USRE19207E - Olefin-polysulphtde plastic - Google Patents
Olefin-polysulphtde plastic Download PDFInfo
- Publication number
- USRE19207E USRE19207E US19207DE USRE19207E US RE19207 E USRE19207 E US RE19207E US 19207D E US19207D E US 19207DE US RE19207 E USRE19207 E US RE19207E
- Authority
- US
- United States
- Prior art keywords
- polysulphide
- plastic
- latex
- olefin
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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- 239000004033 plastic Substances 0.000 title description 48
- 229920003023 plastic Polymers 0.000 title description 48
- 239000006185 dispersion Substances 0.000 description 38
- 229920000126 Latex Polymers 0.000 description 21
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 21
- 239000004816 latex Substances 0.000 description 21
- 239000000347 magnesium hydroxide Substances 0.000 description 21
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 21
- 239000000203 mixture Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 12
- 239000005864 Sulphur Substances 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002270 dispersing agent Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000969 carrier Substances 0.000 description 7
- 239000003292 glue Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 235000019698 starch Nutrition 0.000 description 6
- 239000008107 starch Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 230000001112 coagulant Effects 0.000 description 4
- 235000013601 eggs Nutrition 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxyl anion Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- QSLZFPQJJGGNFN-UHFFFAOYSA-N calcium;sulfane Chemical compound S.[Ca+2] QSLZFPQJJGGNFN-UHFFFAOYSA-N 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000875 corresponding Effects 0.000 description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012047 saturated solution Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- -1 acetic'acid Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L mgso4 Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 210000004369 Blood Anatomy 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon bisulphide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000007965 rubber solvent Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/14—Polysulfides
- C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides
Definitions
- I am the present invention I am able to secure the olefin-polysulphide plastic, and particularly the soft-type plastic above referred to, 'in the form of an aqueous dispersion or latex, which can be readily purified, and from which the plastic material may be coagulated, either with or without the previous incorporation into the latex of desired compounding or stabilizing constituents.
- the plastic material in a dispersed condition as a latex, I am enabled to coat or impregnate fabrics, textiles and various absorbent and non-absorbent bodies with the latex and subsequently cause the coagulation in situ of the desired plastic b'odies.
- I cause the plastic or reaction body to be formed in the presence of a suitable dispersing agent, while maintaining a hydroxyl ion concentration equal to or greater than that existing in a saturated solution of freshly precipitated magnesium hydroxide.
- a suitable dispersing agent I may employ precipitated magnesium hydroxide, or aqueous dispersions of peptized starch, gelatin, glue, blood-albumen, egg-albumen, or the like. In general I prefer to employ freshly precipitated magnesium hydroxide in carrying out the reac-. tion.
- the plastic material may be produced by reaction between an olefin-dihalide and a water-soluble polysulphide having the desired sulphur content. the reaction being quantitative.
- the polysulphide employed may be previously stabilized by heating for a period such that homogeneity is secured, as set forth in my prior application 369,912, filed June 10,1929, and the conditions of reaction, particularly as to temperature, may be controlled by the addition of alcohols as disclosed in said application.
- the proportion of alcohol may vary from 10 to 80% by volume. Where such control isnot desired, the alcohol may be omitted.
- Magnesium hydroxide is formed in this solution, preferably by the addition of a solution of sodium hydroxide, followed by a solution of magnesium chloride or sulphate, or other suitablecompound.
- the amount of magnesium hydroxide may vary within quite wide limits say from 2 to 50 grams per thousand cubic centimeters of the polysulphide solution. Preferably from 5 to 10 grams per liter provides a desirable form of latex-like dispersion product best adapted for handling.
- each 1000 cubic centimeters of the above calcium polysulphide solution there may be added 50 cubic centimeters of a solution containing 290 grams sodium hydroxide per liter and 100 cubic centimeters of a solution of magnesium'chloride containing the chemical equivalent of 105 grams of magnesium hydroxide per liter, these proportions providing a slight excess of sodium hy'- droxide.
- a semi-gelatinous dispersion of mag- 85 nesium hydroxide, the proportion of dihalide added being very slightly less than the equivalent required for reaction.
- 157 cubic centimeters of ethylene dichloride per liter of original calcium polysul-- phide solution is used.
