CA1102045A - 2,5-dimercapto-1,3,4-thiadiazole as a cross-linker for saturated, halogen-containing polymers - Google Patents
2,5-dimercapto-1,3,4-thiadiazole as a cross-linker for saturated, halogen-containing polymersInfo
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- CA1102045A CA1102045A CA313,794A CA313794A CA1102045A CA 1102045 A CA1102045 A CA 1102045A CA 313794 A CA313794 A CA 313794A CA 1102045 A CA1102045 A CA 1102045A
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Abstract
Abstract Of The Disclosure It has been found that saturated, halogen-containing polymers can be cross-linked to yield stable vulcanizates using 2,5-dimercapto-1,3,4-thiadiazole in the presence of certain basic materials in normal vulcanization procedures.
Description
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This invention relates to the cross-linking of halogen-containing polymers. More particularly, this invention relates to a method of cross-linking saturated, halogen-containing polymers with 2,5-dimercapto-1,3,4-thiadiazole and certain basic materials.
This invention relates to the cross-linking of halogen-containing polymers. More particularly, this invention relates to a method of cross-linking saturated, halogen-containing polymers with 2,5-dimercapto-1,3,4-thiadiazole and certain basic materials.
2,5-Dimercapto-1,3,4-thiadiazole is a known compound and has been reported in British Patent No. 974,915 as a curing agent for certain unsatur-ated, halogen-containing polymers (i.e., chlorobutyl rubber and polychloro-prene elastomers). However, the compositions disclosed in British Patent No.
974,915 will not cross-link saturated, halogen-containing polymers.
It has now been discovered that saturated, halogen-containing poly-mers can be cross-linked to yield stable vulcanizates with good aging, com-pression set resistance, and insolubility in organic solvents using 2,5-dimercapto-1,3,4-thiadiazole, or a concentrate thereof in a binder material, in the presence of certain basic materials in normal vulcanization procedures.
Accordingly, in one aspect this invention relates to a process of cross-linking a saturated halogen-containing polymer which comprises heating said polymer in the presence of 2,5-dimercapto-1,3,4-thiadiazole and a basic material se- `!
lected from amines, other than tributylamine~ dicyclohexylamine, hexamethylene tetramine and N,N~-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110 C. and a pK value above about 9.5.
In another aspect, the invention provides a saturated halogen-containing polymer cross-linked by heating in the presence of 2,5-dimercapto-1,3,4-thiadiazole and a basic material selected from amines, other than tri-butylamine, dicyclohexylamine, hexamethylene tetramine and N,N'-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110 C. and a pK value -- 1 -- 3b~
above about 9.5.
In yet another aspect the invention provides a cross-linkable com-position comprising (a~ a saturated, halogen-containing polymer, (b) 2,5-dimercapto-1,3,4-thiadiazole and (c) a basic material selected from amines, other than tributylamine, dicyclohexylamine, hexamethylene tetramine and N,NI-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110 C, and a pK value above about 9.5.
The term "pK value" refers to the dissociation constants of bases and acids in aqueous solution. Representative values of pK are shown in the Handbook of Chemistry and Physics, 53rd Edition, The Chemical Rubber Co., pages D-117 to D-121 (1972-1973).
The saturated, halogen-containing polymers to be cross-linked in accordance with this invention contain at least about 2%, most preferably about 5%, by weight of halogen and less than 0.1 mole % ethylenic unsaturation.
Typical of the saturated, halogen-containing polymers are homopolymers of epichlorohydrin, copolymers of epichlorohydrin and ethylene oxide or propylene oxide, chlorinated high-density polyethylene, chlorosulfonated polyethylene, poly(vinyl chloride), poly(vinyl fluoride), poly(chloroalkylacrylates), poly-(vinylidene chloride), and copolymers of vinylidene fluoride and hexafluoro-propylene. In addition, the process of this invention may be used to cross-link blends of saturated, halogen-containing polymers.
