EP0712418A1 - Composition copolymere de polychloroprene - Google Patents

Composition copolymere de polychloroprene

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Publication number
EP0712418A1
EP0712418A1 EP94923913A EP94923913A EP0712418A1 EP 0712418 A1 EP0712418 A1 EP 0712418A1 EP 94923913 A EP94923913 A EP 94923913A EP 94923913 A EP94923913 A EP 94923913A EP 0712418 A1 EP0712418 A1 EP 0712418A1
Authority
EP
European Patent Office
Prior art keywords
butadiene
parts
composition
copolymer
chloro
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.)
Withdrawn
Application number
EP94923913A
Other languages
German (de)
English (en)
Inventor
Furman Eugene Glenn, Sr.
Fred Kenneth Jones, Jr.
Steven Joseph Klaas
William Kenneth Witsiepe
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 EP0712418A1 publication Critical patent/EP0712418A1/fr
Withdrawn legal-status Critical Current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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers 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
    • C08F236/04—Copolymers 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
    • C08F236/14—Copolymers 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
    • C08F236/16—Copolymers 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
    • C08F236/18—Copolymers 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 containing chlorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L11/00—Compositions of homopolymers or copolymers of chloroprene
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • This patent relates to novel highly resilient polychloroprene compositions which are resistant to crystallization and creep.
  • Polychloroprene rubber has replaced natural rubber in a wide variety of automotive applications because it offers superior heat resistance coupled with comparable elastomeric properties.
  • automotive applications particularly those in which dynamic properties are critical, which require an elastomer having a combination of high resilience, low hysteresis, creep resistance, and durability (fatigue resistance) not attainable using prior art polychloroprene compositions. Consequently, natural rubber has remained the elastomer of choice for vibration isolation applications, especially for engine mount applications.
  • Recent automobile design trends have led to size reductions of the engine compartment and, as a result, engine compartment temperatures are higher than in the past. At these higher temperatures natural rubber compositions degrade rapidly.
  • compositions having enhanced heat resistance which exhibit dynamic elastomeric properties comparable to or which exceed those of natural rubber.
  • the present invention is directed to a class of novel chloroprene copolymers which meet this need.
  • this invention is directed to highly resilient dialkyl xanthogen disulfide-modified or dialkoxy xanthogen disulfide- modified 2-chloro-l,3-butadiene copolymers comprising 92-99 percent by weight copolymerized units of 2-chloro-l,3-butadiene, up to 91%, of said 2- chloro-l,3-butadiene units having a 1,4-trans configuration, and 1-8 percent by weight copolymerized units of at least one comonomer selected from the group consisting of 2,3-dichloro-l,3-butadiene, styrene, methyl methacrylate, acrylonitrile, isoprene, and butadiene, said copolymers when cured having a tan delta of less than 0.20 at 5 Hertz and 23°C.
  • the invention is also directed to a process for preparation of the highly resilient 2-chloro-l,3-butadiene copolymer compositions, which comprises copolymerizing a mixture of 2-chloro-l,3-butadiene and comonomer described above to a conversion of up to 75% in an aqueous alkaline emulsion in the presence of a free radical initiator at a temperature of at least 42°C and in the presence of no greater than 0.8 parts of a dialkyl xanthogen disulfide chain transfer agent or a dialkoxy xanthogen disiilfide chain transfer agent per 100 parts monomer, thereby forming a 2-chloro-l,3- butadiene copolymer having 92-99 percent by weight copolymerized 2- chloro-l,3-butadiene units and 1-8 percent by weight copolymerized units of the comonomer or comonomers.
  • the invention is further directed to blends of the above- described copolymers with sulfur-modified 2-chloro-l,3-butadiene homopolymers or sulfur-modified copolymers of 2-chloro-l,3-butadiene and 2,3-dichloro-l,3-butadiene containing up to 5 percent by weight copolymerized units of 2,3-dichloro-l,3-butadiene, said sulfur-modified homopolymers or sulfur-modified copolymers containing less than 0.6 percent by weight combined sulfur.
