GB1585928A - 2,5 - dimercapto - 1,3,4 - thiadiazole as a crosslinker for saturated halogen-containing polymers - Google Patents
2,5 - dimercapto - 1,3,4 - thiadiazole as a crosslinker for saturated halogen-containing polymers Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
To crosslink a saturated halogenated polymer, it is heated in the presence of a basic material and of 2,5-dimercapto-1,3,4-thiadiazole or of a salt of the latter and of the basic material. This process applies in particular to the preparation of crosslinked products suitable, inter alia, for the manufacture of pipes for conveying hydrocarbon fuels.
Description
(54) 2,5-DIMERCAPTO-1,3,4-THIADIAZOLE AS A CROSS-LINKER FOR
SATURATED HALOGEN-CONTAINING POLYMERS
(71) We, HERCULES INCORPORATED. a
Corporation organised under the laws of the State of Delaware, United States of
America, of 910 Market Street, City of
Wilmington, State of Delaware, United
States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: 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- 1,3,4thiadiazole and a basic material.
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 unsaturated, halogen-containing polymers (i.e., chlorobutyl rubber and polychloroprene elastomers). However, British
Patent No. 974,915 does not suggest the cross-linking of saturated, halogen-containing polymers.
It has now been discovered that saturated, halogen-containing polymers can be crosslinked to yield stable vulcanizates with good aging, compression 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. For purposes of this invention the term "basic material" is meant to includt both bases and materials which
become basic on heating to the crosslinking temperature. Accordingly, this invention relates to a process of cross-linking saturated, halogen-containing polymers with 2,5-dimercapto-1,3,4-thiadiazole in the presence of a basic material, either inorganic or organic, to activate cure. Optionally the thiadiazdle and the basic material have been prereacted.
The saturated, halogen-containing polymers of this invention contain at least 2%, mos preferably 5%, by weight of halogen.
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 hexafluoropropylene.
In addition, the process of this invention may be used to cross-link blends of saturated, halogen-containing polymers or saturated, halogen-containing polymers blended with other polymers. The only requirement is that there be sufficient saturated, halogencontaining polymer present in the blend to effect cross-linking.
As stated above, various bases or materials which will become basic on heating to the cross-linking temperature, i.e., basic materials, are employed as cure activators.
Typical inorganic basic materials are basic metal oxides, hydroxides and their salts with weak acids, for example, lead oxides, zinc oxide, magnesium oxide, calcium oxide, calcium hydroxide, barium oxide, zinc carbonate, lead acetate, barium carbonate, strontium carbonate, calcium carbonate, magnesium carbonate, sodium phenoxide and sodium acetate. The preferred inorganic basic materials are calcium oxide, calcium hydroxide, magnesium oxide and barium carbonate. Organic basic materials may be used either in place of, or in combination with, inorganic basic materials. Typical of these organic basic materials are various primary, secondary and tertiary amines, amine -salts and quaternary ammonium compounds.The preferred organic basic materials are tetramethylammonium bromide, tetrabutylammonium bromide, tetraéthyl- ammonium benzoate, tetraethylammonium acetate, tetraethylammonium nitrate, benzyltrimethylammonium bromide, 2-amino-2thiazoline, diazobicyclo - octane, hexamethylenetetramine, hexamethylenediamine carbamate, and N,Nl-dicinnamylidine-1,6- hexanediamine, dicyclohexylamine, diorthotolylguanidine, diphenylguanidine and the reaction product of butyraldehyde and aniline.
Mercaptides formed by reaction of the 2,5-dimercapto- 1,3 ,4-thiadiazole with a basic inorganic oxide or hydroxide may also be used as cross-linking agents alone or in combination with additional basic material.
Also, reaction products of organic amines wih the 2,5,dimercapto- 1,3,4-thiadiazole can be used as cross-linking agents either alone or in combination with an inorganic basic material.
In the case of many of the saturated, halogen-containing polymers in which the 2,5-dimercapto- 1,3,4-thiadiazole or its abovementioned reaction products with basic materials are relatively insoluble, such as poly(vinyl chloride), poly(vinyl fluoride), poly(chloroalkylacrylates), chlorinated polyethylene, homopolymers of epichlorohydrin, poly(vinylidene fluoride), copolymers of vinylidene fluoride and hexafluoropropylene, chlorosulfonated polyethylene and poly (vinylidene chloride), it may be desirable to use a combination of inorganic and organic basic materials. Dicyclohexylamine, di-orthotolylguanidine, diphenylguanidine or their salts, and the reaction product of butyraldehyde and aniline are particularly preferable organic basic materials for use in combination with inorganic basic materials.