- the olefln-dihalide i., added in small portions with vigorous agitation.
- the polysulphide solution may first be slightly warmed, say to 80 to 100 F., to accelerate the beginning of the reaction.
- the addition of ethylene dichloride is controlled so that the temperature does not rise excessively, say to above to F.
- the reaction may be completed by further warming the mixture to, say, 1'75 to F. for a short period, until 110 or the final 75 as here- 90 phide plastic forms in thisreaction mixture as a fluid dispersion, latex-like in character, which settles out of' the reaction mixture.
- the supernatant solution may be removed by decantation and the latex-like. dispersion may be readily washed with water and settled, the .wash water being decanted. This is repeated until the soluble salts and other undesirable constituents presentare completely removed. This'latex may then be coagulated or compounded and coagulated, as
- ⁇ mixture is then heated to 120 F., and slightly less than equivalent quantity of ethylene dichloride is added in small portions at a time with vigorous agitation, while holding the temperature of the mixture below about 175 F.
- the amount of ethylene dichloride so added is about 208 grams per liter of the original polysulphide solution.
- the latex of olefin-polysulphide plastic forms and is settled and separated from the other products of reaction by decantation or centrifuging, thoroughly washed as in the first example and is then reachr forcoagulating or compounding and coagulating.
- the latex-like dispersion of the olefin-polysulphide plastic produced in accordance with the method of the present invention may be coagulated by acidifying it with any suitable acid, such as hydrochloride or sulphuric acid, or organic acids such as acetic'acid, formic acid, or the like; and on acidulation, the. olefin-polysulphide plastic coagulates to form an elastic, spongy mass, from yellow to white or nearly white in color.
- the coagulum has the characteristics of the soft plastic described in my prior applications above referred to, being pliable and resembling in appearance soft vulcanized rubber.
- Various inert materials such as those of the type used in compounding rubber, for example. fibers, wood flour, carbon black, glue, asbestos. and the like, may be compounded with the latex'either with or without the sulphur carrier. The compoundmay then be suitably heated to effect its stabilization, the time of heating varying with the temperature employed. Temperatures from C. upwards may be used. Thus, by heating in autoclave under 40 lbs. steam pressure for 40 minutes to 1 hour, a completely stable and homogeneous product may be secured.
- such materials may be incorporated in the latexbefore coagulation.
- a sulphur carrier and other compounding ingredicuts into the coagulum such materials may be incorporated in the latexbefore coagulation.
- litharge or zinc oxide may be thoroughly mixed with a thick latex, the mix-- ture then heated (as it does not undergo 008-81118- foon'iplete disappearance of'the olefln-dih'alide is indicated by loss of its odor.
- the olefin-polysultion on heating imder the same conditions as set forth in connection with the compound above, and the heated and stabilized mixture then coagu- 'lated.
- the resulting product has the characteristics of' a soft unvulcanized rubber, does not flow under pressure, is notseparable by organic solvents; it is not aifected or swelled by organic rubber solvents, including carbon disulphide, and has dielectric qualities superior to those of rubber. Furthermore, it completely resists the action of oils, salt water and the like, and has an extremely low power loss when used as a dielectric.
- the latex of the olefln-polysulflde plastic is stable and may be preserved and stored as such, or may be treated with a sulphur carrier,- as hereinbefore set forth, and the stabilized latex preserved and stored for further use. If the latex is stored for periods of a week or more, it may undergo a change somewhat analogous to polymerization. The addition of an acid then produces the subsidence of'a granular product from the liquid. The latex can,'however, be restored to its original condition by subjecting the dispersion; before adding the acid, to temperatures around the boiling point of water for a few minutes, the addition of the proper amount of acid will then produce the. massive coagulum.
- the present method of operation is particularly desirable in the manufacture of the soft-type of olefin-polysulphide plastic and those approaching the soft-type;that is, corresponding to the polysulphides of the formula R8: to RS and upwards. It may also be employed in the production of olefin-polysulphide plastics of lower sulphur content in securing dispersed products but as the proportions of sulphur decrease, the resmlting product loses its latex-like character and assumes a more granular, pulverulent character, as in the process described in my prior application Serial 3 mixtures of olefins such as are secured by the;
- the method of producing an olefln-polysul phide plastic in dispersed form which comprises reacting upon an olefln-dihalide with a solution of a water soluble polysulphide in the presence of a dispersing agent from the group including magnesium hydroxide and dispersions of peptized. starch, gelatin, glue, blood-albumen, egg albumen and the like while maintaining an alkalinity at of freshly precipitated magnesium hydroxide.
