US3084115A - Method of vulcanizing rubber - Google Patents

Method of vulcanizing rubber Download PDF

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Publication number
US3084115A
US3084115A US787100A US78710059A US3084115A US 3084115 A US3084115 A US 3084115A US 787100 A US787100 A US 787100A US 78710059 A US78710059 A US 78710059A US 3084115 A US3084115 A US 3084115A
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US
United States
Prior art keywords
rubber
parts
composition
sbr
ethylene
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 - Lifetime
Application number
US787100A
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English (en)
Inventor
Wendell V Smith
Verne G Simpson
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.)
Uniroyal Inc
Original Assignee
United States Rubber 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
Priority to NL247416D priority Critical patent/NL247416A/xx
Priority to LU38113D priority patent/LU38113A1/xx
Priority to NL124741D priority patent/NL124741C/xx
Priority to US787100A priority patent/US3084115A/en
Application filed by United States Rubber Co filed Critical United States Rubber Co
Priority to GB40333/59A priority patent/GB881281A/en
Priority to DEU6754A priority patent/DE1208069B/de
Priority to FR814034A priority patent/FR1244671A/fr
Priority to BE586059A priority patent/BE586059A/fr
Application granted granted Critical
Publication of US3084115A publication Critical patent/US3084115A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2321/00—Characterised by the use of unspecified rubbers

Definitions

  • This invention relates to the vulcanization of rubber by exposing it to ionizing radiation, and more particularly it relates to the acceleration or enhancement of such vulcanization by having certain acrylate, diacrylate or dimethacrylate compounds present in the rubber during such exposure to ionizing radiation.
  • rubber may be at least partially if not completely vulcanized when placed in a field of ionizing radiation. There are, however, limitations on this process. First, after a certain amount of exposure to such radiations, rubber has been observed to degrade.
  • This invention shows that when small quantities of certain acryla-te, diacrylate or dimethacrylate compounds are mixed in with natural rubber or SBR (i.e., styrenebutadiene rubber, formerly known as GR-S or Buna-S) the amount of ionizing radiation necessary to effect cure is substantially reduced as shown in the working examples and tabulated results below.
  • SBR styrenebutadiene rubber
  • ionizing radiation is used here in its conventional sense as referring to radiation which when absorbed by matter produces ionization.
  • Well known to the art as ionizing radiations are X-rays, gamma rays, high speed electrons, beta rays, and high speed protons, alpha particles and fast neutrons. Of these, X-rays, gamof at least about 8 electron volts.
  • Table 10a on pages 105-115 of Electron 'Impact Phenomena and Properties of Gaseous Ions, by F. H. Field and I. L. Franklin (Academic Press, Inc., 1957).
  • Energy sources for such high energy ionizing radiation may be electron accelerators of the Van de Graatf or linear types or cobalt sources or nuclear reactors, etc.
  • the permissible irradiation dosage is from 4 to 40 watt hours per pound of material with a dosage of from 4 to 20 Watt hours per pound preferred. This permissible dosage is equivalent to 3.2)(10 to 32x10 rad.
  • methacrylates are ineffective in achieving the desired results while both acrylates and dimethacrylates as well as diacrylates are effective.
  • the desired compositions were mixed on a cold mill and test slabs of 6 /2 x 6 /2 x 0.1" were molded in a press for 5 minutes at 260 F.
  • the slabs were then irradiated either in an X-ray machine or by exposure to a beam of 2 million volt electrons obtained from a Van de Graaif accelerator. To prevent undue heating of samples, intermittent exposures were used; the total dosage being controlled by the total time of exposure. Tests on the treated slabs were carried out by using conventional rubber testing equipment.
  • modulus 2 300% modulus with dosages of 0, 4, 10, 20. Control values of modulus are 46, 138, 225, 645 psi. 3 Commercial material sold as Monomer MG-l by Union Carbide and Carbon 00.
  • ma rays and high speed electrons are particularly suitable to this invention.
  • the operative radiation may be described as high energy radiation, the individual particles or photons of which possess energies From these data it may readily be observed that significant results are obtained when .the following compounds are employed.
