CA1160395A - Process for the preparation of oxidation products of ethylene copolymers, and their use - Google Patents

Abstract

ABSTRACT:

Low-melting, easily processable and at the same time hard polar waxes are obtained by treating copoly-mers, which are composed of ethylene and 0.5 to 50% by weight of a monomer containing oxygen-containing groups and have melt indices (MFI 190/2) of between 0.01 and 400 g/10 minutes, in the molten state, dispersed in a dispersing agent which is inert towards oxygen, with oxygen or oxygen-containing gases. Preferably, ethylene/vinyl acetate copolymers are oxidized, and these oxidation products are particularly suitable as the wax component in water-based and/or organic solvent-based polishes and in pastes.

Description

t ~ 6~395 ~ 2 --Numerous processes are known for the preparation of polar waxes by the oxidation of polyolefins with oxy~
gen or oxygen-containing gases. In these processes 9 the oxidation is generally carried out in such a way that ~he polymer is ~reated in the solid or molten state with oxygen~con-taining gases. m e processes have the dis adYantage -that -they lead either to w~xes which are hard but are high-melting and thus difficult to process, or to waxes which are low-melting and easily processable but are soft The hard high-melting waxes wi-th mel-ting points above 105, generally above 110C, can only be emulsified7 for example~ with considerable technical effort, under excess pressure, at temperatures above 100C.
In contrast, because of their low hardness, the low- ~
melting, easily proc~essable waxes produce, for example on further processing t~o give emulsions, preparatlon~ which give tacky fil~s with a high dirt uptake and unsatis~
factory mechanical resistance.
Hard polar waxes are obtained by the oxidation of extensively unbranched polyolefins; they are always h1gh-melting. Polar waxes with low melting points are formed on the oxidation of more highly bra~ched polyolefins.
ey always possess only a low har~ness.
In German Patent Specification 2,035,7Cl6, for example, a process is described In which polyethylenes or copolymers o~ ethylene with C3- to C8~c~-ole~ins are oxiclized in the molten state, in aqueous dispersion, with . ~

1 lB0395 - -~ ~ .
o~ygen containi~g ~asesO In .~act3 very hard waxes, .~nter alia, can also be obtained ~y this process, but they have melting points which are generally signifi-- cantly ahove 110C, and they can thvs only be processed -with great difficulty.
A process for the oxidation of polyethylene or ethylene copolymers with oxygen or oxygen-containing gases is ~nown from East German Patent Speci~ication 11~,625 9 in which process a liquid additlve with a hlgh heat of vaporization, which is inert towards the reac-tants, is continuously metered into the polymerization melt, during the oxidation9 and is carried away again w1-th the reac-tion gases. Suitable ethylene polymers are polye-thylene ~axes with molecular weights ~ 159000 ~5 and also ethylene/vinyl acetate copolymers with vinyl-acetate contents of 1 to 45 % by weight. In fact, l~w-melting, but very soft and tac~y oxidation products, with penetration i.ndices which are generally above 20, are obtained by this process, and -thîs applies to a ~0 particu~arly pronounced ex-tent to the oxidation products of the ethylene/vinyl acetate copolymers which, as is ~nownj are highly branched.
To improve the unsatisfactory properties o~ the ~own oxidation products, it has already been proposed to subaect polyethylene waxes with molecular weights ~ 159Qoo, mixed with high-molecular homopolymers or -copoiymers wlth molecular weights ~155000, to oxidation 1n the melt (East German Patellt Specification 125~131).
I~e oxidation products obtai.ned in this proce~s are 3 g 5 1~ ~ .
non~homo~e7leous and are again also either high-mel-ting with me7ting points abo~e 110C or so~t with penetration lndices above 10. Furthermore~ long reaction times are required and this necessitates considerable ef~or-t and 5 leads to thermal degradation of the products. m us;
East Germ~n Pa~ent Specification 128~507 reco~mends the oxidation of ethylene/vinyl acetate copolymers, inter alia~ in -the melt, with the addition of special me-tal catalysts. Even in this case, only high-melting or 10 so~t waxes are obtained, which also exhiblt colora-tions as a result of the metal catalysts presen-t therein Finally, in an e~`for-t to obtain polar waxes of better quality, a~ttempts have been made initially to thermally degrade high-molecular ole~in homopolymers or 15 co~olymers with the exclusion of oxygen and then to oxidize them in the melt with oxygen-containing gases ~Eas-t German Patent Specification 128,875). However, - even in this way, it is not possible to prepare waxes which are low-melting, easily processable and at the same time hard. Furthermore, this process is uneconomic as a result of the two process steps required.
The object o~the present invention was therefore to make availa~le waxes which are low-melting and therefore easily p~ocessable, but are at the same time ~ery hard.
Surprisingly, it has been ~ound -that this is possible if special ethylene copolymers are oxidized in the molten state1 dispersed in a dispersing agent~ with o~ygen or oxygell-containing gases~
Accordingly, the inventlon relates to a process .