Typical amines having a boiling point above about 110 C. and a pK
value above about 9.5 are the aliphatic and cycloaliphatic primary, secondary and tertiary amines having 5 to 20 carbon atoms, such as n-hexylamine, octyl-amine, dibutylamine, tributylamine, trioctylamine, di(2-ethylhexyl)amine, dicyclohexylamine, and hexamethylene diamine. Various amounts of amine can 2~4C~
be used, depending upon the degree of cross-linking desired and the presence of inorganic basic material. In general, the amount of amine used will be from about 0.25% to about 10%, more preferably from about 0.5% to about 5%, most preferably from about 1.0% to about 3% based on the weight of the polymer.
For economic reasons, it may be desirable to substitute less expensive inor-ganic basic material for some of the amine. However, at least 0.1% of amine ; based on the weight of the polymer must be present with any inorganic basic material to obtain cross-linking of the polymer.
Typical inorganic bases used in combination with the above amine are the alkali metal hydroxides, alkaline earth metal oxides, hydroxides and their salts with weak acids such as sodium hydroxide, sodium carbonate, potassium hydroxide, magnesium oxide, calcium oxide, calcium hydroxide, barium oxide, calcium carbonate, and magnesium carbonate.
In addition to the cross-linking agent and basic material, other ingredients can also be incorporated. The .. ~ .
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types of additives commonly used in rubber vulcanization can be used, as, for example, extenders, fillers, pigments, plasticizers, softeners, etc. rrhe presence of a filler and, in particular, carbon black, is beneficial and, as in hydro-carbon rubber compounding, gives very advantageous results.
There are many cases, however, in which a filler is not required or desired and excellent results are achieved when only the cross-linking agent and baslc materials are added.
Also, most of the saturated, halogen-containing polymers contain a small amount (i.e., from about O.l% to about 2%
- by weight) of antioxidant, added at the time of their prep-aration. It may be desirable in some cases to add a small additional amount of antioxidant before or at the time of cross-linking the polymer. Exemplary of the preferable antioxidants are phenyl-~-naphthylamine, di-~-naphthyl-p-phenylenediamine, sym-di-~-naphthyl-p-phenylenediamine, N-isooctyl-p-amino phenol, the reaction product of diphenyl-amine and acetone, polymerized trimethyldihydroquinoline, 4,4'-thio-bis(6-tert-butyl-m-cresol), the reaction product of crotonaldehyde and 3-methyl-6-tert-butyl-phenol, nickel dibutyldithiocarbamate, the zinc salt of 2-mercaptobenzim-idazole, and nickel dimethyldithiocarbamate.
Particularly in the case of epichlorohydrin polymers, it may be advantageous to add at least one carboxylic acid to the cross-l;nkable composition to act as a scorch re-tarder during the compounding step if calcium oxide or calcium hydroxide is used as an inorganic basic material.
Malic acid and N-acetylanthranilic acid are especially usefuL.
The cross-linking agent, basic material and additives, if any are used, can be incorporated or admixed with the polymer in any desired fashion. For example, they can be uniformly blended with a polymer by simply milling on a conventional rubber mill or mixing in a Banbury mixer. By this means, the cross-linking agent and basic material are uniformly distributed throughout the polymer and uniform cross-linking is effected when the bLend ls subjected to heat. It is generally preferable to mlll at temperatures /
LS
within the range of from about 20C. to about 95C.
However, the blends are generally scorch-resistant below about 120C., unless compounded with a large amount of organic basic material. Other methods of admixing the cross-linking agent with the polymer will be apparent to those skilled in the art.
The condltions under which the cross-linking is effec-ted can be varied over a wide range. Cross-linking can be effected in minutes at elevated temperatures or in days at temperatures slightly above room temperature. In general, the cross-linking temperature will be within the range of from about 30C. to about 280C., more preferably from about 135C. to about 23SC., and most preferably from about 150C. to about 205C. The time will vary in-versely with the temperature and with concentration ofbasic material will range from about 30 seconds to 70 hours, preferably from about 30 seconds to about 120 minutes. While the cross-linking process can be conducted in air at normal atmospheric pressure, it will generally be conducted in a metal mold under a compression of at least about 50 p.s.i. or in a steam autoclave at the pressure required for the desired temperature.
