GB820120A - Process for modifying the structure and properties of addition polymers - Google Patents

Process for modifying the structure and properties of addition polymers

Info

Publication number
GB820120A
GB820120A GB10658/56A GB1065856A GB820120A GB 820120 A GB820120 A GB 820120A GB 10658/56 A GB10658/56 A GB 10658/56A GB 1065856 A GB1065856 A GB 1065856A GB 820120 A GB820120 A GB 820120A
Authority
GB
United Kingdom
Prior art keywords
vinyl
ethers
polymer
esters
modifier
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
GB10658/56A
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 GB820120A publication Critical patent/GB820120A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12Chemical modification
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M14/00Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
    • D06M14/18Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The properties of addition polymers are changed by subjecting the polymer to ionising radiation while it is in intimate contact with at least one organic compound, which chemically bonds (as such or in the form of a polymeric structure) with the addition polymer. The modifier which may be dispersed, diffused or coated upon the polymer is preferably kept in an inert atmosphere or is enclosed by a polyethylene film, aluminium foil or other material which is impervious to air and water while it is being irradiated. Additionally it may be in contact with a compound having protective or anti-oxidant effects with respect to the polymer or the modifier or both and during the irradiation temperature is preferably kept between 0 DEG and 75 DEG C., if necessary by cooling. The process is preferably carried out in the presence of calcium tungstate, zinc sulphate, metallic lead or other radiation transfer agent capable of absorbing radiation and re-admitting it in a lower form of energy. Examples of radiation dosages are given. Organic modifiers for use in the invention may be found among all classes of organic compounds, and may contain, besides carbon, one or more of the elements hydrogen, halogen, nitrogen, oxygen, or sulphur. (Those organic compounds, the bonds of which are easily broken, as for instance chain transfer agents, are preferred.) They may be of low or of high molecular weight, especially of polymeric structure. Thus there may be used Alcohols, such as methanol, ethanol, laurol; Glycols, such as glycerol, pentaerythritol, sorbitol, mannitol and partial esters of these polyols; Ethers, such as dimethyl, diethyl and ethylmethyl ethers, glycol ethers; Oxyalkylated ethers of partial esters of the polyols, such as the polyoxyethylene derivatives of fatty acid partial esters of sorbitol; Polyethers, such as polyoxyethylene glycol; Mercaptans, disulphides and thioethers analogous to the above; Amines, such as methylamine, ethylamine, hexamethylene diamine and dodecylamine; Amides of these amines formed with acids, such as formic acid, adipic acid, suberic acid and stearic acid; organic halides, such as chloromethane, chloroform, carbon tetrachloride, chloroethane, and dichlorodifluoromethane, chloroethylene and dodecafluoroheptyl alcohol. The modifier may be an unsaturated compound, particularly one which may be employed to form addition polymers by vinyl polymerization, e.g. styrene, the acrylic acid esters, vinyl chloride, vinylidene chloride, vinyl acetate, the vinyl ketones, the vinyl ethers, such as divinyl ether, acrylonitrile, methacrylonitrile, methoxydodecamethyleneoxy methacrylate, 1,3-butadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, ethylene, propylene, the acetylenes for instance phenylacetylene, the allyl esters, vinyl compounds (other than those already mentioned) containing halogen, sulphur, nitrogen or phosphorus, and the vinyl silanes. Polymers prepared from such of the above monomeric materials as are polymerizable are also suitable. The modifiers may be incorporated with the polymer before shaping, or they may be applied to the shaped articles, e.g. as solutions or in suitable cases as pure compounds, for instance by spraying, calendering, immersion, padding, or exposure to vapour condensation. In suitable cases a solution of the modifier may be applied to the surface of a shaped article and the solvent flashed off before the irradiation. If desired excess liquid may be removed before irradiation by squeezing. Synthetic addition polymers treated in accordance with the invention are primarily those formed by vinyl polymerization from alkylenically unsaturated monomers, such as styrene, the acrylic acid esters, vinyl halides, vinylidene halides, vinyl esters, ketones and ethers, vinyl compounds containing sulphur, nitrogen or phosphorus and other vinyl compounds containing halogen, vinyl silanes, ethylene, propylene, allyl ethers, acrylonitrile, methacrylonitrile, 1,3-butadiene, isoprene, chloroprene, and 2,3-dimethyl-1,3-butadiene. The polymers treated may be in the form of funicular-shaped structures such as filaments, staple fibres, and yarns comprising them; to woven, knitted, felted or fused fabrics and to their films. Shaped structures to be treated may be made by extrusion, moulding, casting or calendering. The polymers may also be treated in the form of finely comminuted particles which may subsequently be shaped, either in the molten state or in solution, e.g. by extrusion, moulding or casting. In addition to the above other modifications would be useful in other substrates, for example in films, which may be modified to improve adhesion to various coating or laminating agents, to change "slip" or the ease with which one film slides over another, to affect oil resistance or permeability (e.g. of synthetic elastomers), to produce non-reflective or decorative coatings on film or sheet, to improve the ease of printing colours on a sheet &c. Specific shaped articles which may be treated include woven or knitted fabrics, articles made from them for clothing or industrial use, reinforcement for composite structures (such as cords for mechanical rubber goods and fibre for laminates), artificial bristles or artificial straw and rods, bars, sheets, plates and laminates. Those properties which are not primarily a function of surface characteristics (e.g. tenacity, elongation, modulus, and the like) in some cases may be more conveniently modified by incorporating modifiers in the polymeric matrix and then subjecting it to particle irradiation. It may be desirable to incorporate one or more modifiers in the matrix and coat one or more modifiers on the surface of the polymer. Specifications 758,735 and 798,340 are referred to.ALSO:The properties of addition polymers are changed by subjecting the polymer to ionizing radiation while it is in intimate contact with at least one organic compound, which chemically bonds (as such or in the form of a polymeric structure) with the addition polymer. The modifier which may be dispersed, diffused or coated upon the polymer is preferably kept in an inert atmosphere or is enclosed by a polyethylene film, aluminium foil or other material which is impervious to air and water while it is being irradiated. Additionally, it may be in contact with a compound having protective or antioxidant effects with respect to the polymer or the modifier or both and during the irradiation temperature is preferably kept between 0 DEG and 75 DEG C., if necessary by cooling. The process is preferably carried out in the presence of calcium tungstate, zinc sulphate, metallic lead or other radiation transfer agent capable of absorbing radiation and re-admitting it in a lower form of energy. Examples of radiation dosages are given. Organic modifiers for use in the invention may be found among all classes of organic compounds, and may contain, besides carbon, one or more of the elements hydrogen, halogen, nitrogen, oxygen or sulphur. (Those organic compounds, the bonds of which are easily broken, as for instance chain transfer agents, are particularly preferred.) They may be of low molecular weight or of high molecular weight, especially of polymeric structure. Thus there may be used alcohols, such as methanol, ethanol, laurol; glycols, glycerol, pentaerythritol, sorbitol, mannitol and partial esters of these polyols; ethers, such as dimethyl, diethyl and ethylmethyl ethers, glycol ethers; oxyalkylated ethers of partial esters of the polyols, such as the polyoxyethylene derivatives of fatty acid partial esters of sorbitol; polyethers, such as polyoxyethylene glycol; mercaptans, disulphides and thioethers analogous to the above; amines, such as methylamine, ethylamine, hexamethylene diamine and dodecylamine; amides of these amines formed with acids, such as formic acid, adipic acid, suberic acid and stearic acid; organic halides, such as chloromethane, chloroform, carbon tetrachloride, chloroethane, and dichlorodifluoromethane, chloroethylene and dodecafluoroheptyl alcohol. The modifier may be an unsaturated compound, particularly one which may be employed to form addition polymers by vinyl polymerization, e.g. styrene, the acrylic acid esters, vinyl chloride, vinylidene chloride, vinyl acetate, the vinyl ketones, the vinyl ethers, such as divinyl ether, acrylonitrile, methacrylonitrile, methoxydodecamethyleneoxy methacrylate, 1,3-butadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene, ethylene, propylene, the acetylenes for instance phenylacetylene, the allyl esters, vinyl compounds (other than those already mentioned) containing halogen, sulphur, nitrogen or phosphorus, and the vinyl silanes. Polymers prepared from such of the above monomeric materials as are polymerizable are also suitable. The modifiers may be incorporated with the polymer before shaping, or they may be applied to the shaped articles, e.g. as solutions or in suitable cases as pure compounds, for instance by spraying, calendering, immersion, padding, or exposure to vapour condensation. In suitable cases a solution of the modifier may be applied to the surface of a shaped article and the solvent flashed off before the irradiation. If desired, excess liquid may be removed before irradiation by squeezing. Synthetic addition polymers treated in accordance with the invention, are primarily those formed by vinyl polymerization from alkylenically unsaturated monomers, such as styrene, the acrylic acid esters, vinyl halides, vinylidene halides, vinyl esters, ketones and ethers, vinyl compounds containing sulphur, nitrogen or phosphorus and other vinyl compounds containing halogen, vinyl silanes, ethylene, propy lene, allyl ethers, acrylonitrile, methacrylonitrile, 1,3-butadiene, isoprene, chloroprene and 2,3-dimethyl-1,3-butadiene. The polymers treated may be in the form of funicular shaped structures such as filame
GB10658/56A 1955-04-07 1956-04-06 Process for modifying the structure and properties of addition polymers Expired GB820120A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US820120XA 1955-04-07 1955-04-07