  • the invention is directed to curable compositions of the novel copolymers and copolymer blends and to engine mounts made from the copolymer and copolymer blend compositions.
  • the xanthogen disulfide-modified copolymer described above exhibits an unusual combination of properties.
  • the small amount of comonomer copolymerizable with the chloroprene monomer is effective to increase resistance to low temperature crystallization, and xanthogen disulfide modification is effective to increase resilience (low vibration damping), characterized by tan delta of less than 0.2 at 5 Hertz and 23°C, and increase durability.
  • the modified copolymer also exhibits high heat resistance and low creep. This copolymer can be further modified through compounding to develop properties desired for particular applications.
  • Figures 1, 2, and 3 are, respectively, a perspective view, a front elevational view, and a cross-sectional view, all schematically presented, of an A-mount test specimen.
  • each reference numeral refers to the same structural element in each figure.
  • compositions of the present invention are copolymers of 2-chloro-l,3-butadiene (i.e. chloroprene) which are especially adapted for use in high temperature dynamic applica ti ons in which high resilience is required. Under such conditions it is desirable to minimize polymer internal heat buildup by minimizing hysteresis or mechanical energy dissipation.
  • 2-chloro-l,3-butadiene i.e. chloroprene
  • hysteresis losses are the losses of energy irreversibly converted to heat when an elastomer is subjected to dynamic stress.
  • Hysteresis losses for a given material are dependent on the relationship between stress and strain and can be measured as tan delta.
  • tan delta is defined as the ratio of loss modulus, i.e. the component of shear stress that is out of phase with strain, to storage modulus, i.e. the component of stress that is in phase with the strain.
  • tan delta is large when energy dissipation is large. It is small for a highly resilient polymer.
  • the copolymers of the present invention are characterized by the type of copolymerized monomer units present and their ratio. This selection plays a major part in insuring that the tan delta of the polymers is low without compromising other important polymer properties, such as crystallization resistance. That is, the copolymers contain 1-8 weight percent, preferably 3-6 weight percent, of at least one copolymerizable monomer selected from the group consisting of 2,3-dichloro-l,3-butadiene, styrene, methyl methacrylate, acrylonitrile, isoprene, and butadiene, and 92- 99 weight percent chloroprene units.
  • higher copolymers are also within the scope of the present invention, for example terpolymers wherein more than one of the above-described copolymerizable monomers is present or copolymers which additionally contain other copolymerizable monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, lower alkyl acrylamides, lower alkyl methacrylamides, methacrylonitrile, lower alkyl acrylates, other lower alkyl methacrylates, lower alkyl maleates, and lower alkyl fumarates.
  • terpolymers wherein more than one of the above-described copolymerizable monomers is present or copolymers which additionally contain other copolymerizable monomers such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, lower alkyl acrylamides, lower alkyl methacrylamides, methacrylonitrile, lower alkyl acrylates, other lower alkyl methacrylates, lower alkyl
  • At least 92 weight percent of the copolymerized units are chloroprene units and 1-8 weight percent of the remaining units are 2,3-dichloro-l,3-butadiene, 5 styrene, methyl methacrylate, acrylonitrile, isoprene, or butadiene units.
  • 2,3- Dichloro-l,3-butadiene is the preferred copolymerizable comonomer because it has a higher reactivity with chloroprene than do styrene, methyl methacrylate, acrylonitrile, isoprene, or butadiene.
  • use of any of these comonomers will produce compositions which have low tan delta.
  • Tan delta for cured compositions of the present invention is 5 less than 0.20, and preferably no greater than 0.10, at 5 Hertz and 23°C as determined by resilience testing using the dynamic testing procedure and A- mount test apparatus used therein as described hereinafter.
  • the A-mount is a generic engine mount and consequently closely approximates actual use conditions.
  • 10 is a 1008-1010 steel cylinder having an 0 approximate inner diameter of 76.3mm and a length of 48.9mm.