For ease in incorporating the 2,5-dimercapto-1,3,4-thiadiazole into the cross-linkable polymer, and to avoid the use of powders in the compounding step, it may be desir-able to prepare the 2,5-dimercapto-1,3,4-thiadiazole as a concentrate in a binder or carrier which can be added, along with the basic materials, in small amounts to the polymer composition without adverse effect on the properties of the cross-linked composition. Particularly advantageous binders or carriers are polymers which may or may not be cross-linkable by the cross-linking agent. Suitable materials, in addition to the cross-linkable polymers, are, for example, ethylene-propylene rubber, ethylene-propylene terpolymers, ~- 35 butadiene-styrene rubber, natural rubber, low-density poly-ethylene, amorphous polypropylene and polyisobutylene.
Concentrations of the 2,5-dimercapto-1,3,4-thiadiazole in the binders can vary from about 15% to about 9Q%, preferably ~z~g~
from about 30% to about 75%. Other materials which can advantageously be incorporated in the concentrates are scorch retarders, antioxidants and non basic fillers. It is normally undesirable to incorporate the basic material in the concentrate. These polymer concentrates are normally stored and used in the form of sheets~ extruded pellets or rods. Other suitable binders or carriers for use in the preparation of such easily handled concentrates are waxes, resins, or other low-melting solids. Typical useful materials are paraffin wax, stearic acid, microcrystalline wax, rosin, rosin esters and hydrocarbon resins.
The cross-linked products of this invention can be utilized to make hoses, tubes, etc., for use as fuel lines carrying hydrocarbon fuels.
The following examples will illustrate the process of cross-linking in accordance with this invention. All parts and percentages are by weight unless otherwise stated.
Examples 1 - 11 These examples illustrate the cross-linking of chlorinated poly-ethylene using various organic amines.
A masterbatch was prepared of the following:
Parts Chlorinated polyethylene (36% chlorine by weight) 100 Stearic acid High abrasion furnace black 45 Processing oil 8 Phenyl-beta-naphthylamine (antioxidant) 2,5-Dimercapto-1,3,4-thiadiazole 2 ,. . ~., 1~2S~L5 To portions of the masterbatch were added 2.66 x 10 2 moles per 100 parts of polymer of one of the following amines. To other portions of the masterbatch were added 4 parts of magnesium oxide plus the above amount of amine. Each formulation is then heated at 166 C. for twelve minutes in an oscillating disc Rheometer (American Standard Testing Method D2705-68T). The amines, their boiling points and pK values and the torque (in inch-pounds) of each sample are tabulated below.
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E~ ~
. a~
~-~ ~ O ~ O ~ ~ C~
h~ cX~l e~' ~ u~ ~ u) d~ ~ d D c~ ~1 g E-~l ,;, ~ a~ .
o o a~ ~ ~D a)o ~ ~ ~ b~O
b rl C`l O 00~1 ~0 ~' a~ c~
O
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J ~ ~ N I N I ~ S O
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g Examples 12-14 These examples illustrate the cross-linking of chlori-nated polyethylene using various amine salts of 2,5-dimercapto-1,3,4-thiadiazole.
Ingredients 12 13 14 Chlorinated polyethylene (36~ chlorine by weight) 100100 100 Semi-reinforcing furnace black 80 80 80 Polymeric plasticizer 20 20 20 Dioctyl adipate (plasticizer) 10 10 10 Magnesium oxide 4 4 4 Mono(dicyclohexylammonium)-1,3,4-thiadiazole-5-thiol-2-thioate 2.64 Bis(dibutylammonium)-1,3,4-thiadiazole-2,5-dithioatemonohydrate - 3.28 Mono(2,2'-diethyldihexylammonium)-1,3,4-thiadiazole-2,5-dithioate - - 3.12 The above formulations are cross-linked by heating for twelve minutes at 166C. in an oscillating disc rheometer.