., 6~

~or the preparation of polar wax~es which are low-melting, easily processable and at the same time~hard, by the oxidation o~ ethylene copolymers with oxygen or o~ygen-containing gases, a m~lt of the polymer~ dispersed in a disperslng agent which is inert towards oxygen~
being trea-ted with oxygen or oxygen-containing~ses a-t temperatures between the melting point o~ the polymer and 100C above the latter, at an excess pressure between 0 and 100 bars and~ if appropriate~ in the presence o~ we-tting agents and/or catalysts 9 with con-tlnuousi~tenSiV~mixing, which process comprises using those copolymers, with melt indices betwe~n 0.01 and 400 g/10 minutes, in which, in addition to e-thylene, 0.5 to 50 % by weight of other monomers which are olefinic but contain oxygen-containing groups are ... . ~
copolymerlzed.
It was not to be expected that polar waxes which - are low-melting, easily processable and at the same time ~ery hard can be obtained by the process according to the invention, because it had to be assumed ~rom previous experience that it would only be possible to prepare either waxes ~Ihich are low-melting and in 4act easily processable but are soft, or waxes which are high-melting, difficult to process and then also hard. Above ~5 all, however r it must be regarded as surprising that waxes with such a high hardness and other advantageous properties could be obtained from polymers wi-th a high degree of branching, because, from previous e~perie~ce~
particularly soft waxes were to be expected precisely 3 ~ 5 when usln~ br~nched polymers.
Fin~lly, it could not be prediGted that~ in the process according to the invention9 if t~e reaction is carried out with water as the dispersing agent, in accor-dance with the pre~erred procedure~ no noticeable hydro-lys~s of -the ester groups of the polymers used occurs, even in the presence of very large amourl-ts of water9 that is to say oxidation products with a high content o~
esters o~ v~lue in application technology are formed9 which have numerous improved properties compared with known oxidation products.
m e process s-tart~ from raw materials which are available at low cos-t. The reaction also proceeds, .
withou-t the use of catalysts which degrade the products, in a mild and exceptionally rapid manner in a single process step. Light-colored, odorless and homogeneous oxidation products without crosslir~ed portions are formed. The oxidation products have low dropping points but at the same time have high hardnesses a~d numerous other advantageous properties. In particu-lar, they can be further processed with reduced effort and thereby yield products with improvedJnovel use pro-- perties.
In terms of the lnvention~ ethylene copolymers are to be understood as meaning ethylene copolymers in which, in addition to ethylene, l;to 5G % by weigh-t o~
other ole~inic monomers, which con-tain oxygen-con-taining groups, has been copolymerized. 1~e copolymers are pre~
pared in accordance wi-th known processes~ In parti--` 1 160395 cular9 they are obt.ained by f`ree-radical high-pressure polymerization~ solution polymerization, suspenslon polymerization or emulsion polymeriza-tion~ The.ole~inic monomers with oxygen-containing groups, which are used 5 in addition to ethylene ~or the preparation o~ the copoly mers, are, for example, vinyl esters of carboxylic acids~
such as vinyl acetate or vinyl propionate, and also vinyl ethers or a~-ethylenica~ly unsaturated carboxylic acids and deri.va-tives thereof, such as acrylic acid, methacrylic 10 acid9 ethacryliG acid, crotonic acid, f.umaric acid, maleic acid, maleic anhydride, itaconic acid and mesaconic acid, or the esters of these acids. me copolymers can also contain several monomer components of di~ferent ... ..
types, with oxygen-containing groups~ The proportio~
15 o~ the monomer with oxygen-containing groups, in the copolymer, is 0.5 to 50, preferably 1 to 30 and ln parti-cular 1 to 20 % by weight. m e copoly~ers have a melt index o~ between O.Ol and 400, prcferably between O.l and 200 and in particular between O.l and lO0 g/lO minu-tes9 20 determined in accordance with DIN 53,735 at 190C and with a load of 2016 kp (MFI 1gO/2~. m e molecular weights of copolymers of this type are generally above 15,000~ m e copolymers can be co~pletely or partially saponified before ~he oxidationJ Furthermore, the 25 copolymers can be subjected to the oxidation in a mixture with one another or in a mixture with other polyolefins and/or synthetic or natural waxes or para~ins~
The oxidation process is generally carried ou-t in such a way that the ethylene copoly~ler i5 dispersed in a .~ .

\ ~ l dispersing agent which is inert towards oxygen, if appropriate in the presence of catalysts and/or wetting agents, and treated with the reaction gas at a temperature above the melting point of the copolymer, with constant, thorough internal mixing of the reactants. As a result of being dispersed in the dispers-ing agent, the polymer can be brought into very close contact with the reaction gas, so that an exceptionally rapid and at the same time mild reaction takes place.
Water is preferably used as the dispersing agent, but, in addition to this, saturated fatty acids with 2 to 8 C atoms or chlorinated hydrocarbons and the like, for example, can also be used. The dispersing agent is used in an amount by weight which is 0.5 to 20 times, preferably one to 10 times, greater than that of the copolymer. Dispersing agent which escapes with the off-gas is replaced by fresh dispersing agent if necessary. To facilitate the dispersion of the copolymer, wetting agents, for example fatty acids, fatty alcohols, ; ethoxylation products of alcohols or phenols, or metal soaps, metal hydroxides or metal salts, can be added to the reaction mixture.
To reduce the induction time and to accelerate the oxidation process, the reaction can be carried out in the presence of catalysts. Examples o~ suitable catalysts are peroxy compounds or also previously oxidized copolymer in an amount of from one to 10% by weight, relative ~ the copolymer or used dispersing agent~ Furthermore, ozone can be mixed with the oxidiæing gas. Moreover, metal compounds can be added as oxidation catalysts.

