Патент USA US2409278код для вставки
Patented Oct. 15, 1946 , 2,409,276 UNITED’ STATES PATENT OFFICE 2,409,276 COMPOSITIONS COMPRISING BLOWN TER PEN'IC PRODUCTS AND VINYL POLYMERS AND METHOD OF MAKING ' Mortimer T. Harvey, East Orange, N. J.,' assign- ’ on; to Harvel Research Corporation, a comra tion of New vJersey .' Application August 1, 1041, No Dra Serial No. 405,078 11 Claims. (01. zoo-as) 1 The present invention relates to compositions of matter which comprise blown terpenic prod ucts and vinyl polymers in which compositions the present invention is particularly concerned with the various terpenes by which term, are meant unsaturated, non-aromatic hydrocarbons the oxidized terpenes serve as a plasticising sol 'oi' the formula (CsHa)n. where n is an integer vent for the vinyl polymers. greater than 1, as well asressential oils consisting largely of such hydrocarbons. To cover such es sential oils, as for ‘example, cedar wood oil, as - The compositions of the present invention can be used as such, for example, as ?lms, coatings, paints and varnishes for electrical insulation, for well as the individual terpenes, the all-embracing protective coatings, for decorative coatings and _ term "terpene oils” will be used. The method of oxidation particularly de so on where they are applied with a volatile thin 10 ner or solvent which is removed by evaporation scribed is siven for illustration and is by blowins after application and as extruded shapes such as but other methods such as spraying the liquid through an atmosphere of air or oxygen or ?ow tubing for electrical insulation, for woven textiles and for general use Where they are used in the ing the liquid down'inclined surfaces in an at dry state. And the compositions ofthe present 15 mosphere of air or oxygen can be used. By the invention can be used in or with other materials, for example, with arti?cial rubbers of the “Thio kol" “Duprene” and “Buna” types to impart de sired characteristics which are inherently lack ing in the arti?cial rubber. term “blown” as applied to any one of said sub stances in this speci?cation and claims is meant the product produced by subjecting the product to free oxygen to thicken the same. This may be . 20 done by following any one of the aforesaid speci?c An object of the present invention is to provide a plasticizer, or plasticising solvent, for vinyl polymers whereby the vinyl polymers are modi lied to produce dry compositions having rubber 25 like ?exibility and resiliency. methods of blowing. spraying or cascading as heretofore set forth. Method for oxidation The oxidation can be done by placing the liq uid material to be oxidized (the terpenic products Another object or the present invention is to in liquid state) in a closed container having a provide a modifying agent for vinyl polymers conduit extending thereinto to apoint near the whereby the resulting compositions can be used bottom, with openings in the conduit for releasing in arti?cial rubbers of the “Buna" or butadiene types and other types, including “Thiokol” and 30 air or oxygen below the surface of the liquid ' therein. A vent is provided for releasing the air "Duprene" to impart to said arti?cial rubbers or oxygen to prevent too great pressure being characteristics which are inherently lacking. built up and to allow the air or Oxygen to circu Another object of my invention is to provide a late through the liquid. A stirrer is used to agi plasticiser for vinyl polymers which plasticiser can be used in comparatively large amounts or 35 tate the liquid being oxidized and thereby to in crease the contact of the liquid with the air or proportions, with respect to the amount of vinyl oxygen. And heating of the liquid during blow polymer used, and yet obtain a “dry” composition ing is provided. In the illustrative method- the in which the piasticiser is held in and from which blowing is provided. In the illustrative method ' there is no bleeding of the plastiser, such large proportion being, for example, as high as six parts 40 the blowing was done by air by the apparatus and method described in this paragraph and at be of the plasticiser to one part of the vinyl polymer, tween about 