Minimum Torque (inch-lbs.) 12 10 9 , Torque after 6 minutes 41 38 40 Torque after 12 minutes 43 40 47 : .
Examples 15-18 These examples illustrate the cross-linking of various saturated halogenated polymers in accordance with this invention.
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Example Example Example 15 Example 1617 18 Ingredients a b c a b c a b a b __ _ Chlorinated poly-ethylene - 36~
chlorine by weight 100 100 100 - - - - - - -Polyvinyl chloride - - - 100 100 100 - - - -Chlorosulfonated polyethylene - - - - - - 100 100 10 Epichlorohydrin homopolymer - - - - - - - - 100 100 Alkyl phthalate plasticizer - - - 40 40 40 Stearic acid 15 (processing aid) - - - - - - - - 3 3 Semi-reinforcing furnace black 80 80 80 - - - 40 40 Fast extruding furnace black - - - - - - - - 50 50 20 Aromatic processing aid 20 20 20 Polymeric plas-ticizer 10 10 10 - - - - - - -Dioctyl adipate - 25 (plasticizer) 10 10 10 Barium-Cadmium Complex (stabilizer) Magnesium oxide 5 5 5 Calcium hydroxide - - - 10 10 - - - 4 Calcium carbonate - - - - - - 10 2,5-Dimercapto-1,3,4-thiadiazole 2 2 2 - 2 2 1.5 2 1.5 2 Dicyclohexylamine (pK 3.1, b.p. 256) - - 2 5 5 5 22 1 5 Aniline-butyraldehyde condensate - 2 Aniline-acetaldehyde-butyraldehyde condensate 2 40 The above formulations are heated at the temperature re-cited below in an oscillating disc rheometer.
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Example Example Example 15 Example 16 17 18 a b c a b c a b a b Temperature, C. 182 182 182 182 182 160149 160 149 160 5 Minimum Torque (inch-lbs.) 11 11 13 6 - 4650 - 22 15 Maximum Torque (inch-lbs.) 55 56 73 a 62 92100 76136 147 Time to 90% cure -10 minutes 3 3 6 N.C. 1 4 50 0.2 9.5 1.8 a = no increase in torque over a period of 30 minutes .
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974,915 will not cross-link saturated, halogen-containing polymers.
It has now been discovered that saturated, halogen-containing poly-mers can be cross-linked to yield stable vulcanizates with good aging, com-pression set resistance, and insolubility in organic solvents using 2,5-dimercapto-1,3,4-thiadiazole, or a concentrate thereof in a binder material, in the presence of certain basic materials in normal vulcanization procedures.
Accordingly, in one aspect this invention relates to a process of cross-linking a saturated halogen-containing polymer which comprises heating said polymer in the presence of 2,5-dimercapto-1,3,4-thiadiazole and a basic material se- `!
lected from amines, other than tributylamine~ dicyclohexylamine, hexamethylene tetramine and N,N~-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110 C. and a pK value above about 9.5.
In another aspect, the invention provides a saturated halogen-containing polymer cross-linked by heating in the presence of 2,5-dimercapto-1,3,4-thiadiazole and a basic material selected from amines, other than tri-butylamine, dicyclohexylamine, hexamethylene tetramine and N,N'-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110 C. and a pK value -- 1 -- 3b~
above about 9.5.
In yet another aspect the invention provides a cross-linkable com-position comprising (a~ a saturated, halogen-containing polymer, (b) 2,5-dimercapto-1,3,4-thiadiazole and (c) a basic material selected from amines, other than tributylamine, dicyclohexylamine, hexamethylene tetramine and N,NI-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110 C, and a pK value above about 9.5.
The term "pK value" refers to the dissociation constants of bases and acids in aqueous solution. Representative values of pK are shown in the Handbook of Chemistry and Physics, 53rd Edition, The Chemical Rubber Co., pages D-117 to D-121 (1972-1973).