  • the inner cylinder, 12, also of 1008-1010 steel, has an approximate inner diameter of 72.9mm, an outer diameter of 76.3mm, and a length of 48.9mm.
  • a thin layer 14 of compounded composition described hereinafter, having an approximate thickness of 1.5mm is coated on the inner surface of inner 5 cylinder 12.
  • two legs 22 of compounded composition are symmetrically situated 31.5 degrees from the vertical center line 4. Each leg is 15mm wide and 41.6mm thick. The height of each leg is determined by the distance between the centerline 5 of the insert and the horizontal centerline 8 of cylinder 12; this distance is 7.03mm.
  • an adhesive primer layer 16 composed of Thixon ® P15, available from Morton International, Inc., approximately 0.06mm thick, is applied to the surface of inner cylinder 12 and the outer surface of aluminum center insert 30.
  • the adhesive primer layer 16 and the two adhesive layers 18 and 20 serve to bond the legs 22 and layer 14 to the inner surface of cylinder 12 and the legs 22 to the outer surface of insert 30.
  • the distance between points a and b of insert 30 along line 4 is 18.95mm and the distance between points c and d along line 5 is 31.75mm, which is the horizontal centerline of the insert 30.
  • the angle formed by lines 5 and 6 is 31.36°.
  • the length of aluminum insert 30 is 77.32mm. Insert 30 has a hole 32 extending along its length for receiving a rod (not shown), which is attached to a fixture (not shown), which, in turn is attached to the test equipment (not shown).
  • a further characteristic of the copolymers of the invention is that no greater than 91% of the polymerized chloroprene units are in the 1,4-trans configuration. Such copolymers are produced at polymerization temperatures which exceed 42°C. As a result of the high polymerization temperature the amount of copolymerized chloroprene cure-site monomer units which result from 1,2 polymerization is increased compared to copolymers prepared at lower temperatures. It is postulated that the increased crosslink density which is obtained on curing such compositions contributes to a lower tan delta in the cured copolymers.
  • Another important structural feature of the copolymer compositions is that they are modified by dialkyl or dialkoxy xanthogen disulfides. It has been found that cured xanthogen disulfide-modified copolymers exhibit lower values of tan delta than comparable compositions which have been modified by other chain transfer agents such as mercaptans.
  • the chloroprene copolymer compositions of the invention are solids, that is they are neither fluids nor latexes. They have Mooney viscosities, ML ⁇ +4 @ 100°C, of at least 25.
  • An effective method for preparation of the chloroprene copolymer compositions is aqueous emulsion polymerization of chloroprene and comonomer or comonomers in the presence of a free radie-1 catalyst.
  • a free radie-1 catalyst Any of the conventional free radical polymerization catalysts r y be utilized including alkali metal or ammonium ferricyanides and peroxy compounds such as alkali metal or ammonium persulfates, hydrogen peroxide, cumene hydroperoxide, and dibenzoyl peroxide.
  • the amount of free radical catalyst which is employed is between the ranges of 0.001-0.2% by weight, based on the total amount of monomers present.
  • reducing agents such as sodium formaldehyde sulfoxylates or sodium hydrosulfite in combination with the free radical catalyst.
  • any of the conventional emulsifying agents may be used in preparing the monomer emulsion.
  • these include the water-soluble salts, particularly the sodium, potassium, or ammonium salts, of compounds of the following types: long-chain fatty acids; rosins or rosin derivatives, such as wood rosin, tall oil rosin, disproportionated rosins, or partially polymerized rosin; higher alcohol sulfates; and arylsulfonic acids such as alkylbenzenesulfonic acids and the condensation product of formaldehyde with a naphthalenesulfonic acid.
  • the dialkyl xanthogen disulfide chain transfer agents used for modifying the chloroprene copolymer can be represented by the formula
  • R and R' are alkyl radicals having one to eight carbon atoms.
  • dialkyl xanthogen disulfides are those in which each alkyl radical has 1 to 4 carbon atoms.
  • Diisopropyl xanthogen disulfide is particularly preferred because it has a lower toxicity than other dialkyl xanthogen disulfides while maintaining good efficiency.
