USRE24206E - Solvent solutions - Google Patents

Solvent solutions Download PDF

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Publication number: USRE24206E
Authority: US; United States
Prior art keywords: maleate; resins; butyl; copolymer; monohydrogen
Prior art date: 1954-05-03
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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1954-05-03

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1956-08-28

1956-08-28 Application granted granted Critical

1956-08-28 Publication of USRE24206E publication Critical patent/USRE24206E/en

Status Expired legal-status Critical Current

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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride

Definitions

This invention relates to novel vinyl chloride interpolyme'r resins particularly adapted for dissolving in solvents for application as coatings, paints, lacquers, inks, adhesives, and the like.
'Vinyl chloride, resins because of their cheapness, hardness, stability and other desirable properties, have long been considered potentially desirable as coatings, paints, lacquers, adhesives, inks, and the like. inevitably, however, these resins are not soluble in cheap hydrocarbons; are not compatible with alkyd resins; and do not exhibit good adhesion to metallic and other surfaces. For these reasons, the use of vinyl chloride resins in these fields has been somewhat limited.
Another object is to provide such resins which are soluble in cheap hydrocarbon solvents such as benzene, toluene, xylene, and the like.
a further object is to provide such resins'having good compatibility with the alkyd resins.
a further object is to provide such have good adhesion to metallic surfaces.
resins which will i The percentage sfcited are all on the basis of the total weight otthe .resimf Resin'sfcoming within the above compositional, ranges have excellent solubility in hydrocarbon solvents,' fare' stablyfcompatible with alkyd resins, and havegoodadheson to metals. In addition to these desirable and-unique properties, they also preserve unimpaired theexcellent general properties of conventional vinyl chloride resins, particularly their hardness and their good resistance to aging.
the resins of this invention find particular application to coatings, such as paints, especially for outdo'o r-ex'pose d metal equipment; asinksiand as adhesives.
Suitablexzhydroearbon a groups include methyl groups, ethyl groups, 'norrnah and iso-propyl groups, normal-, secondary and tertiary butyl groups, the several amyl groups, n-hexyl groups,c'yclohexyl groups, Z-ethyl hexyl groups,phenyl gr0ups,'-benzyl groups, naphthyl groups, and the like.
Specific exemplary diesters include dimethyl maleate/dimethyl fumarate,diethyl maleate, di-n-butyl 'maleate, di-n-butyl furnarate, di-n-propyl maleate, diisopropyl maleate, diisobutyl maleate, disecondary butyl maleate, di-(Z-ethyl hexyl) maleate, di(cyclohexyl) maleate, and dibenzyl maleate.
Suitable half-esters include
esters used need not be pure compounds; thus mixtures of suitable dialkyl maleates and/ or fumarates and mixtures of suitable monoalkyl monohydrogen maleates or fumarates may be used in lieu of pure esters of these respective types. It will also be understood that the maleates and fumarates will be indistinguishable in the product resins, since their unsaturation will be obliterated in the polymerization.
a particularly useful combination of a specific dihydrocarbon ester and monohydrogen monohydrocarbon ester has been found to be the combination of (A) a commercial material offered as di-n-butil maleate but actually containing approximately equal proportions of di-n-butyl maleate and di-n-butyl f umarate and (B) ,n ono-n-butyl monohydrogenmal eate H; 5 K
the resins of" the; invention are m c y ro arbon solv X ene, e i n. lubst PtQRQfQQHt... 30% of the total weightof the on. Qoafingsionned from these solutions upon. metal and, other sum rs highly adhesive thereto and e not eas remqye by abrasion or flexure of the substrate, esipsof this in on e mpat b e th. e alkyd. r r solvent solutions and also the dried tilfm produced from solvent solutions of mixtures'oftheresin's of this invention with alkyd resins.
the resins of this invention accordingly find extensive use in coating composition-s such as paints for use on metallic and other surfaces, particularly in coatings for metallic equipment subject to outside exposure conditions such as railway vehicles, automobiles, tractors, vending and dispensing machinery and the like.
the resins of this invention are also very suitable for use in solvent-based inks for printing upon plastic
the resins of this invention are further admirably adapted for use in the formulation of adhesives for joining metal, wood, plastics, and the like.
acids containing [4-22] 6 --2 carbon atoms 14-35 Vin chloride a A mnoalkyl monohykogen esteri of an acid se- Dilbutyl g g varie'dper e e l xmt group.
Example V the percentages being based on the total weight of the Parts by weight copolymer.
N H 55475 Mono-cyclohexyl monohydrog en maleate I 5.
Example VI 5. 06,1. Per cent Vinyl chloride) -75
the procedure of Example V was repeated, substituting M mono-benzyl monohydrogen maleate. fan the mono-cyclo- D .h .x l.... 3 3?” hexyl maleate.
the product was substantially the same a 99 93 Y m'..9 .8?
the percentages being based on the total weight of the copolymer.
a copolymer of Per cent Vinyl chloride 55-75 Di-n-butyl maleate 14-35 A monoalkyl monohydrogen ester of an acid selected from the group consisting of maleic, fumaric, and chloromaleic acids containing [3-12] 5-14 carbon atoms 5-10 Trichloroethylene 1.5-6.5
the percentages being based on the total weight of the copolymer.
the percentages being based on the total weight of the copolymer.
the percentages being based on the total weight of the copolymer.
a copolymer of Per cent Vinyl chlor 55-75 Di-ethyl maleflte 14-35 A monoalkylmonohydrogen ester of an acid selected from the group consisting of maleic, fumaric. and chloromaleic acids containing [3-12] 5-14 carbon atoms Trichloroethylene the percentages being based on the total weight of the copolymer.
the percentages being based on the total weight of the copolymer.
a copolymer of Per cent Vinyl chloride 55-75 Dibutyl maleate 14-35 Monocyclohexyl monohydrogen maleate 5-10 Trichloroethylene 1.5-6.5 the percentages being based on the total weight of the copolymer.
the percentages being based on the total weight of the copolymer.