160° F. and about 195° F. for about by weight. ‘ twenty-four hours. the air when it reached the The present application is a continuation in treating apparatus being at normal or room tem-‘ part of my copending application Serial Number 45 perature. Rapid stirring of the liquid during 382,740, ?led March 11, 1941. _ . blowing was produced by revolving blades or pad Illustrative examples of substances which can dles. The volume of lfquid put in the vessel was be blown to produce material suitable for the about one-quarter of the capacity of the vessel so practice of the present invention are methyl abie that advantageous contact with the air was pro tate (CmHzaCOOCHs), known on the market as “Abalyn,” ethyl abietate, decyl abietate, phenyl 50 duced by the stirring. By the term "terpenic products" as employed abietate and the other hydrocarbon .abietates, turpentine, pinene, pine oil, terpineol, dipentine, in this speci?cation and claims. is meant the class of products consisting of turpentine, pinene, pine (limonene, for example), eucalyptol (as oil of oil, terpineol, dipentine, eucalyptol (as oil of eu-‘ eucalyptus) and cedrene (in cedar wood oil). calyptus) and cedrene (in cedar wood oil). 0! the substances mentioned in this paragraph, 2,409,270 4 3 serve to make the "Buna" and the vinyl polymer Uses compatible with each other and bring them to The blown or oxidized terpenic products of the gether into. a workable composition and at the same time will not act deleteriously when the present invention are useful in the arts generally, and are useful particularly, for example, ( 1) for 5 composition is handled and worked into more putting vegetable oils into solution with cellulose advanced and ?nal states (as, for example, by vulcanization through heating) but will remain a nitrate, (2) as solvents for materials such as res part of the ?nal composition either in its orig ins of the glycerol-aldehyde resins, vegetable oils, cellulose nitrate, cellulose acetate and ethyl cellu inal form or in some intermediate or ?nal form. Below is a table showing characteristics of lose, (3) plasticising rubber, (4) ?oatation of ores, 10 mixtures of the starting solvents with a “Vinyl and (5) aiding the solvent properties of soaps. ite” resin and of oxidized solvents with the same Another use is as a mutual solvent for arti?cial “Vinylite" resin. The proportion is ?ve parts by rubbers of “Buna” type and vinyl resins. weight of solvent (or oxidized solvent) to one The term “Buna" as used herein is intended to mean certain synthetic materials made‘ from 15 part of "vinylite” resin. The “Vinylite” resin used in each case is “Vinylite vyn w." butadiene, with or without other materials, by Characteristics of prod. mixed with "vyn w" Characteristics of the mixtures Product mixed 5 to 1 with “vyn wll pH 7 4 7 ; Blown plus 011.... ..... Dipentene _ . _ . . . . . . . . .. 7 Blown dipentsne. ___._ Eucalyptus oil ............ .. 3-4 0 Eucalyptus oil, blown. Cent. viscosity Color 0.864/26... 1.027/25.-. Water clean... Insoluble‘. _ 29 Soluble. _ Soluble hot, .. 0.993/21 _ 0.878/27 . . _ Wstsr clear... Insol. _.. .__ l6. ............. .. Clear brown .. Yellow clear.-. Readily soLbleeds. Soluble bleeds. 1.02/29 ............. .. Very heavy liquid. Opaque ..... _. _. 0.967/20 ............ _. ............. .. Yellow clear... Insoluble. Heavier than water.. 300,000+l27 ..... __ Opaque ..... .. Soluble. I ....... .. comes outcold Brown green.. Partly sol. bleeds. 1.010/25 0848/21 Soluble. Soluble, bleeds. 1.035/25. Cedar wood oil, blown ....... .. Cedar wood . 