  • Dialkoxy xanthogen disulfide modifiers may also be employed. These compounds are compositions of the formula
  • suitable alkyl radicals are methyl, ethyl, butyl, and hexyl.
  • a preferred heterocyclic R group is 5-ethyl- l,3-dioxan-5-yl-methyl.
  • the modifier content of the polymer is from 0.4-0.9 weight percent. The preferred range for modifier content of the polymer is 0.76-0.84 .
  • dialkyl or dialkoxy xanthogen disulfide chain transfer agent per 100 parts monomer is used during the polymerization in order to control Mooney viscosity and to control gel content.
  • the maximum amount of chain transfer agent that may be used to produce polymers of the desired Mooney viscosity is 0.9 parts per 100 parts of monomer.
  • the amount of units derived from comonomers other than chloroprene in the copolymer is 1-8 percent by weight, preferably 3-6 percent by weight.
  • 2,3-Dichloro-l,3-butadiene, the preferred comonomer is substantially more reactive than chloroprene. Therefore, the dichlorobutadiene is incorporated into the copolymer more rapidly than is chloroprene. It is usually necessary to limit conversion to 65-
  • the proportion of dichlorobutadiene in the isolated polymer is higher than the proportion of dichlorobutadiene in the diene monomers charged. For these reasons, the isolated polymer will contain more units derived from 2,3-dichloro-l,3- butadiene than the amount charged to the polymerization vessel.
  • styrene, methyl methacrylate, acrylonitrile, isoprene, and butadiene are less reactive than chloroprene and the proportion of these comonomers in the isolated polymer will be less than their proportion in the monomer mixture charged.
  • the presence of units derived from 2,3-dichloro- 1,3-butadiene and the other copolymerizable monomers can be shown by nuclear magnetic resonance spectroscopy.
  • the amount of comonomer in the copolymer can be determined by chlorine analysis, infrared spectroscopy, and nuclear magnetic resonance spectroscopy of a refined polymer sample.
  • the concentration of organic monomers present in the aqueous emulsion is not critical. In general 30 to 60 percent, by weight, based on the total weight of the emulsion, is the range of concentration of organic monomers used in the preparation of the copolymers.
  • the exact proportion of comonomer used will depend on the reactivity of the particular comonomer or comonomers and the amount of the comonomer desired in the resultant copolymer.
  • the monomer ratio in the polymerization emulsion wherein the comonomer is 2,3-dichloro-l,3-butadiene will generally be 0.6-5.6 parts per 100 parts by weight of total monomer.
  • the proportion of the units derived from chloroprene units in the copolymer which iave a 1,4-trans configuration is a further important feature of the present invention. This proportion is a function of the temperature used during polymerization. Polymers prepared at temperatures above 42°C will have 1,4-trans content of monomer units derived from chloroprene of less than 91% based on the total number of units derived from chloroprene present since this is strictly a function of polymerization temperature when using a free radical polymerization system.
  • a polymerization temperature of 42- 52°C is most preferred because it balances the crystallization resistance and processibility of the copolymer.
  • the 1,4-trans content can be determined by carbon-13 nuclear magnetic resonance spectroscopy, by the methods of Coleman, Tabb, and Brame, Rubber Chemistry and Technology. Vol. 50, (1977), pages 49-62, and Coleman and Brame, Rubber Chemistry and
  • Polymerization is carried out in an inert atmosphere free of oxygen, such as an atmosphere of nitrogen or other inert gas. It is preferred to operate at a pH in the alkaline range as is customary in chloroprene polymerization processes. Polymerization may be stopped at any desired point by the use of conventional short-stopping agents, such as thiodiphenylamine, p-tertiarybutylcatechol, hydroquinone, and sodium diethyldithiocarbamate. Unreacted monomer is removed by known methods, such as by steam stripping.
  • conventional short-stopping agents such as thiodiphenylamine, p-tertiarybutylcatechol, hydroquinone, and sodium diethyldithiocarbamate. Unreacted monomer is removed by known methods, such as by steam stripping.