The saturated, halogen-containing polymers to be cross-linked in accordance with this invention contain at least about 2%, most preferably about 5%, by weight of halogen and less than 0.1 mole % ethylenic unsaturation.
Typical of the saturated, halogen-containing polymers are homopolymers of epichlorohydrin, copolymers of epichlorohydrin and ethylene oxide or propylene oxide, chlorinated high-density polyethylene, chlorosulfonated polyethylene, poly(vinyl chloride), poly(vinyl fluoride), poly(chloroalkylacrylates), poly-(vinylidene chloride), and copolymers of vinylidene fluoride and hexafluoro-propylene. In addition, the process of this invention may be used to cross-link blends of saturated, halogen-containing polymers.
Typical amines having a boiling point above about 110 C. and a pK
value above about 9.5 are the aliphatic and cycloaliphatic primary, secondary and tertiary amines having 5 to 20 carbon atoms, such as n-hexylamine, octyl-amine, dibutylamine, tributylamine, trioctylamine, di(2-ethylhexyl)amine, dicyclohexylamine, and hexamethylene diamine. Various amounts of amine can 2~4C~
be used, depending upon the degree of cross-linking desired and the presence of inorganic basic material. In general, the amount of amine used will be from about 0.25% to about 10%, more preferably from about 0.5% to about 5%, most preferably from about 1.0% to about 3% based on the weight of the polymer.
For economic reasons, it may be desirable to substitute less expensive inor-ganic basic material for some of the amine. However, at least 0.1% of amine ; based on the weight of the polymer must be present with any inorganic basic material to obtain cross-linking of the polymer.
Typical inorganic bases used in combination with the above amine are the alkali metal hydroxides, alkaline earth metal oxides, hydroxides and their salts with weak acids such as sodium hydroxide, sodium carbonate, potassium hydroxide, magnesium oxide, calcium oxide, calcium hydroxide, barium oxide, calcium carbonate, and magnesium carbonate.
In addition to the cross-linking agent and basic material, other ingredients can also be incorporated. The .. ~ .
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Z~
types of additives commonly used in rubber vulcanization can be used, as, for example, extenders, fillers, pigments, plasticizers, softeners, etc. rrhe presence of a filler and, in particular, carbon black, is beneficial and, as in hydro-carbon rubber compounding, gives very advantageous results.
There are many cases, however, in which a filler is not required or desired and excellent results are achieved when only the cross-linking agent and baslc materials are added.
Also, most of the saturated, halogen-containing polymers contain a small amount (i.e., from about O.l% to about 2%
- by weight) of antioxidant, added at the time of their prep-aration. It may be desirable in some cases to add a small additional amount of antioxidant before or at the time of cross-linking the polymer. Exemplary of the preferable antioxidants are phenyl-~-naphthylamine, di-~-naphthyl-p-phenylenediamine, sym-di-~-naphthyl-p-phenylenediamine, N-isooctyl-p-amino phenol, the reaction product of diphenyl-amine and acetone, polymerized trimethyldihydroquinoline, 4,4'-thio-bis(6-tert-butyl-m-cresol), the reaction product of crotonaldehyde and 3-methyl-6-tert-butyl-phenol, nickel dibutyldithiocarbamate, the zinc salt of 2-mercaptobenzim-idazole, and nickel dimethyldithiocarbamate.
Particularly in the case of epichlorohydrin polymers, it may be advantageous to add at least one carboxylic acid to the cross-l;nkable composition to act as a scorch re-tarder during the compounding step if calcium oxide or calcium hydroxide is used as an inorganic basic material.
Malic acid and N-acetylanthranilic acid are especially usefuL.
The cross-linking agent, basic material and additives, if any are used, can be incorporated or admixed with the polymer in any desired fashion. For example, they can be uniformly blended with a polymer by simply milling on a conventional rubber mill or mixing in a Banbury mixer. By this means, the cross-linking agent and basic material are uniformly distributed throughout the polymer and uniform cross-linking is effected when the bLend ls subjected to heat. It is generally preferable to mlll at temperatures /
LS
within the range of from about 20C. to about 95C.