- the method of forming a soft olefin-polysulphide plastic in latex-like dispersion which comprises reacting upon an olefln-dihalide with an aqueous solution of a polysulphide having a formula RSn, wherein n is at least 3 and R is the equivalent of two monovalent positive'radicals in the presence of a dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg albumen and the like, while maintaining a hydroxyl ion concentration at least equal to that existing in freshly precipitated magnesium hydroxide.
- a dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg albumen and the like
- the method of forming a soft olefin-polysulphide plastic in the form of a latex-like dispersion which comprises incorporating a dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg-albumen and the like into an aqueous solution of a polysulphide of formula RSn wherein n is 3 or higher and R is the equivalent of two monovalent positive radicals, and admixing an ol eiin-dihalide with said solution.
- the method of producing a soft olefin-polysulphide plastic in latex-like dispersion which comprises dispersing magnesium hydroxide in an aqueous solution of a polysulphide of formula RS wherein n is at least 3 and Ris the equivalent of iwo monovalent positive radicals, admixing an olefln-dihalide therewith and warming to cause reaction therebetween, whereby a latex-like dispersion of a soft olefin-polysulphide plastic is secured.
- a soft olefin-polysulphide plastic which comprises forming dispersed magnesium hydroxide in an aqueous solution of a polysulphide of formula R Sn, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, and adding an olefin-dihalide thereto, whereby the olefin-polysulphide plastic is formed in latex-like dispersion.
- a soft-type olefinpolysulphide plastic which comprises incorporating a suitable dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg albumen and the like in an aqueous solution of a polysulphide of the general formula RS, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, reacting thereupon with an olefln-dihalide, thereby forming a latex-like dispersion of the olefin polysulphide plastic, washing said latex to remove soluble impurities therefrom and acidifying the latex, thereby causing coagulation of the plastic.
- a suitable dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg albumen and the like
- a polysulphide of the general formula RS wherein n is at least 3 and R is the equivalent of
- the 'method of producing an olefin-polysulphide plastic which comprises reacting with an olefln-dihalideupon a polysulphide of formula 'RSn, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, in aqueous solution, in the presence of a dispersing agent from the group including magnesium.
- the method of forming a soft-type olefinpolysulphide plastic which comprises reacting with an olefln-dihalide upon an aqueous solution of a polysulphide of formula RSn, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, in the presence of a solution of freshly precipitated magnesium hydroxide, thereby forming a latex-like dispersion of the plastic, separating and washing said latex, and acidulating the latex, thereby coagulating the plastic.
- RSn polysulphide of formula RSn
- n is at least 3 and R is the equivalent of two monovalent positive radicals.
- a latex-like dispersion of an organic polysulphide plastic produced by the action of a mixture oi dihalides oi gaseous oieiins on a water I soluble polysulphide oithe formula R811. wherein n is at least 3 and R is the equivalent of two monovalent positive radicals.
- a composition comprising an admixture 01 a latex-like dispersion of a soft-type olefin-pol sulphide plastic and compounding ingredients.
- a composition comprising an intermixture of a latex-like dispersion of a soft-type olefin-r polysulphide plastic and a sulphur carrier.
- a composition comprising an intermixture 01 a latex-like dispersion of a soft-type olefinpolysulphide plastic and a sulphur carrier, said composition being stabilized by heat.
- composition comprising an intermi'xture of a latex-like dispersion of a soft-type olefinpolysulphide plastic andlitharge.
- a composition comprising an intermixture of a latex-like dispersion of an olefln-polysulphide plastic and litharge. said composition being stabilized by heat.
- a composition comprising an intermixture of a latex-like dispersion of a soft-type olefinpolysulphide plastic, inert material, and a suiphur carrier.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Description
Reissued June 12, 1934 UNITED STATES 19,201 OLEFIN-POLYSULPHIDE PLASTIC Joseph 0. Patrick. Trenton, N. J.