4 Sp. gr. at °C. . Soluble. polymerization or copolymerizaticn, to produce The viscosity in each case was taken at the tem perature shown for the corresponding speci?c arti?cial rubber materials, for illustrative exam gravity, and the factor of 4.75 used to multiply ples, those known as and sold under the names of the time in seconds of the ?ow of the liquid by “Buna,” "Buna S," and “Perbunan" ("Buna N"). the centipoise method. The speci?c gravity was “Buna” is a straight butadiene polymer; "Buna taken with the hydrometer in each case except S" is a copolymer of butadiene and styrene; and in the case of “blown” “Abalyn" where it was "Perbunan" ("Buna N") is a copolymer of buta taken with the pycnometer. pH values were diene and acrylonitrile; and the term "Buna” as used herein is intended to cover also other buta 40 taken with Fischer pH paper. Each of the “blown" solvents in the above table diene polymers and copolymers of the “Buna” was oxidized by the illustrative method described type including products obtained by various poly above for oxidizing terpenes and below are given merization methods and steps and products ob— examples of (1) a gel-like composition of blown tained by copolymerising various proportions of turpentine and a vinyl ester and (2) a “Buna" materials such as various proportions of styrene rubber mixture containing the gel-like composi and butadiene or of acrylonitrile and butadiene tions. Each of the other “blown” solvents in and products obtained by copolymerizing other the above table can be substituted for all or any or different materials with butadiene such as oo of the “blown” turpentine in the following exam polymerizing coumarone or indene with buta dlene and to cover generally arti?cial rubbers 50 ples. Example 1.--A. One hundred parts by weight which are butadiene polymers or copolymers. of the "blown" turpentine described above are. The term vinyl polymer is used to designate heated to from about 150° C. to about, 165° C. and polymers of vinyl esters such as polymerized vinyl chloride, polymerized vinyl acetate, copolymers of viny1 chloride and vinyl acetate, polymerized twenty-?ve parts of polymerized vinyl chloride, 65 known on the trade as “vinylite qyna,” having vinyl chloroacetate and other polymerized vinyl esters. These range in consistency from the liq uid state to solid resin-like products depending a molecular weight of from about 20,000 to about 22,000, are added and stirred until solution takes place. This is cooled and ready for various uses. When cooled, this product is a rubbery mass, and on the material and on the degree or extent to which they are polymerized and are used in the 6.0 is a gel, and can be milled into the “Buna" type practice of the present invention in their various } arti?cial rubber, above identi?ed, to improve aging, tear resistance and other physical prop erties. B. To a batch of the product described, in ting them to use. For a number of uses such as 65 paragraph A, above, one hundred and twenty ?ve parts of "Buna S" were added and milled in getting rubber-like gels with the "mutual sol together on rubber-mixing rolls, together with vent," before the “Buna” type rubber is incor porated, vinyl polymers having molecular weights nine parts of zinc oxide, ?ve parts of "Aminox," eight parts of "Toads," and one hundred and between 20,000 and 30,000 are preferred. “Vinyl ite-vyn w" has a molecular weight of about 24,000 70 ten parts of “Gastex." This produces a “rubber" batch suitable for formation into various shapes and "Vinylite qyna” has a molecular weight of which can be vulcanized, for example, at 150° from about 20,000 to about 22,000. The mutual solvent or mutually compatible C. for about ?fteen minutes in a pressure mold. The examples of 5:1 mixtures of “blown” sol vehicle for the “Buna" and the vinyl polymer of the present invention is a material which will 76 vents disclosed above are given as illustrations of states according to the use to which they are to be applied and to the suitability of their consist ency to the method of handling required in put 2,409,270 6 ten parts of vinyl acetate: "vyn f" which is a the practice of the present invention, and these mixtures are suitable for mixing into "Buns" type arti?cial rubbers to give desirable characteristics copolymer- of eighty-seven parts of vinyl chloride and thirteen parts of vinyl acetate: "xyfg" which ' is polyvinyl butyral, formed by treating polyvinyl to the latter. Some of the above mixtures are alcohol with butyric aldehyde to give an acetal called polyvinyl butyral which is soluble in butyl alcohol and having a high tensile strength. substantially dry to the touch, others are tacky and still others are wet on the surface and some ‘of the “wet" bleed to greater or less extent. All of them are gel-like