  • the present invention is further directed to blends of the above-described dialkyl or dialkoxy xanthogen disulfide-modified 2-chloro- 1,3-butadiene copolymer compositions with sulfur-modified chloroprene polymers containing to 5 percent by weight 2,3-dichloro-l,3-butadiene.
  • the sulfur-modified polymer contains less than 0.60 wt.% combined sulfur, preferably less than 0.45 wt.% combined sulfur.
  • These blends are composed of 15-85 parts of the sulfur-modified polymer and 85-15 parts of the dialkyl or dialkoxy xanthogen disulfide-modified copolymer.
  • Preferably 40-60 parts of the sulfur-modified copolymer is present, most preferably 45-55 parts. If less than 15 parts of the sulfur-modified polymer is present fatigue resistance is low. If greater than 85 parts is present, heat resistance and creep resistance are adversely affected.
  • the sulfur-modified homopolymers and sulfur-modified copolymers may be prepared by polymerization techniques which are well- known in the art. Polymerization is conducted in an aqueous en ion and may be, for example, carried out as follows: an aqueous solution or the polymerization initiator, e.g. an alkali metal or ammonium ferricyanide or a peroxy compound, is added to an aqueous emulsion containing chloroprene, sulfur, emulsifiers, and optionally 2,3-dichloro-l,3-butadiene. The pH of the polymerization medium is maintained at about 11-13.
  • an aqueous solution or the polymerization initiator e.g. an alkali metal or ammonium ferricyanide or a peroxy compound
  • 0.2- 0.4 parts sulfur per 100 parts chloroprene monomer is used in the polymerization process. It is important that the amount of sulfur incorporated in the polymer be below 0.60 wt.% , preferably below 0.45 wt.%, to insure that the polymer blends have adequate heat resistance.
  • the polymerization temperature range is quite broad, 0-80°C being suitable, although a temperature of 35-50°C is preferred.
  • Polymerization is carried out to the desired conversion, normally from about 70% to about 90%. When the desired conversion is reached, polymerization is short-stopped by the addition of a convenient short-stopping agent, such as, for example, a mixture of p-t-butyl catechol and phenothiazine.
  • the polymer contains sulfur atoms in its chain, and at high conversion it is appreciably crosslinked. Because such polymers are intractable, the molecular weight must be reduced.
  • This step known as peptization, is normally accomplished by treating the polymer latex with a tetraalkylthiuram disulfide in combination with a sodium dialkyl dithiocarbamate or other sulfur- containing nucleophile. Unchanged monomer is then steam-stripped from the polymer latex and the stripped latex is acidified.
  • the polymer is conveniently isolated on a freeze-roll or by other well known isolation means.
  • the polymer blends may be prepared by latex blending prior to isolation or the already isolated polymers may be mixed, for example on a rubber mill or in a Banbury mixer.
  • Latex blending provides a more homogeneous blend of the polymeric blend components.
  • the blends are particularly suitable for use in applications wherein they are subjected to high flex, such as roll mounts, because such compositions are optimized with respect to flex cracking when compared with the xanthogen disulfide-modified copolymers themselves.
  • the dialkyl or dialkoxy xanthogen disulfide-modified copolymers and copolymer blends of the present invention can be cured and compounded in the same manner as other polychloroprene copolymers.
  • the copolymer compositions are mixed uniformly with the other compounding ingredients using any of the usual mixing devices such as a roll mill, extruder, Banbury mixer, or other internal mixing device which is capable of mixing the materials without undue heating of the mixture.
  • the compounding step and polymer blending step may be combined to produce a compounded copolymer blend composition in one step.
  • a variety of well-known compounding ingredients useful in the compounding of polychloroprene elastomers may be added to the copolymer compositions. These include solid additives such as reinforcing agents, fillers, pigments, and resins. Examples of such materials are carbon black, silica, calcium carbonate, and titanium dioxide, hydrocarbon resins, and phenolic resins. Liquid additives include processing oils and plasticizers, both monomeric and polymeric, and liquid polychloroprene rubber. Other materials such as stabilizers, antioxidants, antiozonants, lubricants, release agents, and additives that improve certain properties of the compound can be added in minor proportions.