1 16039$
_ 9 _ ~oweverç when adding the last~mentioned substances, there is the danger that colored and crosslinked products .
may be formed, but, because of the cexceptionally high reaction rate, compared with known processes, -the pres-.ence of catalysts of this type is not generally nece~sary.
~ he reaction temperature is above the melting point of the copolymer used and exceecls the melting polnt . by up to 100, preferably by up to 80C. The mos-t favorable reactio~ temperatures are between 130 and 180, preferably 140 and 170C. Temperature control does not present any difficulties because the dispersing agent used is an ideal medium ~or supplying and extrac-ting heat.
Heat extraction takes place with the aid of the dispers-ing agent, both via the vessel walls and via the gas 1~ volume by evaporative coollng.
~ m e oxidation can bè carried out at normal pressure or u~der an excess pressure of up to 100 bars e ~ost favorable reaction pressures are between 5 and 1009 in particular between 5 and 30 bars of excess pres-20 sure. m e preferred oxidizing ag.ent is air, the oxygen content of which can also be increased, if appro-priate, by adding o~ygen.
.~ The oxidation can be interrupted after any desired degree of oxidation has been reached.The separation of the dispersing agent and the oxidation product does not present any difficulties. The dispersing agent separates out from the oxidation melt, for example on standing, and can then be run off or drawn off The separation is particularly successful if the oxidation has been. carried .. . . .

~ 10 -out a-t low temperatures 9 for example at 150C. The separation can also be promoted by adding emùlsion breakers~ for example polymerization products of propy~-ene oxide and/or ethylene oxide. Residual dispersing - 5 agent can then be removed by evaporation. Spray-drying - of the mois~ product melt is also possible.
Wlth -the process according to the invention~ it ~s possible to achieve virtually any degree of oxidation under consideration. For example, product acid numbers 10 o~ up to 2Q0 can be achieved. In the case of starting materials which do n~ themselves have acid numbers, in particular oxidation produc-ts with acid numbers of ~etween 3 and 100, preferably between 3 and 50 are of practical importance. r~he op~imum product acid numbers 15 in an individu~l case depend on the type of starting material and on the intended use of the product. Because the hardness of the oxidation products decreases with lncreasing acid numberD it is not generally at-tempted to ob-tain higher acid numbers than are required in order to 20 achieve o-ther propertiesJ for example a good emulsifi-abili-ty or an adequa-tely low melt viscosity. In this colltext, higher acid n~bers are generally necessary in the oase of copolymers with ahigher ethylene content than in the c~se of those with alower ethylene content.
m e new oxidation products have hitherto unknown combinations of properties. The products a~e light-colored and odorless, meir molecular weights are generally between 200 and 20,000, preferably between ~00 ~nd 8,000~and -thei~ melt viscosities are between 200 and .

.. .