It may be undesirable to use zinc oxide or zinc salts as the basic material in certain cases such as with chlorosulfonated polyethylene, chlorinated polyethylene, poly (vinyl chloride) or poly(vinylidene chloride), because zinc chloride formed in situ during the vulcanization process may cause undesirable degradation by breaking of the polymer chains.
Varied amounts of the cross-linking agent and basic material can be added, and the optimum amount will depend upon the degree of cross-linking desired. Generally, the amounts added (based on the weight of the polymer) will be within the following ranges: 2,5 - dimercapto - 1,3,4 - thiadiazole, from 0.1% to 20%, preferably from 0.25% to 5.0%; basic material (either organic or inorganic) from 0.25% to 50%, more preferably from 0.5% to 50%, most preferably from 1.0% to 20%; and, if organic basic material is used in combination with inorganic basic material, the amount of organic basic material may be from 0.01% to 5%, more preferably from 0.05% to 5%, most preferably from 0.1% to 2%.
In addition to the cross-linking agent and basic material, other ingredients can also be incorporated. The types of additives commonly used in rubber vulcanization can be used, as, for example, extenders, fillers, pigments, plasticizers and softeners. The presence of a filler and, in particular, carbon black, is beneficial and, as in hydrocarbon 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 basic materials are added. Also, most of the saturated, halogen-containing polymers contain a small amount (i.e. from 0.1% to 2% by weight of antioxidant, added at the time of their preparation. 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-lF- naphthylamine di-ss-naphthyl-p-phenylene- diamine, sym-di-.P-naphthyl-p-phenylenedi- amine, N-isooctyl-p-aminophenol, the reaction product of diphenylamine and acetone, polymerized trimethyldihydroquinoline, 4,41-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-mercaptobenzimidazole, and nickel dimethyldithiocarbamate.
Particularly in the case of epichlorohydrin polymers, it may be advantageous to add at least one carboxylic acid to the cross-linkable composition to act as a scorch retarder during the compounding step when calcium oxide or calcium hydroxide is used as the 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 is subjected to heat. It is generally preferable to mill at temperatures within the range of from about 20"C. to about 95"C. However, the blends are generally scorch-resistant below about -120 C., 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 conditions under which the crosslinking is effected can be varied over a wider 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 30"C. to 280 C., more preferably from 135"C. to 235"C., and most preferably from 1500C. to 2050C. The time will vary inversely with the temperature and will range from 30 seconds to 70 hours, preferably from 30 seconds to 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-di mercapto- 1 ,3,4-thiadiazole into the crosslinkable polymer, and to avoid the use of powders in the compounding step, it may be desirable to prepare the 2,5-dimercapto1,3,4-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, butadiene-styrene rubber, natural rubber, low-density polyethylene, amorphous polypropylene and polyisobutylene.Concentrations of the 2,5-dimercapto-1,3,4-thiadiazole in the binders can vary from 15% to 90%, preferably from 30% to 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 tie concentrate. These polymers 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, for example, to make hoses and tubes for use as fuel lines carrying hydrocarbon fuels.
In the following Examples, parts are given by weight.
Example 1
This example illustrates the preparation of a concentrate of 2,5-dimercapto-1,3,4thiadiazole in stearic acid.
The concentrate is prepared by dry blending the ingredients tabulated below, warming the concentrate blend to the melting point of the stearic acid, extruding the melted concentrate blend and cutting the extrudate into rods or pellets.
ingredients Parts 2,5-dimercapto- 1 ,3,4-thiadiazole ... ... 66.6
Stearic acid ... ... ... ... 16.7
Kaolin clay ... " ... ... ... ... 7.5
Polymeric plasticizer ... ... ... ... ... 9.2
Form ... ... ... ... ... ... white soft pellets
Suggested use in cross-linking ... ... epichlorohydrin copolymer
In the following examples a Farrel Size "B" Banbury mixer is used to compound the formulations. Ingredients are added to the mixer in the order listed in each example.