  • Vulcanization of the blends is accomplished by known means.
  • the vulcanizing agents can be added to the copolymer compositions using a Banbury mixer, a roll mill, or other mixing device under conditions which avoid premature curing of the compound.
  • Chemical agents usually employed for vulcanization of chloroprene polymers are satisfactory for curing the compositions of the present invention and typically include combinations of zinc and magnesium oxides, alone or with organic accelerators; sulfur donor or sulfur/accelerator systems; and peroxides.
  • a preferred curing system is a combination of zinc oxide, magnesium oxide, and ethylene thiourea.
  • 3-methyl-thiazolidine-thione-2 may be used in place of ethylene thiourea.
  • 5 parts of zinc oxide and 4 parts of magnesium oxide are used per 10 r t>arts polymer.
  • retarder-activators can be used as retarder-activators.
  • the amounts of accelerator and retarder-activator can be varied over a wide range depending on the particular chemical composition, the accelerator, the retarder-activator, and the intended use of the vulcanizate. In most cases, however, it is preferable not to use retarder- activators because the presence of these additives adversely affects various physical properties, especially creep resistance.
  • certain physical properties of the vulcanized compositions can be optimized by varying particular additive parameters. For example, creep resistance of the copolymers and copolymer blends is improved by maintaining a low filler level, generally 10-60 parts per 100 parts polymer, preferably 15-25 parts. In prior art compositions a combination of low tan delta, creep resistance, and durability was not achievable with such low filler concentrations. In addition, in compositions wherein the xanthogen disulfide-modified copolymer is the only polymer component present, it has been found that durability is improved by addition of 0.1-1.0 and preferably 0.1-0.3 parts of sulfur per 100 parts of polymer to the compounding recipe.
  • compositions of the present invention are useful for engine mounts, power transmission belts, bushings, and vibration isolators.
  • Compounded compositions containing the xanthogen disulfide- modified copolymers of the invention as the single polymeric component are best adapted for use in applications wherein the composition is subjected to compressive loads.
  • Compounded compositions containing the polymer blend compositions of the present invention are most suitable for use in applications wherein the compositions are subjected to extensive flexing.
  • Dynamic testing i.e. testing for complex dynamic stiffness (K*) and tan delta, was performed on an MTS 831 Dynamic Characterization Machine.
  • A-mount test specimens as shown in Figures 1, 2, and 3, were prepared from the polymer compositions by a transfer molding process. Tests were conducted at least 24 hours after molding or performance testing.
  • the A-mount test specimen is assembled in two steps. First, a compounded composition containing curing agents is introduced to a mold cavity which is defined by the metal cylinder 12 having an outer diameter of 78.2mm, as shown in Figures 1-3, the aluminum insert 30, as shown in Figures 1-3, and core inserts to give the shape and orientation of legs 22 shown in Figures 1-3.
  • the transfer molding of heated compounded composition to form the A-mount test specimen (legs 22) also forms the layer 14 ( Figure 2) by virtue of the composition flowing between the core inserts and the inner wall of cylinder 12.
  • the part is than cured for 30 minutes at 160°C using conventional transfer molding techniques.
  • the molding process is complete the part is removed from the mold and swaged into the outer steel cylinder 10, thus resulting in an A-mount test specimen wherein the inner cylinder 12 has a final outside diameter of 76.3mm, thereby placing the test legs 22 of compounded composition under compression for the conduct of the dynamic testing.
  • the A- mount specimens were loaded in the test apparatus in such a way that the legs pointed symmetrically downward. Dynamic testing was performed in the vertical direction using the following conditions to capture and report K* and tan delta at constant load control.
  • Durability testing was performed using a servohydraulic fatigue test machine.
  • the test specimen is placed in the fatigue test apparatus and oriented in such a way that the legs of the A-mount are pointed symmetrically downward.