~ 1603~
-- 11 -- . .
50~000y pre~erably between 500 and 10~000 mPas (120C~.
The molecular wei~ht distribution i~ narrow The oxidation products are in themselves.homogeneous and do not contain any crossli~ed portions. ~The dropping 5 ~oints are below 110C, generally below 105C and ~re-quently below 100C. The products ne~er-thele~s have u~.~usually high hardnesses. Their needle penetration is generally less than 10 10 1 mm, usually less than 5 10 ~ mm The hardness (pressure req~red to pro-duce flow) is generally greater -than 200 bars, usually greater than 400 bars This is much more a case of a viscous hardness, with particular advantages in appli-cation technology, than of a brittle harclness. In . ~ ...... . . . . .
addition to the oxygen-containing groups produced by oxidation~ the products contain the oxygen-containing groups originating from the starting material. This man;fests itsel~, ~or example in the case o~ oxidation produc-ts of e-thylene/vinyl acetate copolymers, in the ester numbers~ which, in contrast to those o~ known . 20 oxidation products of po~yethylene waxes, are many times greater, for example 1 to ~0 times grea-ter, than the respective aci.d numbers. The combination o.~ the ~ oxygen-containing groups originally presen-t and those produced by oxidation imparts, to the o~idation products, .25 a particularly balanced polarity, ~rhich leads to improved properties in application technology. The ox;dation produc-ts are distinguished, i.n particular, by a good emulsi~iability, shi.ning capacity, sol~ent-binding capacity, paste-~o~ming capacity, abili.ty to be ~ 12 ~
polished~ adhesive power and compatib31ity with other substances. As a result of these properties, the oxidation products can adv~ltageously be used in numerou.s fields.
The products are pre:~erably suitable for the preparation of aqueous emulsions. The emulsifica-tisn can be carried out under pressure, or also -because of the low dropping poin-ts of the oxidation products - under normal pressure, with low technical effort. F'inely divicled, highly transparent emulsions with considerably fewer specks are for~ed.The em~sions d~ to give films with a high instant shine, and these have an improve~ hardness, scratch resistance, abrasion resistance, flexibility, breaking strength and adhesion ~o the substrate. In particular, they are also distinguished by a reduced dirt uptake and increased slip resistance. Worn films can be regenerated by polishing The emulsions can advantageously be used in the field of cleaning agents, for e~ample in instant-shine emulsions, In addition, they can also be used, f~r example, in the ~ield of paper coating, the ooating of fruit, and rendering textiIes, wood, leather, build-lng materials and the like hydrophobic and pro~iding ~he said materials with a finish.
The produc-ts are furthermore suitable for the preparation of solvent-based polishes, floor waxes and shoe polishes ~ld also of anti-corrosion agents, coat-ing compositions, hot melts, asphalt prepara-tions~
~dhesives, color dispersions, pi~ment concen~rat~s, --. carbon paper coa-tin~s, abrasion-resistant pri.ntîng i~ks, lacquer-matting agents, textile firlishes, pouL~a'o-e seal~
ing compounds, precision castin~ ~laxes, cosmetic pre~
parations, candles 9 greases, lubricating oil ~dditives 7 lubricants for metal working and a~iliari.es for plas-tics processing, ~or example lubric~nts or parting com-pounds ~n preparations, the products general~y improve the compatibility, adhesion, sealing capacity?
~lowability ~nd impermeability.
10 As regards the preferred possible uses of the new oxidation products as the wax component in water-based ~ld solvent-based polishes, in aqueous and solvent-based emulsions and also in pastes, the oxidation pro-. - . -- ~ . . . .
ducts used for this purpose arey in particular, those which have been obtained from e-thylene~vinyl acetate ~opolymers wi~h a melt index of 0.1 to 200 g/10 minutes ..
~determined in accordance with DIN 53,735 at 190C and with a load of 2.16 kp ~MFI 190/2]) ~nd with a ~inyl acetat~ content of 1 to 30, preferably 5 to 20 and in particular 5 to 10% by weight, and which have acid numbers of 10 to 50, preferably 15 to 25, melt viscosi-ties at 120C OI 500 to 20,000 mPas, and saponification numbers of 70 to 140. Oxidation products with an acid number of 15 to 20, a saponification number of 80 to 110 and a density at 20C of about o. g6 gfc 3 are preferred The hardness uf an oxidation product of this type is about 600 kg/cm2 and the melt viscosity is about 19 500 to 5,000 9 in particular about 2~000 ~Pas.
In the polishes for~ulated usin~ the new 39~

oxidatlon products, the amount of ~.rax is 0.01 to 50~/0 by welght, relative to the finished polish9 the low con-cen-trations applying to the wipe-on waxes for use in a hi~lly dilute ~orm, ~hilst the amo~ts o.~ wax in pas-tes and emulsion polishes are between 1 and 50~ by weightO
ln the preparations, ~urther constituents ~Thich are cus~omary in polishes of these types and ~hich depend on the ~ol~ulation and the intended use can also be present, such as, ~or example, other waxes, paraffins, 10 ionic and/or non-ionic emulslfiers, substances with a cleaning action, solvents, wetting agents and levelling agents, po~ymer dispersions, film-forming auxiliaries, temporary and permanent plasticizers, antista-tic agents, bactericides, preser~atives, dyestuffs, metal salts and .
corrosion inhibitors.
The ~act that the use of the oxidation products in the field of cleaning agents and pol.ishes would give surprising resillts could in no way be predicted since, because o~ their high hardnesses9 and also as in the case o:E comparable polyethylene waxes, films were -to be expected which are hard, dirt-repellent and mechanically resistant, but are not non-slip It was also l~eces-sary to take accou~lt of the fact that the vinyl acetate component in the polymers has an unfavorable action on other properties o~ the polish films, or example their waterproofness and alkali resistc~noe. The ~act that, in the present case, the polish ~ilms ha~e a high hard-ness and a very good slip resistance, without their other use properties being impaired, also had to be 1 16~39~ - .

regarded by the expert as astonishing. Wi-th the aid of the new.oxida-tion products.~ it is thus possible to meet the long~-existing need for polish films with maæi-mum slip protection and flexibility and at the same time 5 optimum utilization of the technical progress with reg~rl to hardness, viscosi-ty and resistance to tread mark~s9 ln a better and simpler way than is made possible, ~or example, by the incorporation of anti-slip additives, which have many other disadvantages ~compare German 10 O~fenlegungsschrift 2,707,938; Braun and Roeme~, Fette - Seifen - Anstrichmittel, 76 (1974), page 169], - Fin~lly, the new waxes can also be used in com-bination with other waxes, for example ester waxes, paraffin waxes, microcrystalline waxes and the like, In addition, the oxidation products can be chemically modified for special applications, for example by par-tial or co~ple-te esterification with monohydric or polyhydric alcohols and/or by saponification wi-th mono-valent or polyvalent metal ions, and also by amidation or by partial or complete hydrolysis or transesterifica-tion of ester groups ob-tained, Oxidative after-~ treatment of the oxidation produc-ts lS also possible, for exa~ple using hydrogen peroxide or chromosulfuric acid, The following examples se~e to illustrate the invention fur-ther, Ex~ple 1 20 liters of distilled water, 7,6 kg o~ a~
, .