Example 2
Ingredients Parts
Epichlorohydrin-ethylene oxide copolymer (26% Cl) ... ... ... 100
DS-207 (Trademark for a mixture of dibasic lead salts of C1,--C,, fatty acids sold by National Lead Co.) (process aid) ... ... ... 1
Carbon black (reinforcing filler) ... ... ... ... ... ... 40
Nickel dimethyldithiocarbamate (antioxidant) ... ... ... ... 1
Magnesium oxide ... ... ... ... ... ,.. ... ... 4 2,5-dimercapto- 1 3,4-thiadiazole ... ... ... ... ... ... 1.5
Samples of the mixture are cross-linked by heating for 30 minutes at a temperature of 1600C in a compression mold.The physical properties of the cross-linked product are tabulated below:
Air Oven Aged Original 70 his. @ 1500C.
Tensile strength (p.s.i.) ... ... 1790 1785
% Elongation ... . . . ... .-.. 380 195 100% Modulus (p.s.i.) 845 1030
Shore A Hardness .. .. ... 77 79
% Compression Set (ASTM D-395,
Method B) ... ... ... 46
Example 3
Ingredients Parts
Epichlorohydrin-ethylene oxide copolymer (26% C1) ... ... ... 100
Hydrex 440 (Trademark for hydrogenatel fatty acids and glycerides sold
by Wallace and Tiernan Inc., Harchem Div.) (process aid) ... 1
Carbon black ... ... ... ... ... . 40
Nickel dibutyldithiocarbamate (antioxidant) ... 1
Calcium hydroxide ... . 3.5
Maleic acid (scorch retarder) ... ... ... ... 0.27
N-Acetylanthranilic acid (scorch retarder) ... ... ... 2.5
2,5-dimercapto-1,3,4-thiadiazole ... ...... ... 1.5
The formation is cross-linked by heating for 30 minutes at a temperature of 1600C.
in a compression mold. The cross-linked product has the following physical properties:
Air Oven Aged
Original 70 Hrs. @ 150 C.
Tensile Strength (p.s.i) ... 1735 1735
% Elongation ... 290 185
100% Modulus (p.s.i.) 925 1050
Shore A Hardness ... ... ... 77 77
% Compression Set (ASTM D-395,
Method B) ... ... ... ... 58.5
Mooney Scorch (at 1210C.) (ASTM
D-1646-68)
Minimum viscosity ... ... ... 30
Time in minutes for 3 point rise in
viscosity ... ... ... ... 7.7
Time in minutes for 5 point rise in
viscosity ... ... ... ... 8.7
Time in minutes for 10 point rise in
viscosity ... ... ... ... 10.3
Examples 4-5
ingredients Parts
Example 4 Example 5
Epichlorohydrin homopolymer (38% Cl) 100 100
DS-207 (Trademark for a mixture of di
basic lead salts of C16-C18 fatty acids
sold by National Lead Co.) (process
aid) ... ... ... ... 1 1
Carbon black (reinforcing filler) ...... 50 50
Nickel dimethyldithiocarbamate (anti-
oxidant) ... 1 1
Calcium oxide -.. ... ... ... 3 3 Tetramethylammonium bromide . 2.0 - Tetrabutylammonium bromide ... ... 0.1 2,5-Dimercapto-1,3,4-thiadiazole ... 1.0 1.0
The above formulations are cross-linked by heating for 30 minutes at a temperature of 160 C. in a compression mold. The cross-linked products have the following physical properties:
Example 4 Example S Air Over Air Oven Aged 70 hers. Aged 70 hrs Original @ 150 0C. Original @ 1500C.
Tensile strength (p.s.i.) ... 1850 2125 1540 1900
% Elongation ... 290 200 300 200
100%- Modulus (p.s.i.) . 900 1385 700 1175
Shore A Hardness 77 83 72 81
% Compression Set (ASTM 70 - 58
D-395, Method B) - Mooney scorch (at 1210C.)