in consistency and mill easily An advantage or the compositions of the pres ent invention is that they have a greatly improved into rubber on rubber mixing rolls, and can be made up into vulcanizable "rubber” compositions 10 tear strength or resistance as compared with similar compositions made of ‘,‘Buna" type arti ?cial rubber without the vinyl polymers. similar to that given in Example 13 above by substituting any ofthe “blown” terpene products In addition to illustrating the method of bring ing arti?cial rubber-of the “Buna" type into solu pentine of Example 1, above. Also, in each case 16 tion or compatibility with vinyl polymers, these examples also illustrate the use of these solutions ' any of the preferred "Vinylite” resins can be used of "Buna” type arti?cial rubber with vinyl poly in place of "Vinylite qyna” and any of the "Buna" mers in “rubber” mixtures or compositions suit type arti?cial rubbers can be used in place of the able for molding by heat and pressure or suitable - “Buna S" of the examples. The proportionsof ingredients in the “rubber” mixture are illustra 20 for sheeting in calender or sheeting rolls and for general use to which rubber compositions can be tive and variations can be made in practising the placed. art of compounding of “Buns.” rubber composi The “Buna”-polyvinyl resin-mutual solvent tions and any or the mixtures of any of the compositions of the present invention can be vul preferred “Vinylite" resins described herein with any of the oxidized terpenes of the present inven 25 canized with sulphur alone or with various other vulcanizers and can be used generally in the man tion can be used in any of the "Buna” rubber ner of rubber mixes as illustrated above in the compositions described in my copending applica-. examples given. tion Ser. No. 382,740. According to the present invention butadiene Also for some purposes, whether for general use or for making “Vinylite" gels for general use or 30 arti?cial rubbers are made to have characteris tics and qualities which they do not have of them for use in “Buna” rubbers the terpene products selves and this by the addition of comparatively can be oxidized (as by blowing with air or other small quantities of polyvinyl resins having high wise) while they are in mixtures with other ma molecular weights, that is of the order of from terials such as terpenes-Cl-hO reaction products. For example, a mixture of equal parts by weight 35 about 20,000 to about 40,000, the addition being disclosed above or any mixture of two or more of them for all or any part of the "blown" tur made through the medium of a mutual solvent which is non-volatile up to at least 150° C. A and turpentine was blown by the method above number of the mutual solvents disclosed herein described, also a mixture of equal parts of rosin do not have boiling points at normal pressures. and a condensation product of CHzO and turpen tine; a mixture of equal parts of turpentine and 40 and cannot be distilled at normal pressures with out decomposition. ' > . CHzO-turpentine reaction product; and a mix General examples of compositions of the pres-I ture of equal parts of pine oil and CHzO-turpen tine reaction product was blown by the same A‘ ent invention which illustrate the ratios of poly vinyl ester, butadiene arti?cial rubber and mutual ' manner. In other cases CHzO-terpene reaction products were blown with each of the unreacted 45 solvent are as follows: of methyl abietate and a condensation of CHaO terpenes named herein in proportions ranging Parts by weight from 10 to 1 on oneside toil-t’ ' Dio'nthe. other side, giving useful products.“ ' ‘I > Any of the oxidized solvents of the present invention can be heated to remove light volatiles 50 therefrom before mixing with the selected “Viny Butadiene arti?cial rubber--.- lite” resin to get desired states, of dryness, tacki Polyvinyl ester.............. -. Mutual so1vent_....; .............................. .. A B O 75 00 5 20 2 . 