" PATENT OFFICE};
No Drawing. Original no. 1,950,744, dated March 18, 1934, Serial No. 393,830, September 19, 1929. Application for reissue April 17, 1934, Serial No.
26 Claims. (Cl. 260-8) The present invention relates to improvements in olefin-polysulphide plastics and more particularly in the type of plastic described in my prior application 239,808, filed December 13, 1927.
Inaccordance with the present invention, I am the present invention, I am able to secure the olefin-polysulphide plastic, and particularly the soft-type plastic above referred to, 'in the form of an aqueous dispersion or latex, which can be readily purified, and from which the plastic material may be coagulated, either with or without the previous incorporation into the latex of desired compounding or stabilizing constituents. In addition, by securing the plastic material in a dispersed condition as a latex, I am enabled to coat or impregnate fabrics, textiles and various absorbent and non-absorbent bodies with the latex and subsequently cause the coagulation in situ of the desired plastic b'odies.
In carrying out the present invention, I cause the plastic or reaction body to be formed in the presence of a suitable dispersing agent, while maintaining a hydroxyl ion concentration equal to or greater than that existing in a saturated solution of freshly precipitated magnesium hydroxide. As suitable dispersing agents, I may employ precipitated magnesium hydroxide, or aqueous dispersions of peptized starch, gelatin, glue, blood-albumen, egg-albumen, or the like. In general I prefer to employ freshly precipitated magnesium hydroxide in carrying out the reac-. tion.
As pointed out in my prior application above referred to, the plastic material may be produced by reaction between an olefin-dihalide and a water-soluble polysulphide having the desired sulphur content. the reaction being quantitative.
Ordinarily an excess of one of the reaction constituents is desired, and since the polysulphide is the least expensive reagent, it is preferred that there be 'an excess of the polysulphide present. The polysulphide employed may be previously stabilized by heating for a period such that homogeneity is secured, as set forth in my prior application 369,912, filed June 10,1929, and the conditions of reaction, particularly as to temperature, may be controlled by the addition of alcohols as disclosed in said application. Thus, when used, the proportion of alcohol may vary from 10 to 80% by volume. Where such control isnot desired, the alcohol may be omitted.
The invention may beillustrated by the following examples:
21. An aqueous solution of calcium polysulphide is prepared, having a density of 31 B.,
the empirical formula of which is, by analysis,
Gas. Magnesium hydroxide is formed in this solution, preferably by the addition of a solution of sodium hydroxide, followed by a solution of magnesium chloride or sulphate, or other suitablecompound. The amount of magnesium hydroxide may vary within quite wide limits say from 2 to 50 grams per thousand cubic centimeters of the polysulphide solution. Preferably from 5 to 10 grams per liter provides a desirable form of latex-like dispersion product best adapted for handling. Thus, to each 1000 cubic centimeters of the above calcium polysulphide solution, there may be added 50 cubic centimeters of a solution containing 290 grams sodium hydroxide per liter and 100 cubic centimeters of a solution of magnesium'chloride containing the chemical equivalent of 105 grams of magnesium hydroxide per liter, these proportions providing a slight excess of sodium hy'- droxide. A semi-gelatinous dispersion of mag- 85 nesium hydroxide, the proportion of dihalide added being very slightly less than the equivalent required for reaction. Thus, with the solution above described, 157 cubic centimeters of ethylene dichloride per liter of original calcium polysul-- phide solution is used. 'To avoid excessive heatv ing, the olefln-dihalide i., added in small portions with vigorous agitation. If desired, the polysulphide solution may first be slightly warmed, say to 80 to 100 F., to accelerate the beginning of the reaction. The addition of ethylene dichloride is controlled so that the temperature does not rise excessively, say to above to F. After the dihalide has been completely added, the reaction may be completed by further warming the mixture to, say, 1'75 to F. for a short period, until 110 or the final 75 as here- 90 phide plastic forms in thisreaction mixture as a fluid dispersion, latex-like in character, which settles out of' the reaction mixture. The supernatant solution may be removed by decantation and the latex-like. dispersion may be readily washed with water and settled, the .wash water being decanted. This is repeated until the soluble salts and other undesirable constituents presentare completely removed. This'latex may then be coagulated or compounded and coagulated, as
I suitably in the same proportions as set forth in connection with the first example above. The
\ mixture is then heated to 120 F., and slightly less than equivalent quantity of ethylene dichloride is added in small portions at a time with vigorous agitation, while holding the temperature of the mixture below about 175 F. The amount of ethylene dichloride so added is about 208 grams per liter of the original polysulphide solution. The latex of olefin-polysulphide plastic forms and is settled and separated from the other products of reaction by decantation or centrifuging, thoroughly washed as in the first example and is then reachr forcoagulating or compounding and coagulating.