  • the amount of additive used is in all cases at least 1 /2 parts, per 1100 parts of rubber.
  • the amount used typically varies with the amount of active component in the compound.
  • acrylate or methacrylate component per 100 parts of rubber.
  • the compound contains only about 40% acrylate hence at least 4 parts are used.
  • alkyl monomethacrylates are ineffective while dimethacrylates are effective.
  • the preferred additives are:
  • Alkyl acrylates/alkyl from C to C Diacrylates and dimethacrylates of polyethylene glycol, having a molecular weight of from about 170 to 1000. Diacrylates and dimethacrylates of ethylene, propylene and tetramethylene glycols.
  • Durorneter 5 TABLE 4-Continued Smoked Sheet With Octyl Acrylwte and Daryl Meth- Stock N 9 10 11 12 SBB 1500 100 100 100 100 acrylate and Control Philblack O 55 50 55 60 Octyl acrylate 10 20 Octyl methaerylate Stock N o 22 23 24 25 26 Rubber SS 100 100 100 100 100 Philblack O 50 55 60 55 60 Torsional hysteresis at room Octyl acrylate 10 20 temperature Ogtyl methacrylnte 10 20 Tensile strength, lbs/in. Rizgiation dose, weight hrsJ Elongation, percent 200% modulus, lbs/in.
  • Torsional hysteresis at room temperature Torsional hysteresis at 280 F.
  • a method of vulcanizing a rubber composition com.- prising subjected said composition to a dosage of from 4 to 40 Watt hours of high energy ionizing radiation per pound of said composition, the said composition comprising 100 parts by weight of a rubber selected from the group consisting of Hevea rubber and SBR, and, as an accelerator, from 1.5 to parts of a material selected from the group consisting of alkyl acrylates, acrylic esters of saturated dihydric alcohols, methacrylic esters of saturated dihydric alcohols, acrylic esters of polydihydric alcohols, and 'methacrylic esters of polydihydric alcohols.
  • a method of vulcanizing a rubber composition comprising subjecting said composition to a dosage of from 4 to 'Watt hours of high energy ionizing radiation per pound of said composition, the said composition comprising 100 parts by weight of a rubber selected from the group consisting of Hevea rubber and SBR, and, as an accelerator, *from 1.5 to 15 parts of a material selected from the group consisting of alkyl acrylates in which the alkyl group has from 4 to 12 carbon atoms, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene diacrylate, ethylene dimethacrylate, propylene diacrylate, propylene dimethacrylate, tetramethylene diacrylate and tetramethylene dimethacrylate.
  • a vulcanized rubber composition comprising parts by weight of a rubber selected from the group consisting of Hevea rubber and SBR, and, as an accelerator, from 1.5 to 15 parts of a material selected from the group consisting of alkyl acrylates, acrylic esters of saturated dihydric alcohols, methacrylic esters of saturated dihydric alcohols, acrylic esters of polydihydric alcohols and methacrylic esters of polydihydric alcohols, said composition having been vulcanized by the method of claim 1.
  • a vulcanized rubber composition comprising 100 parts by weight of a rubber selected from the group consisting of Hevea rubber and SBR, and, as an accelerator, from 1.5 to 15 parts of a material selected from the group consisting of alkyl acrylates in which the alkyl group has from 4to 12 carbon atoms, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, ethylene diacrylate, ethylene dimethacrylate, propylene diacrylate, propylene dimethacrylate, tetramethy-lene diacrylate, and tetramethylene dimethacrylate, said composition having been vulcanized by the method of claim 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Polymerisation Methods In General (AREA)
US787100A 1959-01-16 1959-01-16 Method of vulcanizing rubber Expired - Lifetime US3084115A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL247416D NL247416A (en)) 1959-01-16
LU38113D LU38113A1 (en)) 1959-01-16
NL124741D NL124741C (en)) 1959-01-16
US787100A US3084115A (en) 1959-01-16 1959-01-16 Method of vulcanizing rubber
GB40333/59A GB881281A (en) 1959-01-16 1959-11-27 Improvements in vulcanizing rubber
DEU6754A DE1208069B (de) 1959-01-16 1959-12-18 Verfahren zum Vulkanisieren von Kautschuk mit ionisierender Strahlung
FR814034A FR1244671A (fr) 1959-01-16 1959-12-23 Procédé perfectionné de vulcanisation du caoutchouc
BE586059A BE586059A (fr) 1959-01-16 1959-12-28 Procédé perfectionné de vulcanisation du caoutchouc.