8 ness or wetness to serve the purpose of its de sired use. For example blown “Abalyn” was heated up to‘ 240° C. to remove 10% of its weight 55 Generally the ratio of butadiene arti?cial rubber to polyvinyl ester can be stated to range from and blown dipentene was heated to remove 20% about 50 to 1 to about 2 to 1, and the ratio of of its weight and in each case they gave dry gel mutual solvent to polyvinyl ester to obtain a gel like mixtures with the “vyn w" in the proportions like product can be stated to range from about of 5 to 1 respectively. Also various proportions of oxidized terpene-CHaO reaction product to 80 10 to 1 to 1 to 1. For melting the mutual solvent and polyvinyl resin together the range is from "Vinylite" resin can be used to serve desired pur about 10 to 1 to about 2.5 to 1, and in the ratios poses, for example, from about one part to about. from about 2.5 to 1 to about 1 to 1 the two ingre ten parts of the said oxidized terpene-CFhOre dients can be brought together by milling them action product to about one part of the “Vinylite” 65 into each other on rubber mixing rolls, the prod resin. ucts along the whole range (10 to 1 to 1 to 1) being The following trade-mark names or trade rubber-like gels. Having thus described my invention, what I claim and desire to protect by Letters Patent is: names are ‘identi?ed as follows: "Gastex" and “JP-33"‘ are carbon blacks; "Speedon," “Altax” and “Tuads" are vulcanization accelerators: vand “Aminox” is an antioxidant. ' 70 substituted for all or any part of the “Vinylite vyn w" wherever that is used: "Qyna" which is polymerized vinyl chloride; "vyn s" which is a coplymer of ninety parts of vinyl chloride and 1. l The method which comprises heating to gether from about one part to about ten- parts by weight of a blown terpenic product with one part of a polyvinyl ester to form a gel when cold. 2. A rubber-like composition comprising a poly 76 vinyl ester having a molecular weight between In the examples above the following ‘can be‘ I 9,409,276 7 . about 20,000 and about 40,000 and a blown ter penic product. ' 3. A composition oi’ matter comprising buta diene arti?cial rubber, a polyvinyl ester having a molecularvweight 01’ at least 20,000, and a mutual solvent which is non-volatile up to 150° C., said being a blown terpenic product, the boiling point of said mutual solvent being at least as high as the mixing temperature, and then mixing in said arti?cial rubber. ' 7. A gel of a polyvinyl ester and a blown ter penic product, which said gel is compatible with butadiene arti?cial rubber. . butadiene arti?cial rubber being present in 8. A rubber-like composition comprising a poly amount at least 50% by weight of the total of vinyl ester having a molecular weight between the three said components, and said mutual sol 10 about 20,000 and about 40,000 and blown turpen vent being a blown terpemc product. e. ‘ 4. A rubber-like composition comprising a poly! 9. A rubber-like composition comprising a poly vinyl ester having a molecular. weight between vinyl ester having a molecular weight between about 20,000 and about 40,000, a blown terpenic about 20,000 and about 40,000, blown turpentine product and a butadiene arti?cial rubber. 5. A composition of matter comprising buta 15 and a butadiene arti?cial rubber. 10. A composition or matter comprising buta diene arti?cial rubber, a polyvinyl ester having a diene arti?cial rubber, a polyvinyl ester having a molecular weight of at least 20,000, and a. mutual solvent which is non-volatile up to 150° C., the ratio of said butadiene arti?cial rubber ranging irom 2 to 50 parts for each part by weight of said polyvinyl ester, said mutual solvent being a blown terpenic product. 6. The method 01 making a compatible mixture of a butadiene arti?cial rubber and a polyvinyl molecular weight of at least 20,000, and a mutual solvent which is non-volatile up to 150° C., the ratio of said butadiene arti?cial rubber ranging from 2 to 50 parts for each part by weight of said polyvinyl ester, said mutual solvent being blown turpentine. ‘ 11. A gel of a polyvinyl ester and blown turpen ester which comprises mixing said polyvinyl ester 25 tine, which gel is compatible with butadiene arti at about 150° C. with a material which is a mutual solvent for said polyvinyl ester and said butadiene arti?cial rubber to form a gel, said mutual solvent ?cial rubber. MORTIMER T. HARVEY.