.The latex-like dispersion of the olefin-polysulphide plastic produced in accordance with the method of the present invention may be coagulated by acidifying it with any suitable acid, such as hydrochloride or sulphuric acid, or organic acids such as acetic'acid, formic acid, or the like; and on acidulation, the. olefin-polysulphide plastic coagulates to form an elastic, spongy mass, from yellow to white or nearly white in color. The coagulum has the characteristics of the soft plastic described in my prior applications above referred to, being pliable and resembling in appearance soft vulcanized rubber. Its characteristics may be improved by incorporating into it, suitably on a rubber mill, any desirable proportion of a metallic oxide such as litharge, zinc oxide, magnesium oxide or other compounds of the class of sulphur carriers well known in the rubber industry. Various inert materials, such as those of the type used in compounding rubber, for example. fibers, wood flour, carbon black, glue, asbestos. and the like, may be compounded with the latex'either with or without the sulphur carrier. The compoundmay then be suitably heated to effect its stabilization, the time of heating varying with the temperature employed. Temperatures from C. upwards may be used. Thus, by heating in autoclave under 40 lbs. steam pressure for 40 minutes to 1 hour, a completely stable and homogeneous product may be secured. Instead of first coagulating the latex and incorporating a sulphur carrier and other compounding ingredicuts into the coagulum, such materials may be incorporated in the latexbefore coagulation.- Thus, from 1 to 10% of litharge or zinc oxide may be thoroughly mixed with a thick latex, the mix-- ture then heated (as it does not undergo 008-81118- foon'iplete disappearance of'the olefln-dih'alide is indicated by loss of its odor. The olefin-polysultion on heating) imder the same conditions as set forth in connection with the compound above, and the heated and stabilized mixture then coagu- 'lated. Other compounding ingredients maybe in- The resulting product has the characteristics of' a soft unvulcanized rubber, does not flow under pressure, is notseparable by organic solvents; it is not aifected or swelled by organic rubber solvents, including carbon disulphide, and has dielectric qualities superior to those of rubber. Furthermore, it completely resists the action of oils, salt water and the like, and has an extremely low power loss when used as a dielectric.
The latex of the olefln-polysulflde plastic is stable and may be preserved and stored as such, or may be treated with a sulphur carrier,- as hereinbefore set forth, and the stabilized latex preserved and stored for further use. If the latex is stored for periods of a week or more, it may undergo a change somewhat analogous to polymerization. The addition of an acid then produces the subsidence of'a granular product from the liquid. The latex can,'however, be restored to its original condition by subjecting the dispersion; before adding the acid, to temperatures around the boiling point of water for a few minutes, the addition of the proper amount of acid will then produce the. massive coagulum.
The present method of operation is particularly desirable in the manufacture of the soft-type of olefin-polysulphide plastic and those approaching the soft-type;that is, corresponding to the polysulphides of the formula R8: to RS and upwards. It may also be employed in the production of olefin-polysulphide plastics of lower sulphur content in securing dispersed products but as the proportions of sulphur decrease, the resmlting product loses its latex-like character and assumes a more granular, pulverulent character, as in the process described in my prior application Serial 3 mixtures of olefins such as are secured by the;
formation of unsaturated hydrocarbon gases derived from pressure cracking processes, natural gas-cracking processes, and the like. Furthermore, as also disclosed in my prior applications, a
wide range of soluble polysulphides may be employed in securing the reaction products.
I claim:
1. The method of producing an olefln-polysul phide plastic in dispersed form,-'which comprises reacting upon an olefln-dihalide with a solution of a water soluble polysulphide in the presence of a dispersing agent from the group including magnesium hydroxide and dispersions of peptized. starch, gelatin, glue, blood-albumen, egg albumen and the like while maintaining an alkalinity at of freshly precipitated magnesium hydroxide.