(ASTM D-1646-68)
Minimum viscosity ... 38 34
Time in minutes for 3
point rise in viscosity 5.3 4.6
Time in minutes for 5
point rise in viscosity 6.1 5.2
Time in minutes for 10
point rise in viscosity 7.2 6.2 Examples 6-7 Ingredients Parts Example 6 Example 7
Chlorinated polyethylene (36% chlorine by weight) ... ... ... ... 100
Chlorinated polyethylene (48% chlorine 100
by weight) ... ...... ... - 100
Carbon black (reinforcing filler) ... ... 85
Magnesium oxide ... ... ... ... 4 4
Dioctyl adipate (plasticizer and softener) 15 15
Polymerized 1,2,-dihydro-2,2,4-trimethyl
quinoline (antioxidant) ... ... ... 0.1 0.1
Di-ortho-tolylguanidine ... ... .., 1 1 2,5-Dimercapto- 1 ,3,4thiadiazole ... 1.25 1.25
The above formulations are cross-linked by heating for 30 minutes at a temperature of 1600C. in a steam autoclave. The cross-linked products have the following physical properties:
Example 6 Example 7
Tensile Strength (p.s.i) ... ... ... 2010 2475
% Elongation ... ... ... ... 200 107
100% Modulus (p.s.i.) ... ... ... 1635 2315 Shore A Hardness ... ...... 86 91 Compression Set (ASTM D-395,
Method B) ... ... ... ... 66 82
Mooney scorch at 1210C.) (ASTM D-1646-68) ... ... ... ... ...
Minimum viscosity ... ... ... 69 56
Time in minutes for 3 point rise in
viscosity ... ... ... ... 14.0 12.3
Time in minutes for 5 point rise in
viscosity ... ... ... ... 20.0 15.2
Time in minutes for 10 point rise in
viscosity ... ... ... ... 25.0 21.0
Example 8
Ingredients Parts
Epichlorohydrin homopolymer ... ... ... ... ... ... 50
Hycar 1053 (low molecular weight medium acrylonitrile-butadiene copoly
mer manufactured by B. F. Goodrich: "Hycar' is a registered Trade
Mark) ... ... ... ... ... ... ... ... ... ... 50
DS-207 (Trademark for a mixture of dibasic lead salts of C16C1g fatty
acids sold by National Lead Co.) (process aid) ... ... ... ... 0.5
Zinch stearate (process aid) ... .. ... ... ... ...... 0.5
Carbon black (reinforcing filler) ... ... ... ... ... 45
Magnesium oxide ... ... ... ... ... ... ... ... 1.5
Zinc oxide* ... ,.. ... ... ... ... ... ... ... 5
Octylated diphenylamine (antioxidant) ... ... ... ... ... 1
Benzothiazyl disulfide* ... ... ... ... ... ... 0.5
Sulfur* ... ... ... ... ... ... ... ... ... ... 1.25
2,5-dimercapto- 1 3,4-thiadiazole ... ... ... ... ... ... 0.625
Tetramethylammonium bromide ... ... ... ... ... ... 1.0
*Curing agents for Hycar 1053
The formulation is cross-linked by heating for 30 minutes at a temperature of 160 C. in a compression mold. The crosslinked product has the following physical properties:
Tensile strength (p)s.i.) ... 3150
% Elongation ... ... 400
100% Modulus (p.s.i.) 585 - -Shore A Hardness .. 67
Example 9
Ingredients Parts
Epichlorohydrin-ethylene oxide copolymer (26%Cl) ... 100
Stearic acid (process - aid) ... ... ... ... ... ... 1 2,5-Dimercapto-1,3,4-thiadiazole ... ... ... 1.5
Tributylamine ... ... ... ... ... ... ... ... 5
The above formulation is cross-linked by heating at 1600C. for thirty minutes in an oscillating disc Rheometer (American
Testing Method D2705-68T). The properties measured are:
Minimum torque (inch-pounds) ... ... 6
Torque after 30 minutes (inch-pounds) 35
Torque after 60 minutes (inch-pounds) 40
Examples 10-11
Parts
Example 10 Example 11
Chlorinated polyethylene (36% chlorine
by weight) ... ... ... ... 100 100
Carbon black (reinforcing filler) ...... 85 85
Dioctyl phthalate (plasticizer and softener) 20 20 Magnesium oxide ... ... .. ...... 5 5
2,5-dimercapto-l ,3,4-thiadiazole ... .... 1.5 1.5 Diphenylguanidine ... ... ... 1.5
Butyraldehyde-aniline reaction product - 1.5
The above formulations are cross-linked by heating at 1600C. for thirty minutes in a compression mold. The physical properties of the cross-linked products are:
Example 10 Example 11
Tensile strength (p.s.i.) ... ... ... 2070 2120
% Elongation ... ... .... ... 250 240
100% Modulus (p.s.i.) ... ... ... 1100 1250
Shore A Hardness ... 80 81
Example 12
Ingredients Parts
Poly(vinyl chloride) ... ... ... ... ... ... ... ... 100
Santocizer 160 (phthalate ester plasticizer sold by Monsanto) ...... 40
Ba-Cd 1203 (coprecipitated Ba-Cd soap stabilizer sold by Ferro Corp). 1.2
Calcium carbonate ... ... ... ... ... ... ... . 20
2,5-dimercapto-1,3,4-thiadiazole ... ... ... ... ... 1.2
Butyraldehyde-aniline reaction product ... ... ... ... ... 1
The above formulation is heated at 1350 C. for - thirty minutes in an oscillating disc
Rheometer (American Standard Testing Method D2705-68T). Satisfactory cross-linking is obtained with noticeable discoloration.