However, the blends are generally scorch-resistant below about 120C., unless compounded with a large amount of organic basic material. Other methods of admixing the cross-linking agent with the polymer will be apparent to those skilled in the art.
The condltions under which the cross-linking is effec-ted can be varied over a wide range. Cross-linking can be effected in minutes at elevated temperatures or in days at temperatures slightly above room temperature. In general, the cross-linking temperature will be within the range of from about 30C. to about 280C., more preferably from about 135C. to about 23SC., and most preferably from about 150C. to about 205C. The time will vary in-versely with the temperature and with concentration ofbasic material will range from about 30 seconds to 70 hours, preferably from about 30 seconds to about 120 minutes. While the cross-linking process can be conducted in air at normal atmospheric pressure, it will generally be conducted in a metal mold under a compression of at least about 50 p.s.i. or in a steam autoclave at the pressure required for the desired temperature.
For ease in incorporating the 2,5-dimercapto-1,3,4-thiadiazole into the cross-linkable polymer, and to avoid the use of powders in the compounding step, it may be desir-able to prepare the 2,5-dimercapto-1,3,4-thiadiazole as a concentrate in a binder or carrier which can be added, along with the basic materials, in small amounts to the polymer composition without adverse effect on the properties of the cross-linked composition. Particularly advantageous binders or carriers are polymers which may or may not be cross-linkable by the cross-linking agent. Suitable materials, in addition to the cross-linkable polymers, are, for example, ethylene-propylene rubber, ethylene-propylene terpolymers, ~- 35 butadiene-styrene rubber, natural rubber, low-density poly-ethylene, amorphous polypropylene and polyisobutylene.
Concentrations of the 2,5-dimercapto-1,3,4-thiadiazole in the binders can vary from about 15% to about 9Q%, preferably ~z~g~
from about 30% to about 75%. Other materials which can advantageously be incorporated in the concentrates are scorch retarders, antioxidants and non basic fillers. It is normally undesirable to incorporate the basic material in the concentrate. These polymer concentrates are normally stored and used in the form of sheets~ extruded pellets or rods. Other suitable binders or carriers for use in the preparation of such easily handled concentrates are waxes, resins, or other low-melting solids. Typical useful materials are paraffin wax, stearic acid, microcrystalline wax, rosin, rosin esters and hydrocarbon resins.
The cross-linked products of this invention can be utilized to make hoses, tubes, etc., for use as fuel lines carrying hydrocarbon fuels.
The following examples will illustrate the process of cross-linking in accordance with this invention. All parts and percentages are by weight unless otherwise stated.
Examples 1 - 11 These examples illustrate the cross-linking of chlorinated poly-ethylene using various organic amines.
A masterbatch was prepared of the following:
Parts Chlorinated polyethylene (36% chlorine by weight) 100 Stearic acid High abrasion furnace black 45 Processing oil 8 Phenyl-beta-naphthylamine (antioxidant) 2,5-Dimercapto-1,3,4-thiadiazole 2 ,. . ~., 1~2S~L5 To portions of the masterbatch were added 2.66 x 10 2 moles per 100 parts of polymer of one of the following amines. To other portions of the masterbatch were added 4 parts of magnesium oxide plus the above amount of amine. Each formulation is then heated at 166 C. for twelve minutes in an oscillating disc Rheometer (American Standard Testing Method D2705-68T). The amines, their boiling points and pK values and the torque (in inch-pounds) of each sample are tabulated below.