~1 ~6039~

e~hylene/villy-l acetate copolymer ~vinyl aceta-te content:
8,5% by wei.ght9 density: 0,928 g/cm~, mel.t index (~FI
190/2): 2.5 g/10 mi.nutes] and, as the catalyst, 0 4 kg o.~ an oxidation produc-t of the ethylene/vinyl acetate copolymer, with an acid number o~ 13, are introduced into a 40-liter stainless steel kettle The contents o~ the kettle are heated to the reac-tion temperature of 1~0~. During heating, the pa~sage of an airstream o~ 3 Nm3/hour through the mixture is started, whilst sti.rring vigorously and maintaining an excess pressure o~ 15 bars After the reac-tion temperature has been reached, sarnples are continuously taken from the ke-ttle by.direc.t e.~pan.sion, the samples being ob-tained in the fo~m of a spray powder~ To end the oxidation, the air supply and the stirrer are stopped. The water which settles out is separated from the oxida-tion pro-duct, and the oxidation product melt is dried by evaporating of~ the remaining water. ~he properties of the intermediate samples taken and o~ the resulting 20 end product are represented in Table 1.
The resulting oxidation products are easily emulsifiable when the acid numbers are 15 or more~
Fi.nely divided, speck-free~ highly transparent emul-sions are formed, which dry with a high instant shine.
The films which are formed are extremely resistant and non~slip.

16~395 7 ~

. ~ ~ ~ ~ ~ ~ ~ ,.~ ~ ~
rl bn ~ co 0 ci a~ ~ ~ ' c) o ~ a~
_ .
. ~ V .
,~r ~ o J oor~ lr~ O W ~
u~ O J J ~ ~ O ~ 0 a~
O O' O' O O _ O O O
_ _ C4 ,_ O O O O O O O O
a~ u~ v o o ~ o ~ o h O G~ 0 C~ O J
t~ O ~ I I I I I ~ I
S~ l O O O O O O O O
d _~ O O L~ O O 1~ 0 O
0 r~ t r~
_ _ .
~1 .
a) oo c~J C~J

~ O O O O O O O O
I h ~ O O O ~:1 0 1~
a) ~ bO If ~ CO r ~r~ O 0 ;1 3 r~ r~ 1 .
. . _ . I
.... -1~ `OOOOOO O
. O O O O O ~ 0 ~ O I ~ C~l ~D ~ t~ C- t~
. . ..
a~ ~ ~ C\l ,~ ,~
' ~ , ~
h a) c) ~ o ~ C) u~ ~ ~ o o ~ ~ ~ ~ ~ +~ o ~ ,SI .
r~ ~ ; r~ ~) ,~
~ _ __ - . , .
~D ~ (`J ~1 0 1~ 0:) ~D
~rl~ OOOOO C~a~
O O O ~ I rl r~ t~ -1 ~, P~ `--_ _ -- . .
I S~

,~
g o rlo u~ r~ ~ O
'~ r~o~ ~ ~ a) ~ ~ o .~ r~
~ o t~ t~
u~ ~
hq~ _ ~ o~o r~ o u~ o ~ ~o 0 oo .,~ r~ t~ r~ ;t _ _ g ,_ .
~ ~ ~ ~ ~O O ~ r~ ~ ~ Ct) +~ O ~ i a~ ,., _ ~ . . . _ ~

.~1 ~ ~ co :'' - ~s 2 to ~1 -Yarious ethylene/vinyl acetate copolymers are oxidized as ln Example 1, 2.375 kg of copolymer and 125 g of the respective oxidation produot, with an acid number of 18 9 being used in each case. The starting materials and -the results are summarized in Table 2 The oxidation products can be processed to give outstanding emvlsions when the melt viscosities are below 7,000 mPas (120C). Products with higher melt viscosities can be em~sified by adding waxes of lower viscosity, for example microcrystalline waxes and/or ~ster waxes based on natural wax.
The oxidation produc-ts are outstandingly suit-able as lubricants in plastics processing. In P~
~5 processing, they preferably act as internal lu~ricants and give rise to a high transparency and high extl~sion rates~

, , ~ : , :

.
, 1 16~3~5 _= .. ,._. ., . . ~. .