2. The method of producing an organic polysul- 1 least equal to that existing in a saturated solution ethylene dihalide with a solution of a water soluble polysulphide in the presence of magnesium hydroxide, thereby forming alatex-like dispersion of an organic polysulphide body.
4. The method of producing an organic polysulphide plastic which comprises reacting upon a mixture of dihalides of gaseous olefin hydrocarbons with a solution 'of a water-soluble polysulphide in the presence of magnesium hydroxide, thereby forming a latex-like dispersion of an organic polysulphide body.
5. The method of forming a soft olefin-polysulphide plastic in latex-like dispersion which comprises reacting upon an olefln-dihalide with an aqueous solution of a polysulphide having a formula RSn, wherein n is at least 3 and R is the equivalent of two monovalent positive'radicals in the presence of a dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg albumen and the like, while maintaining a hydroxyl ion concentration at least equal to that existing in freshly precipitated magnesium hydroxide.
6. The method of producing a soft olefln-poly sulphide plastic in latex-like dispersion wherein an olefin-dihalide is reacted upon with an aqueous solution of a polysulphide of formula RS wherein n is at least 3 and R is the equivalent of two monovalent positive radicals in the presence of freshly precipitated magnesium hydroxide.
'7. The method of forming a soft olefin-polysulphide plastic in the form of a latex-like dispersion, which comprises incorporating a dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg-albumen and the like into an aqueous solution of a polysulphide of formula RSn wherein n is 3 or higher and R is the equivalent of two monovalent positive radicals, and admixing an ol eiin-dihalide with said solution.
8. The method of producing a soft olefin-polysulphide plastic in latex-like dispersion, which comprises dispersing magnesium hydroxide in an aqueous solution of a polysulphide of formula RS wherein n is at least 3 and Ris the equivalent of iwo monovalent positive radicals, admixing an olefln-dihalide therewith and warming to cause reaction therebetween, whereby a latex-like dispersion of a soft olefin-polysulphide plastic is secured.
9. The method of producing a soft olefin-polysulphide plastic, which comprises forming dispersed magnesium hydroxide in an aqueous solution of a polysulphide of formula R Sn, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, and adding an olefin-dihalide thereto, whereby the olefin-polysulphide plastic is formed in latex-like dispersion.
10. The method of producing a soft olefin-polysulphide plastic which comprises reacting upon a polysulphide containing a proportion of sulfur adapted to produce a soft-type plastic, while in aqueous solution, with an olefln-dihalide in the impurities from said latex, and coagulating the latex.
11. The method of producing a soft-type olefinpolysulphide plastic which comprises incorporating a suitable dispersing agent from the group including magnesium hydroxide and dispersions of peptized starch, gelatin, glue, blood-albumen, egg albumen and the like in an aqueous solution of a polysulphide of the general formula RS, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, reacting thereupon with an olefln-dihalide, thereby forming a latex-like dispersion of the olefin polysulphide plastic, washing said latex to remove soluble impurities therefrom and acidifying the latex, thereby causing coagulation of the plastic.
12. The 'method of producing an olefin-polysulphide plastic, which comprises reacting with an olefln-dihalideupon a polysulphide of formula 'RSn, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, in aqueous solution, in the presence of a dispersing agent from the group including magnesium. hydroxide and dispersions of peptized starch, gelatin, glue, blood albumen, egg albumen, and the like while maintaining an alkalinity at least equal to that existing in a saturated solution of freshly precipitated magnesium hydroxide, thereby forming a latex-like dispersion of an olefin-polysulphide plastic, washing said latex and acidulating the washed latex, thereby precipitating the olefin polysulphide plastic.
13. The method of forming a soft-type olefinpolysulphide plastic, which comprises reacting with an olefln-dihalide upon an aqueous solution of a polysulphide of formula RSn, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, in the presence of a solution of freshly precipitated magnesium hydroxide, thereby forming a latex-like dispersion of the plastic, separating and washing said latex, and acidulating the latex, thereby coagulating the plastic.