  • the following test conditions using load control were applied. Frequency 5.0 Hz sinusoidal
  • Parts are visually inspected for any cracks, tears or failures after intervals of 100,000 cycles but continuous monitoring of the dynamic properties enables 5 the point of failure to be more exactly determined. Failure is defined as any crack that exceeds 5mm in length, wherein the crack involves solely rubber to rubber separation within a leg of the A-mount test specimen.
  • the creep resistance test is a static test which measures deflection under compressive load at elevated temperature.
  • a pre-test free o height of the A-mount test specimen is recorded by measuring the free position of diamond-shaped aluminum insert 30, as shown in Figure 1, relative to the outer cylinder.
  • the test specimen is placed in the creep test apparatus and oriented so that the legs are pointed symmetrically downward.
  • the test chamber is heated to a temperature of 100°C.
  • the part is 5 maintained at a temperature of 100°C for 30 minutes prior to application of a 56.75kg compressive load. Once the load is applied deflection at zero minutes is recorded. Deflections are recorded at 24 and 144 hours.
  • a mixture of 1.13 parts 50% aqueous sodium hydroxide, 0.40 0 parts formaldehyde-naphthalene sulfonic acid condensate, 0.15 sodium sulfite, and 1.65 x 10"6 parts p-tertiarybutyl catechol was dissolved in 105.8 parts deionized water and added to a solution of 97 parts of chloroprene, 3 parts of 2,3-dichloro-l,3-butadiene, 3 parts of disproportionated tall oil resin, 0.6 parts of diisopropyl xanthogen disulfide, and 0.75 parts mixed oleic and 5 elaidic acids.
  • the resultant mixture was emulsified in a high-speed mixer for 5 minutes in a nitrogen atmosphere.
  • the emulsion was then heated to 48°C and polymerization was initiated by addition of a solution composed of 5 parts potassium persulfate and 0.125 parts sodium anthraquinone-beta sulfonate dissolved in 2000 parts water.
  • the rate of addition of the initiator solution was 2ml per minute initially.
  • a suitable rate of polymerization was maintained by control of initiator addition rate, external cooling, and agitator speed. Polymerization was continued to a conversion of 70% as determined by attainment of a specific gravity of 1.053g/cc of the emulsion.
  • the polymerization was stopped by addition of 1.40 parts per hundred monomer of an aqueous emulsion containing 1.76% phenothiazine, 2.08% p-tertiarybutyl catechol, 5% sodium dodecylbenzene sulfonate, and 67.6% toluene. Unreacted monomer was steam-stripped from the latex and the stripped latex was acidified to a pH of 5.5-5.6 with a 10% acetic acid solution containing 2% of the sodium salt of a condensate of formaldehyde and naphthalenesulfonic acid. The polymer was isolated on a freeze roll and - ir dried at 100°C.
  • the resultant xanthogen disulfide-modified polymer ha ⁇ a Mooney viscosity, MLj + 4 @100°C, of 50 and contained 4.23% copolymerized units of 2,3-dichloro- 1,3-butadiene.
  • the copolymer was compounded with the components shown in Table I.
  • An A-mount specimen was prepared and tested to determine complex dynamic stiffness, tan delta, durability, and creep resistance of the cured copolymer composition. Results are shown in Table I.
  • Two xanthogen disulfide-modified copolymers were prepared in substantially the same manner as described in Example 1 using the same components and conditions except that the amounts of diisopropyl xanthogen disulfide added and conversion were varied as shown in Table II. Mooney viscosities, ML1+4 @ 100°C, of the products are also shown in Table II.
  • a sulfur-modified chloroprene polymer was prepared essentially in accordance with the procedure of Example 1 of U.S. Patent 4,124,754 using 0.36 parts sulfur per 100 parts chloroprene and 70% polymerization conversion.
  • the resultant sulfur-modified polymer had a Mooney viscosity MLj + 4 @100 °C of 50.