Example 13
Ingredients Parts
Copolymers of vinylidene fluoride and hexa fluoropropylene ... ... 100
Calcium oxide ... ... ... ... ... ... ... ... ... 5
Di-ortho-tolylguanidine ... ... ... ... .. . ... ... ... 3 2,5-dimercapto-1,3,4-thiadiazole ... ... ... ... ... ... 2
The above formulation is heated at 1600 C.
for thirty minutes in an oscillating disc
Rheometer (American Standard Testing
Method D2705-68T). Satisfactory cross-- linking is obtained.
Examples 14-15 These examples illustrate the pre-reaction of 2,5-dimercapto-1,3.4thiadiazole with an organic basic material. The reaction prodcut is then used to cross-link a saturated.
halogen-containing polymer.
A mixture of 15. grams (0.1 mole) 2,5dimercapto-1,3,4-thiadiazole and 37 grams (0.2 mole) tributylamine in 200 ml tetrahydrofuran is- heated at 45"C, for 20 minutes. A yellow precipitate results which is separated from the solution by crystallization, filtered and washed with methylene -chloride. The product is dried overnight in a vacuum oven at 500 C. and a pressure of about 18 mm mercury. Analysis of- the pro- duct indicates a bis salt.
The reaction product obtained above is used to cross-link an epichlorohydrinethylene oxide copolymer by formulating as follows:
Ingredients Parts
Example 14 Example 15
Epichlorohydrin-ethylene oxide copolymer l(26% C1) ... ... ... ... ... 100 100
Stearic acid (process aid) ... ... . . . - 1 1
Barium carbonate ... ... ... ... 7.5
Reaction product of 2,5-dimercapto-1,3,4
thiadiazole and tributylamine ... ... 5.2 5.2
The above formulations are cross-linked by heating at 1600 C. for thirty minutes in an oscillating disc Rheometer (American Standard Testing Method D2705-68T). The properties measured are:
Example 14 Example 15
Minimum torque (inch pounds) .... - 7 - 10
Torque after 30 minutes (inch-pounds) ... 48 80
Torque after 60 minutes (inch-pounds) .. 50 81
WHAT WE CLAIM IS:- 1. The process of cross-linking a-saturated halogen-containing polymer containing at least 2 per cent by weight of halogen which comprises heating said polymer in the presence of a basic material and 2,5 dimercapto-1,3,4-thiadiazoley which, optionally, may have been prereacted.
2. The process of Claim - 1-wherein the basic material is a basic metal oxide.
3. The process of Claim 2 wherein the basic metal oxide is magnesium oxide.
4. The process of Claim 2, wherein the basic metal oxide is calcium oxide.
5. The process of Claim 1, wherein the basic material is a basic metal salt.
6. The process of Claim 5 wherein the basic metal salt is a basic metal carbonate.
7. The--process of-- Claim 6 wherein the basic metal salt is barium carbonate.
8. The process of Claim 6 wherein the basic metal carbonate is calcium carbonate.
9. The process of Claim 6 wherein the basic metal carbonate is magnesium carbonate.
-10. The process of Claim 6 wherein the basic metal salt is strontium carbonate.
11. The process of Claim 1 wherein the basic material is a basic metal hydroxide..
12. The process of Claim 11 wherein the basic metal hydroxide is calcium hydroxide.
13. The process of Claim 1 wherein the
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (29)
1. The process of cross-linking a-saturated halogen-containing polymer containing at least 2 per cent by weight of halogen which comprises heating said polymer in the presence of a basic material and 2,5 dimercapto-1,3,4-thiadiazoley which, optionally, may have been prereacted.