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

Description

United States A Patent v 24,205 VINYL CHLORIDE RESINS FOR APPLICATION AS SOLVENT SOLUTIONS George P. Rowland, Jr.,

Pa., assignors to The Firestone Tire & Rubber Company, Akron, Ohio, a corporation of Ohio a 15 Claims. (Cl. 26078.5)

Matter enclosed in heavy brackets [I] appears in the original patent but forms 'no part of this reissue specifi and Robert A. Piloni, Pottstown, 1

cation; matter printed in italics Indicates the additions made by reissue.

This invention relates to novel vinyl chloride interpolyme'r resins particularly adapted for dissolving in solvents for application as coatings, paints, lacquers, inks, adhesives, and the like. 'Vinyl chloride, resins, because of their cheapness, hardness, stability and other desirable properties, have long been considered potentially desirable as coatings, paints, lacquers, adhesives, inks, and the like. fortunately, however, these resins are not soluble in cheap hydrocarbons; are not compatible with alkyd resins; and do not exhibit good adhesion to metallic and other surfaces. For these reasons, the use of vinyl chloride resins in these fields has been somewhat limited.

Accordingly, it is an object of this invention tov provide novel vinyl chloride resins suitable as solventapplied coatings, paints, lacquers, inks, adhesives, and the like. 1

Another object is to provide such resins which are soluble in cheap hydrocarbon solvents such as benzene, toluene, xylene, and the like.

A further object is to provide such resins'having good compatibility with the alkyd resins.

A further object is to provide such have good adhesion to metallic surfaces.

ance with this invention, in vinyl chloride, resins, having copolymerized therein:

resins which will i The percentage sfcited are all on the basis of the total weight otthe .resimf Resin'sfcoming within the above compositional, ranges have excellent solubility in hydrocarbon solvents,' fare' stablyfcompatible with alkyd resins, and havegoodadheson to metals. In addition to these desirable and-unique properties, they also preserve unimpaired theexcellent general properties of conventional vinyl chloride resins, particularly their hardness and their good resistance to aging. The resins of this invention find particular application to coatings, such as paints, especially for outdo'o r-ex'pose d metal equipment; asinksiand as adhesives. I I

TI-IE'fMAlLEIQAND' FU MARIC DIESTERS AND The maleic and fuinaric dihydrocarbon esters, and monohydroc'arbon" monohydroge'n halt-esters employed as starting materials in the p'r'eparationoi resins in accordance with this invention areYes'ters, within the cited classes, in which the radicals, esteritied by the maleic or furnarici acidare hydrocarbon radicals which contain from 1 to lqcarbon stems; "On this' basis, the diesters will contain fro [4 to- 22] 6 to 24 carbon atoms, and the half-esters will contain from [3 to 12] 5 to 14 carbon atoms. Suitablexzhydroearbon a groups include methyl groups, ethyl groups, 'norrnah and iso-propyl groups, normal-, secondary and tertiary butyl groups, the several amyl groups, n-hexyl groups,c'yclohexyl groups, Z-ethyl hexyl groups,phenyl gr0ups,'-benzyl groups, naphthyl groups, and the like.' Specific exemplary diesters include dimethyl maleate/dimethyl fumarate,diethyl maleate, di-n-butyl 'maleate, di-n-butyl furnarate, di-n-propyl maleate, diisopropyl maleate, diisobutyl maleate, disecondary butyl maleate, di-(Z-ethyl hexyl) maleate, di(cyclohexyl) maleate, and dibenzyl maleate. Suitable half-esters include "methyl hydrogen maleate, n-butyl I and other surfaces.