  • a compounded polymer blend was prepared by mixing the components shown in Table III in a Banbury internal mixer. A sample of the compounded polymer blend was formed into an A-mount test specimen. Physical properties of the cured copolymer blend are reported in Table III.
  • a latex blend of the xanthogen disulfide-modified copolymer of Example 1 and the sulfur-modified polymer of Example 3 was prepared as follows. Fifty-three parts of steam-stripped Example 1 emulsion (37.98% solids) was blended with 47 parts of steam-stripped Example 3 emulsion (41.83% solids). The resultant emulsion blend was acidified to a pH of 5.6 with a 10% aqueous acetic acid solution containing 2% of a condensation product of formaldehyde and naphthalene sodium sulfonate. The acidified emulsion was then isolated on a freeze roll. The polymer blend was air- dried at 100°C.
  • the blend had a Mooney viscosity, ML ⁇ + 4 @ 100°C, of 50.7.
  • This polymer is designated Polymer Blend A. It was compounded on a mill with the components shown in Table IV and an A-mount test specimen was prepared from the compounded composition. Physical properties of the cured copolymer blend composition are also shown in Table IV.

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

Abstract

Sont décrits des copolymères de chloroprène modifié par du disulfure de xanthogène à haute élasticité et des mélanges de ceux-ci avec des polymères de chloroprène modifié par du soufre, qui conviennent notamment pour des applications dynamiques à haute température, telles que dans des supports moteur.
EP94923913A 1993-08-04 1994-07-29 Composition copolymere de polychloroprene Withdrawn EP0712418A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US102028 1987-09-29
US10202893A 1993-08-04 1993-08-04
PCT/US1994/007458 WO1995004766A1 (fr) 1993-08-04 1994-07-29 Composition copolymere de polychloroprene

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EP0712418A1 true EP0712418A1 (fr) 1996-05-22

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JP2009024046A (ja) * 2007-07-17 2009-02-05 Bridgestone Corp 防振ゴム組成物及びそれを用いてなる防振ゴム
JP5255255B2 (ja) * 2007-10-22 2013-08-07 電気化学工業株式会社 水性接着剤
JP6092707B2 (ja) * 2013-05-20 2017-03-08 デンカ株式会社 クロロプレンゴム組成物、クロロプレンゴム及びその製造方法
CA2918437C (fr) 2013-07-16 2018-07-03 Skinprotect Corporation Sdn Bhd Compositions de formation de film elastomere et articles fabriques a partir du film elastomere
CN105793290B (zh) * 2013-11-26 2018-04-27 电化株式会社 硫改性聚氯丁二烯
WO2018110369A1 (fr) * 2016-12-14 2018-06-21 デンカ株式会社 Caoutchouc de chloroprène modifié par un xanthogène ainsi que composition de caoutchouc associée, et corps moulé par vulcanisation
JP6753035B2 (ja) * 2018-07-23 2020-09-09 壽男 小野 ゴム組成物
JP7263386B2 (ja) * 2018-11-08 2023-04-24 デンカ株式会社 クロロプレン・不飽和ニトリル共重合体組成物及び加硫成形体
US11993671B2 (en) 2018-11-09 2024-05-28 Denka Company Limited Chloroprene/unsaturated nitrile copolymer, chloroprene/unsaturated nitrile copolymer composition and vulcanized molded article

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DE2156452C2 (de) * 1971-11-13 1981-09-17 Bayer Ag, 5090 Leverkusen Verfahren zur Polymerisation von Chloropren zu einem benzollöslichen Chloroprenpolymeren und Mischung aus dem benzollöslichen Polymeren mit einem benzolunlöslichen Chloroprenpolymeren
GB1404766A (en) * 1971-12-07 1975-09-03 Bp Chem Int Ltd Chloroprene styrene copolymers
DE3725042A1 (de) * 1987-07-29 1989-02-09 Bayer Ag Polychloroprenmischungen

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CN1128540A (zh) 1996-08-07
JPH09501459A (ja) 1997-02-10
WO1995004766A1 (fr) 1995-02-16

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