14. A latex-like dispersion of a soft-type olefinpolysulphide plastic, the type formula of the olefin being CnHhi. r
15. A latex-like dispersion of an olefin-polysulphide plastic having a sulphur content corresponding to a polysulphide of the formula. RSn. wherein n is at least 3 and R is the equivalent of two monovalent positive radicals.
16. A latex-like dispersion of an organic polysulphide derivative produced by theaction of an olefin dihalide on a water soluble polysulphide of the formula RSn, wherein n is at least 3 and R is the equivalent of'two monovalent positive radicals. said dispersion containing precipitated magnesium hydroxide as the dispersing agent.
17. A, latex-like dispersion of an organic poly-. sulphide derivative produced by the action of ethylene dihalide .ona water-soluble polysulphide of the formula RS1, wherein n is at least 3 and R is the equivalent of two monovalent positive radicals, said dispersion containing precipitated.
taining precipitated magnesium hydroxide as the dispersing agent.
an ethylene- 19. A latex-like dispersion of polysulphide havinga sulphur content corresponding to a polysulphide of the formula R811,
wherein n is at least 3 and R is the equivalent of two monovalent positive radicals.
20. A latex-like dispersion of an organic polysulphide plastic produced by the action of a mixture oi dihalides oi gaseous oieiins on a water I soluble polysulphide oithe formula R811. wherein n is at least 3 and R is the equivalent of two monovalent positive radicals.
21. A composition comprising an admixture 01 a latex-like dispersion of a soft-type olefin-pol sulphide plastic and compounding ingredients.
22. A composition comprising an intermixture of a latex-like dispersion of a soft-type olefin-r polysulphide plastic and a sulphur carrier.
23. A composition comprising an intermixture 01 a latex-like dispersion of a soft-type olefinpolysulphide plastic and a sulphur carrier, said composition being stabilized by heat.
24. A composition comprising an intermi'xture of a latex-like dispersion of a soft-type olefinpolysulphide plastic andlitharge.
25. A composition comprising an intermixture of a latex-like dispersion of an olefln-polysulphide plastic and litharge. said composition being stabilized by heat.
26. A composition comprising an intermixture of a latex-like dispersion of a soft-type olefinpolysulphide plastic, inert material, and a suiphur carrier.
JOSEPH c. PATRICK.
Publications (1)
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USRE19207E true USRE19207E (en) | 1934-06-12 |
Family
ID=2083145
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US19207D Expired USRE19207E (en) | Olefin-polysulphtde plastic |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2470529A (en) * | 1945-06-13 | 1949-05-17 | Goodrich Co B F | Pesticidal composition of polyethylene polysulfide and nicotine sulfate |
US2489567A (en) * | 1946-11-02 | 1949-11-29 | Heveatex Corp | Inorganic polysulfide-organic dihalide reaction product |
US2588796A (en) * | 1949-09-28 | 1952-03-11 | Monsanto Chemicals | Compositions containing organic polymeric sulfides and metal salts of 8-hydroxyquinoline and method of preparing same |
US4197229A (en) | 1978-02-27 | 1980-04-08 | Blount David H | Process for the production of an aqueous dispersion of poly(organic-poly-sulfide-silicate) copolymer |
WO1980001919A1 (en) * | 1979-03-09 | 1980-09-18 | D Blount | Process for the production of an aqueous dispersion of poly(organic-polysulfide-silicate)copolymer |
-
0
- US US19207D patent/USRE19207E/en not_active Expired
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2470529A (en) * | 1945-06-13 | 1949-05-17 | Goodrich Co B F | Pesticidal composition of polyethylene polysulfide and nicotine sulfate |
US2489567A (en) * | 1946-11-02 | 1949-11-29 | Heveatex Corp | Inorganic polysulfide-organic dihalide reaction product |
US2588796A (en) * | 1949-09-28 | 1952-03-11 | Monsanto Chemicals | Compositions containing organic polymeric sulfides and metal salts of 8-hydroxyquinoline and method of preparing same |
US4197229A (en) | 1978-02-27 | 1980-04-08 | Blount David H | Process for the production of an aqueous dispersion of poly(organic-poly-sulfide-silicate) copolymer |
WO1980001919A1 (en) * | 1979-03-09 | 1980-09-18 | D Blount | Process for the production of an aqueous dispersion of poly(organic-polysulfide-silicate)copolymer |
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