2. The process of Claim - 1-wherein the basic material is a basic metal oxide.
3. The process of Claim 2 wherein the basic metal oxide is magnesium oxide.
4. The process of Claim 2, wherein the basic metal oxide is calcium oxide.
5. The process of Claim 1, wherein the basic material is a basic metal salt.
6. The process of Claim 5 wherein the basic metal salt is a basic metal carbonate.
7. The--process of-- Claim 6 wherein the basic metal salt is barium carbonate.
8. The process of Claim 6 wherein the basic metal carbonate is calcium carbonate.
9. The process of Claim 6 wherein the basic metal carbonate is magnesium carbonate.
-
10. The process of Claim 6 wherein the basic metal salt is strontium carbonate.
11. The process of Claim 1 wherein the basic material is a basic metal hydroxide..
12. The process of Claim 11 wherein the basic metal hydroxide is calcium hydroxide.
13. The process of Claim 1 wherein the
basic material is a combination of inorganic basic material and organic basic material.
14. The process of Claim 13, wherein the organic basic material is di-ortho-tolylguanidine.
15. The process of Claim 13 wherein the organic basic material is the reaction product of butyraldehyde and aniline.
16. The process of Claim 13 wherein the organic basic material is diphenylguanidine.
17. The process of Claim 1 wherein the basic material is an organic basic material.
18. The process of Claim 17 wherein the organic basic material is selected from primary, secondary and tertiary amines, amine salts and quaternary ammonium compounds.
19. The process of Claim 18 wherein the organic basic material is dicyclohexylamine.
20. The process of any one of the preceding claims wherein the saturated, halogencontaining polymer is a homopolymer of epichlorohydrin.
21. The process of any one of Claims 1 to 19 wherein the saturated, halogencontaining polymer is a copolymer of epi chlorohydrin and ethylene oxide.
22. The process of any one of Claims 1 to 19 wherein the saturated, halogencontaining polymer is chlorinated polyethylene.
23. The process of any one of Claims 1 to 19 wherein the saturated, halogencontaining polymer is poly(vinyl chloride).
24. The process of any one of the preceding claims which comprises pre-reacting the basic material and 2,5-dimercapto-1,3,4thiadiazole.
25. The process of any one of the preceding claims which further comprises adding at least one organic carboxylic acid to the polymer prior to heating.
26. The process of any one of the preceding claims wherein the 2,5-diamercapto1,3,4,-thiadiazole is incorporated in the reaction mixture as a concentrate comprising a binder material and at least 15 per cent by weight of said thiadiazole.
27. A cross-linkable composition comprising (a) a saturated, halogen-containing polymer containing at least 2 per cent by weight of halogen, (b) basic material, and (c) 2,5-dimercapto- 1 ,3,4-thiadiazole, the basic material and the thiazone having optionally been prereacted.
28. A process of cross linking a saturated halogen-containing polymer substantially as described in the foregoing Examples.
29. A saturated, halogen-containing polymer containing at least 20 per cent by weight of halogen crosslinked by the process of any one of Claims 1 to 26 or 28.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84283977A | 1977-10-17 | 1977-10-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1585928A true GB1585928A (en) | 1981-03-11 |
Family
ID=25288371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB4987077A Expired GB1585928A (en) | 1977-10-17 | 1977-11-30 | 2,5 - dimercapto - 1,3,4 - thiadiazole as a crosslinker for saturated halogen-containing polymers |
Country Status (17)
| Country | Link |
|---|---|
| JP (1) | JPS5458750A (en) |
| AT (1) | AT372693B (en) |
| AU (1) | AU519452B2 (en) |
| BE (1) | BE861505A (en) |
| BR (1) | BR7708086A (en) |
| CA (1) | CA1124445A (en) |
| CH (1) | CH628069A5 (en) |
| DE (1) | DE2754060C2 (en) |
| DK (1) | DK159280C (en) |