~ . a) ~ ~D O ~ ~ ~
~ _ _ _ ._ O t t- U ~ ~ _ ~ ~ U a~
_ oooooooooooooooooooo Lq O OOOOOOOOOO 'OO
o) ~ U t- ~ ~ O 1~ U~ 3 O~ ~ ~ ~ ~
' ,~.0 ~ O UO~ ~ U~ ~ ~ ~ ~ ~ U~ ~
C~ "~ ;t .
N 1~ ;t ~ ~ -$ ;~ ~ ~ ~ U~ N ~:t N ;~ o ~ ~ -o o 8 8 8 8 ~ 8 8 8 8 2 8 o ~ o o 8 'D 8 o cn o r~ o u~ 0 0 ~ r- rt U~ N CO cn ,1 ~ ~D 0 r~ rt W U~ ~0 ~
N ~ In ~D N ~0 0 rl ;1' N ~ 1~ N N rt 1~ r~ N ~ 1 ___ ~
P~ t OC.) ~ t t ~ cn o~ o~ cn ~ c~ c8 ~r~ oN~ 1~
, _~___ _ _ ~~ ~ 0 ~o ~ cn ,~ ~D r r- ~ o 0 0 u~t rtt 0 ~t ~ ~ N
a~ ~ -C)~ ~
¢ ~ E3 X rt ;t C~ ~ ~ 'J ~ 0 N N ;I' t t ~ ~ r~ U t t --a ~ --~ _ .
o ~ N U~ ~0 0 N 1~ U~ 0 tt~ ~ CO 11`1 ~0 ~0 ~i ~ ~ it~ N ~0 Et O ri O O O ,i rt ri rt O O O O O r; t~i ~t rt ~I rt rt _ ~
U~ U~ U~ ~O UO~ O ~D U~ U~ ~ t U1 I r2t r~ rl E c~ N cn Cn c N N N ~ c~ ~ ~O ~D~ ;l U~ 2 2 ~bD OO'O`O'O`O'O`O'O'O'OO'OO'O'OOOOO
~:0 ^ ~ ~ t- r- -E ~ O' Cn c~ c~ ~ ~i I NO 1~ r ~ ~ ~ ~ t u~
,t ~ ~S u~ u~
o~--3 0 CJ~ 0~ a~ ~ N ~ ~ ~ ~ ~ ,t rt r-l rl N ~1 N N C5 ~ _ ~ _ _ _ .~ X~z '~ -- - - . .

.

1 16~395 ~ on F~
.
A low--molecular ethylene/vinyl acetate copolymer with a ~inyl acetate content of 8% by weight, a melt vis~
cosity o~ 920 mPas (120C), a molecular weight of 4,580 and a density of O g~0 g/cm3 is oxidized, according to East German Paten-t Specifica-tion 11.6,625, Exampl.e 21, in the melt~ with the continuous addition o~ 15 ml o~
water/hour/kg of copolymer. A catalyst is not used.
A solt greasy oxidation product with an acid nu~ber of 17 is obtained, w'nich has a saponification~number of 103, a droppi.ng point of 87C and a needle penetration o~
21~10 1 mm. Because of the lack of hardness, the product is unsuitablel for example~ for the preparation of usable cleaning agent emulsions.
~
A high-molecular ethylene/vinyl acetate copoly-mer with a ~inyl acetate content o~ 10% by weight, a melt index of 370 g/10 minutes and a density of 0.926 g/cm3 is oxidized according to East ~erman Patent 20 Specification 116,625, Example 25. The reaction is . also carried out in the melt and 27 ml o~ water/hour/kg : of oopolymer are added continuously. The m~nganese/
` tin salt of a fatty acid is present as the catalyst.
A~ter a reaction time o~ 8 hours, no no-ticeable increase in the acid number can be determined. The product then crosslinks to give an infusible, colored, unusable mass E m~_es 22 to 26 ~ mixture o~ e~ual par-ts of c~n ethylene/vinyl ~ ~0395 : -acetate cop~lymer (~inyl acetate con-tent: 8~ by weight, melt index: 2.5 gJlo minutes, density: 0~928 g/cm3) and of an ethyle~e homopolymer (melt index: 18 g/10 minutes, density: 0,918 g/cm~) is oxidized as descrlbed ln Rxample 2. The results obtained are summarized ln T~.ble 3.
The pro~ucts can be processed to give emulsions - which dl~y to give hard, abrasion-resistant filMs ~ith a high shine. The films conta.ined fewer specks and had a higher slip resistance than films of known oxida-tin products, '~

'~

' .

.

~ ~6~3~5 _ .
S~ ~ $

1~ . C~ D O u~ 0 O ~D
U~ O 0~
OOOOO
Ul O O O C) O
C~ o U~ ~ ~ ~ i h~.Q O ~ O O O
_~ ~
I rl h O ;~ .

. .~
__ o oV o ~ o g ~ ~.
t~ U~ o 0 o ~
~I ~ ~ ~ .
a~ ~ ~ ~t ~ ~
..
. .
s~ &: ^ o ~ o~ o~ o O O ~~ ~ rl ~ r~ rl . i~
~1 ~o rlQ O~ 0 0 ;t ~O
W 0 ~ i . O . .

~,~ ~D CO r~
Cc ~ ~ ~ ~ i _ _ ~ ~ C~ 0 ~i~ O O O O r-i ~: ~
~__ .

~ ~ o C~ o ri t~ ~ t~ i ,~ Xj _.
~_ 11 ~ 6Q39 j5 les 27 -to 30 In each case, 1 kg of various copolymers Q~
ethylene and acrylic acid or acrylates is oxidized at 165C, as indicated in Example 1, bu-t without the addi-tion of a previously prepared oxidation product. Thestarting materials and the results are shown in Table 40 .