~ZQ~S
, I ~ x~
b o ~ O C`l C`l ~1 a~ .
u~ ~ ,1 ~ ~ d~ OD G~ ~ 0 0~
o X ~ ~ d lD OD ~7Il~ U~) ~) r~l r~l N0 E-l ~
E~ ~
. a~
~-~ ~ O ~ O ~ ~ C~
h~ cX~l e~' ~ u~ ~ u) d~ ~ d D c~ ~1 g E-~l ,;, ~ a~ .
o o a~ ~ ~D a)o ~ ~ ~ b~O
b rl C`l O 00~1 ~0 ~' a~ c~
O
') O ~0~ ~ O ~ F d o d-d~ OD OU) O O O d- ~ 1 4 .>
'; C~C~
.~ ,s d d ~ ~ X
S- ~1rl~1 ~ F3~tc~ c~ o I ,1 * ~j ~ ~ ~~ æ ~ ~O ~O d ~ ~ ~
J ~ ~ N I N I ~ S O
O J,~ , " ~ O ~1 ' ~, . -- 8 --`
g Examples 12-14 These examples illustrate the cross-linking of chlori-nated polyethylene using various amine salts of 2,5-dimercapto-1,3,4-thiadiazole.
Ingredients 12 13 14 Chlorinated polyethylene (36~ chlorine by weight) 100100 100 Semi-reinforcing furnace black 80 80 80 Polymeric plasticizer 20 20 20 Dioctyl adipate (plasticizer) 10 10 10 Magnesium oxide 4 4 4 Mono(dicyclohexylammonium)-1,3,4-thiadiazole-5-thiol-2-thioate 2.64 Bis(dibutylammonium)-1,3,4-thiadiazole-2,5-dithioatemonohydrate - 3.28 Mono(2,2'-diethyldihexylammonium)-1,3,4-thiadiazole-2,5-dithioate - - 3.12 The above formulations are cross-linked by heating for twelve minutes at 166C. in an oscillating disc rheometer.
Minimum Torque (inch-lbs.) 12 10 9 , Torque after 6 minutes 41 38 40 Torque after 12 minutes 43 40 47 : .
Examples 15-18 These examples illustrate the cross-linking of various saturated halogenated polymers in accordance with this invention.
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Example Example Example 15 Example 1617 18 Ingredients a b c a b c a b a b __ _ Chlorinated poly-ethylene - 36~
chlorine by weight 100 100 100 - - - - - - -Polyvinyl chloride - - - 100 100 100 - - - -Chlorosulfonated polyethylene - - - - - - 100 100 10 Epichlorohydrin homopolymer - - - - - - - - 100 100 Alkyl phthalate plasticizer - - - 40 40 40 Stearic acid 15 (processing aid) - - - - - - - - 3 3 Semi-reinforcing furnace black 80 80 80 - - - 40 40 Fast extruding furnace black - - - - - - - - 50 50 20 Aromatic processing aid 20 20 20 Polymeric plas-ticizer 10 10 10 - - - - - - -Dioctyl adipate - 25 (plasticizer) 10 10 10 Barium-Cadmium Complex (stabilizer) Magnesium oxide 5 5 5 Calcium hydroxide - - - 10 10 - - - 4 Calcium carbonate - - - - - - 10 2,5-Dimercapto-1,3,4-thiadiazole 2 2 2 - 2 2 1.5 2 1.5 2 Dicyclohexylamine (pK 3.1, b.p. 256) - - 2 5 5 5 22 1 5 Aniline-butyraldehyde condensate - 2 Aniline-acetaldehyde-butyraldehyde condensate 2 40 The above formulations are heated at the temperature re-cited below in an oscillating disc rheometer.
~7 Z~
Example Example Example 15 Example 16 17 18 a b c a b c a b a b Temperature, C. 182 182 182 182 182 160149 160 149 160 5 Minimum Torque (inch-lbs.) 11 11 13 6 - 4650 - 22 15 Maximum Torque (inch-lbs.) 55 56 73 a 62 92100 76136 147 Time to 90% cure -10 minutes 3 3 6 N.C. 1 4 50 0.2 9.5 1.8 a = no increase in torque over a period of 30 minutes .
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Claims (28)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. The process of cross-linking a saturated, halogen-containing poly-mer which comprises heating said polymer in the presence of 2,5-dimercapto-1, 3,4-thidiazole and a basic material selected from amines, other than tributylamine, dicyclohexylamine, hexamethylene tetramine and N,N'-dicinnamy-lidine-1,6-hexanediamine, having a boiling point above about 110°C. and a pKa value above about 9.5.
