
Priority to GB1211243A priority Critical patent/GB573965A/en
Publication of GB573965A publication Critical patent/GB573965A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/26Esters of unsaturated alcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
    • C08F236/16Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen containing halogen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Polymeric materials are prepared by polymerizing a halogen-substituted 1 : 3 butadiene with an ester of a monohydric unsaturated alcohol of not more than 10 carbon atoms and an alpha-unsaturated alpha, beta-dicarboxylic acid, i.e. an acid having only two carboxyl groups which are attached to adjacent carbon atoms of which at least one is directly attached to an ethylenic double bond. The preferred starting materials are 2-chloro-1 : 3-butadiene and the diallyl or di-(beta-methylallyl) esters of maleic or fumaric acids. Also specified are the following : 2 - bromo - 1 : 3 - butadiene, 2 - iodo - 1 : 3 - butadiene, 1 - chloro-, and 2 - chloro - 3 - methyl-, 1 - methyl - 2 - chloro-, 2 : 3 - dichloro-, and 1 : 2 : 4 - trichloro - 1 : 3 - butadienes; the following esters: diallyl maleate, di(alphamethyl-ally) maleate, ditiglyl maleate, di(alpha - methyl - allyl) citraconate, di - (1 : 2 - butadiene - 4 - yl) ethyl maleate, diallyl chloro - maleate, di-propargyl bromomaleate, di - (2 : 4 - hexadiene - 6 - yl) maleate, di - (1 - butene - 4 - yl) phenyl maleate, dicinnamyl bromomaleate, dicrotyl itaconate, digeranyl ethyl maleate, diallyl glutaconate, di-(alpha-methyl allyl) fumarate, dipropargyl fumarate, di-(1 : 2-butadiene4-yl) fumarate, dicrotyl chlorofumarate, dicinnamyl mesaconate, ditiglyl propylfumarate, and di-(alpha-methyl allyl) phenyl fumarate. Other alcohols mentioned are allyl carbinol, 2 : 4-hexadiene-1-ol, ethinyl dimethyl carbinol, and styryl carbinol; other acids are, in general, the various mono- or disubstitution products of maleic and fumaric acids. The polymerization may be carried out by any of the conventional methods such as in bulk without solvents or diluents, in the presence of an inert diluent, or preferably, in emulsion. To obtain products of predominantly rubber-like properties, at least 50 per cent by weight of the total polymerizables should be haloprene. The preferred initial ester concentration is 15 to 40 per cent or, more preferably, 20 to 30 per cent. In aqueous emulsion the polymerization is preferably carried out under essentially neutral or slightly acidic conditions. It is desirable to employ emulsifying agents which function under acidic conditions, for example sodium octyl, cetyl, and oleyl sulphates, sodium isopropyl naphthalene sulphates and the potassium or ammonium salts; N-stearyl betaine, N - hydroxy propyl-C-cetyl betaine, C-cetyl betaine, organic or inorganic salts of long chain aliphatic amines such as octyl, lauryl, oleyl, stearyl amines and cetyl para-dimethyl aminobenzoate. Under alkaline conditions there may be used the sodium or potassium salts of oleic, palmitic, stearic, linoleic, linolenic, abietic (rosin) acids. Polymerization catalysts which may be added include ammonium, potassium or sodium persulphates, sodium or potassium perborates, hydrogen peroxide, acetyl peroxide, benzoyl peroxide; when an alkaline emulsion system is employed, such additions are usually necessary for example in a sodium rosinate solution. The preferred polymerization temperature is about 20 DEG to 50 DEG C. Modifying agents employed include mercaptans, for example octyl, lauryl, or xylyl mercaptans, hydrogen sulphide and thioglycollic acid, toluene sulphinic acid and sulphur dioxide. The polymeric products made from the haloprenes may be plasticised with a small amount of a thiuram sulphide, preferably a tetra-substituted thiuram disulphide such as tetra methyl-, tetra ethyl-, tetra butyl-, or dipentamethylene-thiuram disulphide and other agents described in U.S.A. Specification 2,234,215 including the thionaphthols and the substituted ammonium salts of disubstituted dithiocarbamic acids. Prior to coagulation of the copolymers it is desirable to incorporate small amounts of anti-oxidants, particularly secondary aromatic amines such as phenyl alpha or phenyl beta naphthylamine and diphenylamine. Coagulation may be carried out by addition of an aqueous solution of sodium chloride, magnesium sulphate, aluminium sulphate, by the addition of acids, bases, or alcohols or by freezing. The products may be compounded with zinc oxide, magnesium oxide and lead oxide; reinforcing or semi-reinforcing carbons blacks and sulphur may also be incorporated. Other polymerizable or non-polymerizable compounds may be present such as styrene, vinyl acetate or propionate, esters of acrylic or methacrylic acids, acrylonitrile, methacrylo nitrile, asymmetrical dichloro ethylene, vinyl chloride, and also film-forming materials such as natural or synthetic resins, drying oils, cellulose derivatives. The haloprene should comprise at least half of the total weight and the unsaturated ester should be present in greater amount than the vinyl or vinylidene compound or film-forming material. In examples: (1) chloroprene and diallyl fumarate are interpolymerized and the treated coagulant compounded with magnesium and zinc oxides and carbon black; (2) chloroprene and di(beta-methyl-allyl) fumarate are similarly polymerized; (2) chloroprene and di(beta-methyl-allyl) maleate are also interpolymerized as in example (1).
GB1211243A 1943-07-26 1943-07-26 Manufacture of new rubber-like polymeric materials Expired GB573965A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB1211243A GB573965A (en) 1943-07-26 1943-07-26 Manufacture of new rubber-like polymeric materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1211243A GB573965A (en) 1943-07-26 1943-07-26 Manufacture of new rubber-like polymeric materials

Publications (1)

Publication Number Publication Date
GB573965A true GB573965A (en) 1945-12-14

Family

ID=9998587

Family Applications (1)

Application Number Title Priority Date Filing Date
GB1211243A Expired GB573965A (en) 1943-07-26 1943-07-26 Manufacture of new rubber-like polymeric materials

Country Status (1)

Country Link
GB (1) GB573965A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022193837A1 (en) * 2021-03-15 2022-09-22 北京化工大学 Fumarate/conjugated diene copolymer type bio-based rubber, preparation method therefor, and vulcanized rubber product thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022193837A1 (en) * 2021-03-15 2022-09-22 北京化工大学 Fumarate/conjugated diene copolymer type bio-based rubber, preparation method therefor, and vulcanized rubber product thereof

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