~6~.~9~. -_ _ .
~ ~ 0 . .
~D ~D 0 V . ~ o~
~ ~o o' o o ~, ~-~o o o o h ~ J .
~1 ~ O O C~ O
. . ~ O' t~
~_ J ~ c~.l . ~I) h 10 Ir~ .
0 5~ ~ ;t' ;~ 1 O'~
~ I _ _ .1 OU 'O O O O
t.> ~u~ O O C~ ~ 0 . 1~ ~ O
O'1-1'1~ r~l .~ ~
~ t) ~4 bO ~ ~ O O g tO
h-~l O O r-l r~ l ~ P~ _ _ _ rl rl h $ :
~ ~ .
O ~J ~ O , .
bC ~ CO 0r--~1_ Ei ~ ~d .. ...
~0 ~ O ~ 00. 'C~l ~
o ~ b~C) ~O r- U`\ ~ .
~ . I ~ .
t0 . .~;
~ O Ei O ~ C,U~
a)~ C o ~ o o ~-1~ ~
_ I

~0 '~O ~ c~ : ~ :
: ~ ~ h bO o o o o ~d X o ~ Lr~ u~
~ ~~ ~ u~ c- o ~
~0 ~ O .

. + h .I h ~e ~.1 ~ 0 N ~ ~
;l _~ j r,~
~ ~1 X ~o t- 0 O~ O ,_ .
E~

11 .~ &0395 ~ 25 :13x~al,~ , ~ 00 g of the oxîdation product with an acid number of 48 (sample 8), obtained in accordance with Example 1, are esterified by stirring it in the melt, a~, 5 a temperature of 125C, with 11,7 g of n--propanol, with the addition of catalytic amo~nts of sulfuric acid, A light-colored ester wax with an acid number of 14, a saponification number of 117 and a dropping point of 91C is obtained. The wax is outstclndingly suitable for the preparation of emulsions and pastes or as a lubri-cant for plastics processing, Ex~mele 32 50 g of sample 6 with an acid number of 28, obtained in Example 19 are saponified by stirring it in the molten state, at a temperature of 130C, with 1 g of calcium hydroxide, A light-colored wax soap with an acid numbér of 6, a saponification number of 74 and a dropping point of 104C is formed, ~hich can be used predominantly as an internal lubr.icant in PVC proces,s-ing,Examples 33 to 35 These examples sho~ the advantages gained by using the new oxidation products as the wax component in polishes, Solvent-based ~aste ~floor wax, .
4,0 parts by weight of an oxidized ethylene!
~inyl acetate copolymer with an acid number of 18 and a saponification n~nber of 85 (obtained from a copolymer 3~;~
. 2~ - .
with a vinyl ac~tate coIltent, o~ about 8~), 4.0 parts by weight of a plaskic microcrysta].line wax and 12.0 ~arts by weight of cake paraffin with a meltlng point of 60 to 62C were dissolved, ~t about 70G, in 80.0 parts by weight of ~Jhite sp.iritO
After cooling, whilst stirring, lO0.0 parts bv weight of a pasty solvent-based product were obtained (paste A), -For comparison purposes, pas-tes were prepared from an unoxidized polyethylene wax with a molecular weight o~ about 3,000 and a hardness of abou-t 600 kg/
cm2 (paste B), from an unoxidized polyethylene wax wi-th a molec~ar weight of about 1,500 and a hardness of about 300 kg/cm~ (paste C~ and from an oxidized poly-ethylene wax with an acia number of l~, a molecular weight of about 1,700 and a hardness of about 250 kg/cm2 - (paste D).
The properties of the pastes in application techn~`ogy are shown i~ Ta~le 5.

:.

1 ~60395 .

.
Pxoperty Pas ~3 A ¦ 33 B ~ 3~ C ¦ 33 D
~ _ _ _ . _ _ Paste hardness 650 580 1 260 610 (g/cm2) .
Traffic properties . .
on linoleum . .
Dirt uptake low low high low Slip resistance ~ery poor. good moder . ~.
10 (subjec~ive) good . ate .
Adhesive friction . . .
coefficient ~) . .
with metal shoes 0,56 0 4~ 0~54 0~50 with leather shoes 0.63 0. 4a o. 59 0~57 ~) Determination of the adhesive friction coef~ici.ent in accordance with the method described in the Journal "Fette, Seifen, Anstrichmittel", 76 (1974), pages 163 169, in the article by ~ Braun and B Roemer entitled "Einfluss von Wachsen auf Haft- und Gleit-reibung" ("Influence of Waxes on Adhesive Friction and Sliding Friction"3 ~ ' '., .
~ Instant~shine_emulsion (to be applied undiluted) A wax emulsion con-taining 18% of solids was initially prepared by saponifying a hot melt, at 130C, o~ .
15.0 parts by weight of the wax mentioned in Example 33, in the presence of 3.0 parts by weight o~ isotridecyl polyglycol ether 3~