2. The process of claim 1 wherein the saturated halogen-containing polymer is a homopolymer of epichlorohydrin.
3. The process of claim 1 wherein the saturated halogen-containing polymer is a copolymer of epichlorohydrin and ethylene oxide.
4. The process of claim 1 wherein the saturated halogen-containing polymer is chlorinated polyethylene.
5. The process of claim 1 wherein the saturated halogen-containing polymer is poly(vinyl chloride).
6. The process of claim 1 wherein the saturated halogen-containing polymer is chlorosulfonated polyethylene.
7. The process of claim 1, 2 or 3 wherein the amine is selected from primary, secondary and tertiary aliphatic amines containing four to twenty carbon atoms.
8. The process of claim 4, 5 or 6 wherein the amine is selected from primary secondary and tertiary amines containing four to twenty carbon atoms.
9. The process of claim 1, 2 or 3 wherein the amine is 2,2'-diethyldi-hexylamine.
10. The process of claim 4, 5 or 6 wherein the amine is 2,2'-diethylhexy-lamine.
11. The process of claim 1, 2 or 3 wherein the amine is dicyclohexylethy-lamine.
12. The process of claim 4, 5 or 6 wherein the amine is dicyclohexyl-ethylamine.
13. The process of claim 1, 2 or 3 wherein the amine is cyclohexyldi-ethylamine.
14. The process of claim 4, 5 or 6 wherein the amine is cyclohexyl-diethylamine.
15. The process of claim 1, 2 or 3 wherein the amine is benzylmethyl-amine.
16. The process of claim 4, 5 or 6 wherein the amine is benzylmethyl-amine.
17. The process of claim 1, 2 or 3 wherein the amine is 2-methylpi-peridine.
18. The process of claim 4, 5 or 6 wherein the amine is 2-methylpiperi-dine.
19. The process of claim 1, 2 or 3 wherein the amine is di-n-butylamine.
20. The process of claim 4, 5 or 6 wherein the amine is di-n-butylamine.
21. The process of claim 1, 2 or 3 wherein the amine is tri-n-octylamine.
22. The process of claim 4, 5 or 6 wherein the amine is tri-n-octylamine.
23. The process of claim 1, 2 or 3 wherein the amine is 1,5-diazobicyclo-[5.4.0]-undec-5-ene.
24. The process of claim 4, 5 or 6 wherein the amine is 1,5-diazobicyclo-[5.4.0]-undec-5-ene.
25. The process of claim 1, 2 or 3 wherein the amine is 1,5-diazobicyclo-[4.3.0]-non-5-ene.
26. The process of claim 4, 5 or 6 wherein the amine is 1,5-diazobicyclo-[4.3.0]-non-5-ene.
27. A saturated halogen-containing polymer cross-linked by heating in the presence of 2,5-dimercapto-1,3,4-thiadiazole and a basic material selected from amines, other than tributylamine, dicyclohexylamine, hexamethylene tetra-mine and N,N'-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110°C and a pKa value above about 9.5.
28. A cross-linkable composition comprising (a) a saturated, halogen-containing polymer, (b) 2,5-dimercapto-1,3,4-thiadiazole and (c) a basic material selected from amines, other than tributylamine, dicyclohexylamine, hexamethylene tetramine and N,N'-dicinnamylidine-1,6-hexanediamine, having a boiling point above about 110°C, and a pKa value above about 9.5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US94285678A | 1978-09-15 | 1978-09-15 | |
| US942,856 | 1978-09-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1102045A true CA1102045A (en) | 1981-05-26 |
Family
ID=25478706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA313,794A Expired CA1102045A (en) | 1978-09-15 | 1978-10-19 | 2,5-dimercapto-1,3,4-thiadiazole as a cross-linker for saturated, halogen-containing polymers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1102045A (en) |
-
1978
- 1978-10-19 CA CA313,794A patent/CA1102045A/en not_active Expired
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