hydrogen maleate', n-b'utyl' hydrogen fumarate, n-propyl hydrogen maleate benzyl'hydrogen--maleate, cyclohexyk hydrogen maleate, and the like. The esters used need not be pure compounds; thus mixtures of suitable dialkyl maleates and/ or fumarates and mixtures of suitable monoalkyl monohydrogen maleates or fumarates may be used in lieu of pure esters of these respective types. It will also be understood that the maleates and fumarates will be indistinguishable in the product resins, since their unsaturation will be obliterated in the polymerization. A particularly useful combination of a specific dihydrocarbon ester and monohydrogen monohydrocarbon ester has been found to be the combination of (A) a commercial material offered as di-n-butil maleate but actually containing approximately equal proportions of di-n-butyl maleate and di-n-butyl f umarate and (B) ,n ono-n-butyl monohydrogenmal eate H; 5 K

THE PREPARATION on Frnnmrrn twnxsior The em ly ne s; fith sinvsnfib .m y beg b i mixing together the several monomeric starting iiiaterials and subjecting them to any of 'theusualfree-radical; poly; merization systems andconditions, for instance in solution in solvents, and in em 1 free-radical generating tical production, howe polymerize-these mater by the known suspensio polym general this techniqueinvolv in an aqueous medilnit, C9

purpose are hydropl ilie h as gelatin, polyvinyl alcohol, d, methyl 1 9s. and dium constitutes about at leas lialf of e'polymerization mass. The reaction'is promotedby the presence of free-radical-generating agentgsoluble;in mono; mer phase of the suspensio s ucht'as benzoyl peroxide, perbenzoic acid, p-chlorobenzyl peroxide, t-butyl hydroperoxide d thanks- T e suse n hase an t monomer phase are agitatedtoggither; sofas t the latter n h o m nand he ma ignant,

is adjusted to values, such. toviniti tion reaction, usua;lly. on th monomers in the s ended Y d uspen l nv Qt n" esin. nt s mm th s qu ouss sn nsi nths rssinis lated by filtration,

PROPERTIES AND, USES on'mn OF;

THIS I'NVE'NFHQN The resins of" the; invention are m c y ro arbon solv X ene, e i n. lubst PtQRQfQQHt... 30% of the total weightof the on. Qoafingsionned from these solutions upon. metal and, other sum rs highly adhesive thereto and e not eas remqye by abrasion or flexure of the substrate, esipsof this in on e mpat b e th. e alkyd. r r solvent solutions and also the dried tilfm produced from solvent solutions of mixtures'oftheresin's of this invention with alkyd resins. The resins of this invention accordingly find extensive use in coating composition-s such as paints for use on metallic and other surfaces, particularly in coatings for metallic equipment subject to outside exposure conditions such as railway vehicles, automobiles, tractors, vending and dispensing machinery and the like. The resins of this invention are also very suitable for use in solvent-based inks for printing upon plastic In view of their excellent adhesion to a wide variety of surfaces, the resins of this invention are further admirably adapted for use in the formulation of adhesives for joining metal, wood, plastics, and the like.

sa able. n sa h o uene SPY, p: to

nd coqlinaias s andi ith n,

With the foregoing general discussion mind, there are given" herewith detailedexamples of -the practice of this invention. All parts given are by weight.

chloroethylene of 67 .9/2l.2[8.l/2.8. The above ingredients were chargedto a reactor provided'with a heating 0 per minute, and continued throughout the-react followed. The temperature was adjusted to 65 C., held t thi alue p hre hour a d hsn 9W9 $1; 9 a sla .u,=- r. -h A he e dof hi ime theiunrea ticds invl" chl r VQPWLI ndv the charge was cooled to 25 C., discharged, dewateredand ashednn afilts 'w htdsion sd ateljta d tr d T es a sinh d a rslat evis a wi 0 salmiw H QQQnQ -3 iahd 9 m, ,aclsar 25%: 9 p. n olu ne 1 he was ex atedo co patibil t w th a W d variety or. c nmercialzgl n a a n nefol ows;

i Stock so ution, 'AY

V nyl. chlor d es (pr ared. iustj cr bedl Me l n' tre Compatibility mixture:

SolutionA" 1'-5 parts I Hydrocarbon solvent solution of (per Table I). alkyd-resin lj5 7]-5 '-l-pa rts 5 1 (per Table I);

- At stoclt splutionwas madeup fromtheingredientslisted at A and was used inall thetests. to-follow, The tests wer .wndustedasbl pys; v.nti i-A wa mixed i samples of as- $9. 1!??? .ia elm-a1 eiinawhish were supplied as concentrates in various hydrocarbon solvents. The weight; ratios; in which the solutions, were mixed were: 1:5, 1:2, 1:1, 2:1, and 5:1. Each of the [reultant] resultant: mixtures was visually examined andrated for compatibility; Likewise rglass microscope. slides were dipped into the solutions and dried for 48 hours, andthe resultant films visually rated for compatibility.