| ES (1) | ES464735A1 (en) |
| FI (1) | FI68851C (en) |
| FR (1) | FR2405971A1 (en) |
| GB (1) | GB1585928A (en) |
| IT (1) | IT1088559B (en) |
| LU (1) | LU78636A1 (en) |
| NL (1) | NL7713345A (en) |
| SE (1) | SE429556B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069191A1 (en) * | 2004-12-21 | 2006-06-29 | Dow Global Technologies Inc. | Vulcanizable halogenated elastomer compositions |
| CN107531952A (en) * | 2015-05-04 | 2018-01-02 | 电化株式会社 | Chloroprene rubber composition, sulfidization molding body and application thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2845125A1 (en) * | 1977-10-17 | 1979-04-19 | Hercules Inc | Vulcanisation of halogenated polymers - using 2,5-di:mercapto 1,3,4-thiadiazole in presence of a base |
| JPH0322968U (en) * | 1989-07-13 | 1991-03-11 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787376A (en) * | 1970-12-31 | 1974-01-22 | Nippon Zeon Co | Process for vulcanizing polyepihalo-hydrin rubbers |
| US3919143A (en) * | 1974-02-04 | 1975-11-11 | Goodrich Co B F | Vulcanizable compositions containing halogen-bearing elastomeric polymers |
| GB1536593A (en) * | 1976-06-28 | 1978-12-20 | Hercules Inc | Vulcanizing halogen-containing polymers |
-
1977
- 1977-11-28 CA CA291,845A patent/CA1124445A/en not_active Expired
- 1977-11-29 FI FI773616A patent/FI68851C/en not_active IP Right Cessation
- 1977-11-30 GB GB4987077A patent/GB1585928A/en not_active Expired
- 1977-12-01 AU AU31119/77A patent/AU519452B2/en not_active Expired
- 1977-12-02 NL NL7713345A patent/NL7713345A/en not_active Application Discontinuation
- 1977-12-02 IT IT3034777A patent/IT1088559B/en active
- 1977-12-02 JP JP14406177A patent/JPS5458750A/en active Granted
- 1977-12-03 ES ES464735A patent/ES464735A1/en not_active Expired
- 1977-12-05 BR BR7708086A patent/BR7708086A/en unknown
- 1977-12-05 SE SE7713775A patent/SE429556B/en not_active IP Right Cessation
- 1977-12-05 AT AT869077A patent/AT372693B/en not_active IP Right Cessation
- 1977-12-05 DK DK540577A patent/DK159280C/en active
- 1977-12-05 CH CH1486777A patent/CH628069A5/en not_active IP Right Cessation
- 1977-12-05 BE BE183172A patent/BE861505A/en not_active IP Right Cessation
- 1977-12-05 LU LU78636A patent/LU78636A1/xx unknown
- 1977-12-05 FR FR7736540A patent/FR2405971A1/en active Granted
- 1977-12-05 DE DE19772754060 patent/DE2754060C2/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006069191A1 (en) * | 2004-12-21 | 2006-06-29 | Dow Global Technologies Inc. | Vulcanizable halogenated elastomer compositions |
| US8399572B2 (en) | 2004-12-21 | 2013-03-19 | Dow Global Technologies Llc | Vulcanizable halogenated elastomer compositions |
| US8519059B2 (en) | 2004-12-21 | 2013-08-27 | Dow Global Technologies Llc | Vulcanizable halogenated elastomer compositions |
| CN107531952A (en) * | 2015-05-04 | 2018-01-02 | 电化株式会社 | Chloroprene rubber composition, sulfidization molding body and application thereof |
| CN107531952B (en) * | 2015-05-04 | 2020-07-10 | 电化株式会社 | Chloroprene rubber composition, vulcanized molded body and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| ES464735A1 (en) | 1978-07-01 |
| FR2405971A1 (en) | 1979-05-11 |
| DE2754060C2 (en) | 1986-06-26 |
| FI68851B (en) | 1985-07-31 |
| FI68851C (en) | 1985-11-11 |
| CH628069A5 (en) | 1982-02-15 |
| NL7713345A (en) | 1979-04-19 |
| DK159280B (en) | 1990-09-24 |
| AU519452B2 (en) | 1981-12-03 |
| ATA869077A (en) | 1983-03-15 |
| DK159280C (en) | 1991-02-25 |
| FR2405971B1 (en) | 1984-07-20 |
| IT1088559B (en) | 1985-06-10 |
| DE2754060A1 (en) | 1979-04-26 |
| BE861505A (en) | 1978-06-05 |
| BR7708086A (en) | 1979-06-19 |
| AT372693B (en) | 1983-11-10 |
| AU3111977A (en) | 1979-06-07 |
| SE429556B (en) | 1983-09-12 |
| DK540577A (en) | 1979-04-18 |
| JPS611472B2 (en) | 1986-01-17 |
| FI773616A (en) | 1979-04-18 |
| JPS5458750A (en) | 1979-05-11 |
| SE7713775L (en) | 1979-04-18 |
| CA1124445A (en) | 1982-05-25 |
| LU78636A1 (en) | 1978-07-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19971129 |