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US787100A US3084115A (en) 1959-01-16 1959-01-16 Method of vulcanizing rubber

Publications (1)

Publication Number Publication Date
US3084115A true US3084115A (en) 1963-04-02

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ID=25140417

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US787100A Expired - Lifetime US3084115A (en) 1959-01-16 1959-01-16 Method of vulcanizing rubber

Country Status (7)

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US (1) US3084115A (en))
BE (1) BE586059A (en))
DE (1) DE1208069B (en))
FR (1) FR1244671A (en))
GB (1) GB881281A (en))
LU (1) LU38113A1 (en))
NL (2) NL124741C (en))

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226312A (en) * 1960-04-26 1965-12-28 Lamm Alphonse Processes for the manufacture of natural and synthetic rubbers reinforced with fillers
US3438933A (en) * 1966-12-05 1969-04-15 Pcr Patent Dev Corp Molding process and composition
US3988227A (en) * 1975-04-28 1976-10-26 General Motors Corporation Oil-resistant EPDM elastomer
US4179531A (en) * 1977-08-23 1979-12-18 W. R. Grace & Co. Polythiol effect, curable monoalkenyl aromatic-diene and ene composition
US4234676A (en) * 1978-01-23 1980-11-18 W. R. Grace & Co. Polythiol effect curable polymeric composition
EP0023715A1 (de) * 1979-08-04 1981-02-11 Metzeler Kautschuk Gmbh Verfahren zur Herstellung von Gummiartikeln
WO1986006561A1 (en) * 1985-05-02 1986-11-06 Raychem Corporation Cable sealing
US4721832A (en) * 1985-05-02 1988-01-26 Raychem Corporation Electrical connection sealing device
US4851063A (en) * 1969-07-02 1989-07-25 Mildred Kelley Seiberling Radiation cure of tire plies in a continuous operation
US4963698A (en) * 1985-05-02 1990-10-16 Raychem Corporation Cable sealing
US6423760B1 (en) * 1999-12-03 2002-07-23 China Petro-Chemical Corporation Fully vulcanized powdery rubber having a controllable particle size, preparation and use thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
PT69761A (en) * 1978-06-16 1979-07-01 Amerace Corp Improved process for producing flexible microporous composition rubber base articles and articles so produced namelya battery separator
FR2513256A1 (fr) * 1981-09-18 1983-03-25 Commissariat Energie Atomique Element separateur en elastomere, son procede de preparation et son utilisation dans les systemes de suspension hydropneumatique
US4904422A (en) * 1988-02-04 1990-02-27 University Of Maryland, College Park Ozone and wear resistance in styrene-butadiene rubber

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE546816A (en)) *
US2155590A (en) * 1936-05-02 1939-04-25 Goodrich Co B F Vulcanizable plasticizer
US2505067A (en) * 1947-09-29 1950-04-25 Alexander H Kerr & Co Catalytic photopolymerization process and compositions
US2609353A (en) * 1946-07-10 1952-09-02 Dow Chemical Co Polymerizable composition of styrene, unsaturated alkyd resin, and elastomer
US2668133A (en) * 1953-04-13 1954-02-02 United Shoe Machinery Corp Adhesive bonding processes
US2670483A (en) * 1951-10-05 1954-03-02 United Shoe Machinery Corp Stiffening portion of shoes
GB732047A (en) * 1951-11-10 1955-06-15 Atomic Energy Authority Uk Improvements in or relating to treatment of polymeric substances
US2973309A (en) * 1956-08-14 1961-02-28 Exxon Research Engineering Co Stable butyl latices

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1040227B (de) * 1955-05-27 1958-10-02 Siemens Ag Verfahren zum Herstellen eines gummielastischen Gegenstandes aus thermoplastischem Kunststoff

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE546816A (en)) *
US2155590A (en) * 1936-05-02 1939-04-25 Goodrich Co B F Vulcanizable plasticizer
US2609353A (en) * 1946-07-10 1952-09-02 Dow Chemical Co Polymerizable composition of styrene, unsaturated alkyd resin, and elastomer
US2505067A (en) * 1947-09-29 1950-04-25 Alexander H Kerr & Co Catalytic photopolymerization process and compositions
US2670483A (en) * 1951-10-05 1954-03-02 United Shoe Machinery Corp Stiffening portion of shoes
GB732047A (en) * 1951-11-10 1955-06-15 Atomic Energy Authority Uk Improvements in or relating to treatment of polymeric substances
US2668133A (en) * 1953-04-13 1954-02-02 United Shoe Machinery Corp Adhesive bonding processes
US2973309A (en) * 1956-08-14 1961-02-28 Exxon Research Engineering Co Stable butyl latices

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226312A (en) * 1960-04-26 1965-12-28 Lamm Alphonse Processes for the manufacture of natural and synthetic rubbers reinforced with fillers
US3438933A (en) * 1966-12-05 1969-04-15 Pcr Patent Dev Corp Molding process and composition
US4851063A (en) * 1969-07-02 1989-07-25 Mildred Kelley Seiberling Radiation cure of tire plies in a continuous operation
US3988227A (en) * 1975-04-28 1976-10-26 General Motors Corporation Oil-resistant EPDM elastomer
US4179531A (en) * 1977-08-23 1979-12-18 W. R. Grace & Co. Polythiol effect, curable monoalkenyl aromatic-diene and ene composition
US4234676A (en) * 1978-01-23 1980-11-18 W. R. Grace & Co. Polythiol effect curable polymeric composition
EP0023715A1 (de) * 1979-08-04 1981-02-11 Metzeler Kautschuk Gmbh Verfahren zur Herstellung von Gummiartikeln
US4352765A (en) * 1979-08-04 1982-10-05 Metzeler Kautschuk Gmbh Method for producing rubber articles by subjecting powdered caoutchou composition to intensive mixing and high-speed electrons
WO1986006561A1 (en) * 1985-05-02 1986-11-06 Raychem Corporation Cable sealing
US4721832A (en) * 1985-05-02 1988-01-26 Raychem Corporation Electrical connection sealing device
US4963698A (en) * 1985-05-02 1990-10-16 Raychem Corporation Cable sealing
US6423760B1 (en) * 1999-12-03 2002-07-23 China Petro-Chemical Corporation Fully vulcanized powdery rubber having a controllable particle size, preparation and use thereof

Also Published As

Publication number Publication date
DE1208069B (de) 1965-12-30
FR1244671A (fr) 1960-10-28
GB881281A (en) 1961-11-01
BE586059A (fr) 1960-04-19
NL247416A (en))
LU38113A1 (en))
NL124741C (en))

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