An identical series was run for comparison, using, in place of the vinyl chloride resin according to the present invention, a vinyl chloride resin which is the only commercial resin offered 'at present as having good solution properties and compatibility with glyptal resins. The data for the two series of tests are [sen-t] set forth in Table I, the data for the resin of this invention being placed to the left and above the diagonal lines in the rectangles in the table, and the data for the commercial resin being placed to the right and below the said diagonal lines.

manor I Oommerolall reperedGlyptelResin solntionoonoentrste Compatibility (See Codes Below) OonstituentsoiAlkyd Bem 1 "3%? msoiu'mm Inrmn o :5, Retio oiVinylOhloride'Resin'Bolutlon to RatlooiVinylOhlorideResln'Sog Oil Solvent 5 'Glyptal Resin Solution lutiontoGlyptal Resin Solution Phthelic Phenolic a v E" Anhydride v Resin g (Percent) Type Perirereent) E 1:5 1:2 1 1 2:1 :1

t cent o v v a 25 Petroleum 70 I C P P l P N I N 's u-lu. I I

an ...do.. '60- I" C I O 0 y a I O G as; xylene"; so 0 P P I, V 3 I to P r /P 28 "Drying i .do..... so -/0/ comes r012 CEOMPATIBILITY Liquid compatibility:

0 Compatible P Partially compatible (cloudy solution) I Incompatible (lmmiseibility and gel (oi-motion) Film compatibility:

C Compatlb e continuous tilm 781 Hz Very sh m cloud in mm 81 Hz Slightly hazy, cloudy film Hz Hazy, cloudy film (suitable tor pigmented coatings) N Non-continuous film (mottled, rough nhn our-lace) Rating (or rosin oi this invention.

- 1 --------"Ratingioroommereialresln From an inspection of the table, it will be" evident that Parts by weight the resins of this inven "on out-performed the commer- Mono-n-butyl monohydrogen maleate I 5 cial resin over substantially the entire-range of cOm- Trichloroethylene' 2 parison. t Benzoyl peroxide 1 ExampleII I PVM/MA (as in Example 'I) 0.1

Part8 Water (deionized) 128 Vinyl ChlOl'l-dfi I 50 I I Diethyl maleate I 13 A series of runs was made using various difierent maleate Mono-n-butyl monohydrogen maleate 5 diesters in the several runs as set out in Table II here- Trichloroethylene 4 inafter. In each run the selected maleate diester, and L p CD3 2 other ingredients in the proportions set out in the above 0 P' y 9 =55 recipe, were charged into a reactor, polymerized and the lde P dl'bfltyl Phthalate, manufactured by resultant resin recovered as described in Example I. Set yLucldol .Novadd'Agene forth herewith'in Table Il-are the properties of the resins. Methyl cellulose I I I I I 0.8 1 1 I (15 cps. grade) l 1 TABLE 11 Aerosol MA 0.4 I

(Dihexyl I sodium sulfosuccinate, I Properties of the Resin I tured by American Cyanamid C D.) 1 a 7 1 W Water (deionized) ........'.i;.....--..;...--;....-....- 128 Maleate Dlester Used l Solution Run a y Relative 25% Compati- No. The above materials were eharzedinto a eaetor and gg g 2%? polymerized at C. for 24 hours. Theresin recovered I my amytds I from the resultant suspension had a relative visoosity of 1.26 in 1% cyclohexanone solution, gase clear 25% solu- D1Qthy]male5t9 1, Hazy P 1 tions in toluene, and hadexcellent adhesion to metals gtfig ggv fgg {5 ---gg----- g and compatibility with alkyd resins. 7o Dl-lso ut yl meleate 1130 ie 0 4 Example IIL-Various diesters: Diseo-buty 1.28 "-32.--- o a Dilsopropl I 1.22 do. 0 6 Yam by w ight Dl-( thylhexyl) melee L32 ezy---. 0 7

13 in 1% oylohexanone solution. 4 i Home code as in Table I; the test alkyd was that oi item No- N (Selected per Table II) I the testwas made withalzlratlo oi solutions.

some.