Publications (1)

Publication Number Publication Date
GB820120A true GB820120A (en) 1959-09-16

Family

ID=22168175

Family Applications (1)

Application Number Title Priority Date Filing Date
GB10658/56A Expired GB820120A (en) 1955-04-07 1956-04-06 Process for modifying the structure and properties of addition polymers

Country Status (1)

Country Link
GB (1) GB820120A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137674A (en) * 1960-12-09 1964-06-16 Grace W R & Co Polyethylene modified with a vinyl compound
US4537734A (en) * 1977-10-07 1985-08-27 Radiation Dynamics, Inc. Method for reducing the monomer content in acrylonitrile containing polymers
US6455447B1 (en) 1998-12-18 2002-09-24 Kimberly-Clark Corporation Paper machine substrates resistant to contamination by adhesive materials
US6638579B2 (en) 1999-12-15 2003-10-28 Kimberly-Clark Worldwide, Inc. Process of making paper machine substrates resistant to contamination by adhesive materials

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3137674A (en) * 1960-12-09 1964-06-16 Grace W R & Co Polyethylene modified with a vinyl compound
US4537734A (en) * 1977-10-07 1985-08-27 Radiation Dynamics, Inc. Method for reducing the monomer content in acrylonitrile containing polymers
US6455447B1 (en) 1998-12-18 2002-09-24 Kimberly-Clark Corporation Paper machine substrates resistant to contamination by adhesive materials
US6638579B2 (en) 1999-12-15 2003-10-28 Kimberly-Clark Worldwide, Inc. Process of making paper machine substrates resistant to contamination by adhesive materials

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