7 :8 All of these resins formed clear 35% solutions in. i What is claimed is: methyl ethyl. ketone, and adhered well tometalswhen 1.. Avqqpolymeiinf. Per cent coated thereon. Y yl qnd a -75 Adialkylesterofanac selewedfroni Example IV. Var1ous proportions of comonon ers 5 consisting ofzfmalel c, fumaric, and chlorornaleie.

. acids containing [4-22] 6 --2 carbon atoms 14-35 Vin chloride a A mnoalkyl monohykogen esteri of an acid se- Dilbutyl g g varie'dper e e l xmt group. Q i ina e s i Mono(n-butyl) monohydrogen mal'eate Table III gii gglggi 5 Trichloroethylene Benzoyl' p x M 1 Triehloroe thyleneih ;.t 1.5-6.5 v /M zes'in '1-:e 1iei 0.1; h p rc n e beinaf th tal weight of the Water (deionized)v 128.4 qo olynier- I A series of runs was made," using the ifn'onpizner'ic; Q I g g i l in l fe n pmpqr lon mth everal runs ass t A m e: dimbutyl inmate aimbmyl f fumarate in approximately equal proportions l4-35 Amonoalkyl monohydrogen ester; of an acid selected from the group; consisting of maleic,

' Relative Viscosity i inyl Dibutyl: hutyl V chloro Chloride Maleate Maleate ethylene Insoluble I11 1% cyclohexanone solution. A v 1 Same code as in Table I' the test alkyd resin was that of item No.

6, and the test was made with a 1:1 ratio of solutions.

Example V the percentages being based on the total weight of the Parts by weight copolymer. Vinyl chloride 42 ,-P,ercent Di(n-butyl) maleate 13;. N H 55475 Mono-cyclohexyl monohydrog en maleate I 5. d -bgtyi v Trichloroethylene 2 r approximately equal proportions 14-.35 Luperco C in 21 1) 2 Mono-n-butyl monohydgogen mgleate 5I0 SurfiaNo1k12188 I If g6 y Ifrlchloroethylene 1.5-6.5

11 a yary ester su onate, 0 active inmatings; AATCC ygaltfBmk 1950i pf, I 5.0 gesibeing-i-based-on...the..total Weight of the [6351365, manufactured by .E. F. Hflu hri Q 7 ton-58 COJ 7 i 4. A eo oly er of' P r en I V nyl chlor1de- 679 Water ---*-.-e-1r-?-e---.-e-r?-? A1 di fl l t di b lh Th a ve ingredient wer p lymer zed-asin-Ex mple-l- 55 iumai'i te iu ap roximately: equalf-proportions n 21.2 e r uct r si fq med ah z 5 lu ion n q uenc, Mono-ii-butyl'imohbhydrogenfmaleatei; 8.1 a clear soluti n-in methyl ethylketqne,-, was 9111 Trichloroethyleno; 2.8

patible with alkyd resin in 1:1 ratio by the test of TebIe'I,

item No. 6, and had fair adhesion to metals. the percentages being based on an total welght' of the 6 copolymer. Example VI 5. 06,1. Per cent Vinyl chloride) -75 The procedure of Example V was repeated, substituting M mono-benzyl monohydrogen maleate. fan the mono-cyclo- D .h .x l.... 3 3?" hexyl maleate. The product was substantially the same a 99 93 Y m'..9 .8? ofan F as that of Example V, except that the 25% toluene solu- F- P if' 3 tion was only slightly hazy, and the test on allgyd comw fl l l wntammgm patibility showed fa slight cloudiness. Y F m From the o c in a discussion an Tagghlmi 1 15.65 specific examples, it will be evident that'fliis inyention the Percentages g 1. -L hof the provides novel vinyl chloride resins admirably suited for 1 31 pp i n lv ol s iiiroma hydrocarbon. 6. A copol y'm'onof v e Per cent ve n coat ngs,.. a q e. .s,, paints, res.- vinyl chlqizide 55-75 andv the like. The..resins...are .allncharacterizedmbywgood DifLz-qilllyl l1C{XlLll}ltQ, v lei-.35 compatibility with alkyd resinsand gogd -adhfifli neiq mb Mgpo-mbpty n onoh d r 57 ,0 tallic and othersurfaces. 1;; Trichloroethyl'ene the percentages being based on the total weight of the copolymer.

7. A copolymer of Per cent Vinyl chlor 67.7 Di-(Z-ethyl hexyl) maleate 21.0 Mono-n-butyl monohydrogen maleate 8.1 Trichloroethylene 3.2