(containing -8 mol,~of ethylene - oxide), with 0.5 part by weight of 43% 5tL ength KOH solution, ,stirring the melt into 81.5 parts by weight o~ boiling ~ater and then cooling the mixture rapidly to room temp~
erature.
10~.0 parts by weight of wax emulsion (emulsion A) were ~ormed.
For comparison, emulsions were p:repared from an oxidized polye-thylene wax with an acid number of 27, a molecular weight o~ about 5~000 and a hardness o~ about 800 kg/cm2 (em~sion B~ and from an oxidized polyethylene - wax with an acid number of 18, a molecular weight of about 1,500 and a hardness of about 250 kg/cm2 (emulsion ~: C~
In each case, 30 parts by ~eight of` the result-ing wax emulsion were formulated, at room temperature, - to give ready-for-use instant-shine emulsions by simply stirring the wax emulsion together with the following components in the amount and order indicated.
30,0 parts by weight of w~x emulsion A, B or C, contain-~ ing l~/o of solids, ,.
5~0 parts by weight of a 1~% strength alkaline solu-tion of crosslinked resin (colo-phony/maleate resin), 70;0 parts by weight o~ a ~5/Q s',;rength acrylatè co-polymer di.spersi.on with a film--forming te~perature of a~out 55,~Y, ~ .

~ ?~ 6'~3P~5 _ ~9 _ ,

2.2 parts by weight of ethyldiglycol, O ~ part by weight o~ tributoxyethyl phosphate, 0 7 part by weight of dibutyl phthalate, 1 0 part by weight of a 1% strength aqueous solution o~ a fluorinated sur~actant 109.6 parts by weight o.f instant-shine emulsion The emulsions were applied undiluted to PVC in an amoun-t of 20 ml/m2.
Table 6 _ _._ _ _ _ _ ._ ___ 0 Property of the wax film Polish emulsion in accord-ance with Exc~ple 34 A ~ ~ C
~ . ~ _ _ _ __ .
Dirt uptake low very low high Slip resis-tance very poor good 15 (subjective) good .
Adhesive friction coefficient .
with metal shoes 0 62 0~49 0 52 with leat}:le~ shoes 0.76 0.68 0.71 . _..................... .. _ ~ 0 ~ _ e 35 on wax ~to b 1:l00 with wat ~
The wax emulsions prepared first in accordance with Exam~le ~ were formulated, at room temperature, to give ~ipe-on wax concentrates by simply stirring the wax emulsions together with the following components in the smount and order indicated.
50 0 parts by weight of wax em~lsion A, B or C, contain-ing ]89b of' sol.ids, , ~
39~0 par-ts by weight of water, 2~0 parts by we.ight of sodium tetraborate decahydrate (borax.), -. 9,0 parts by weight o~ nonylphenol polyglycol ether containing 10 moles o.~ ethylene oxide ~ .
100.0 parts by ;weight of wipe-on wax concentrate.
To estimate the slip protection OIl PVC, the con-centrat,es were diluted in a ratio of 1:100 with water, and 20 ml of` the dilution were spread per m2 of PVC
~loor, From this, it is calcula-ted that 14 mg of wax are used per m2 of surface or tha-t the layer thickness of the wax film is 0,000014 mm, Notwlthstanding the ~.
1~ low amounts used, the following di~erences were found in the film propert~es claimed:
Table 7 . . .
. _ . Property of the wi.pe-on Wipe-on wax ~rom the wax wax ~.ilm emulsion .in accordance with : ~0 Example ,,.
: ~4 A ¦ 34 B ~ 34 C
_ . , ~ _._ . .
; : SIip resis-tance good poormoderate ~subjective) .
~dhesive friction .
25 - coefficient . with metal shoes 0.38 0,32 0036 : w-th leather shoes 0~58 0.52 0,55 __ _, ~

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A process for the preparation of an easily processable, hard polar wax by the oxidation of an ethylene copolymer with oxygen or an oxygen-containing gas in which a melt of the ethylene copolymer, dispersed in a dispersing agent which is inert towards oxygen, is treated with oxygen or an oxygen-containing gas at a temperature between the melting point of the polymer and 100°C above the melting point at an excess pressure between 0 and 100 bars with continuous intensive mixing, and in which a copolymer is used having a melt index between 0.01 and 400 g/10 minutes and which is a copolymer of ethylene with 0.5 to 50% by weight of at least one other monomer which is olefinic but contains an oxygen-containing group.

2. A process as claimed in claim 1 in which the copolymer is an ethylene/vinyl acetate copolymer.

3. A process as claimed in claim 2 in which the ethylene/vinyl acetate copolymer has a vinyl acetate content of 1 to 30% by weight and a melt index of 0.1 to 200 g/10 minutes.

4. A process as claimed in claim 1, claim 2 or claim 3 in which a mixture of ethylene copolymer with at least one ethylene polymer which does not contain oxygen and/or with natural or synthetic waxes is oxidized.

5. A process as claimed in claim 1, claim 2 or claim 3 wherein the dispersing agent is water.

6. A process as claimed in claim 1, claim 2 or claim 3 in which the oxidation is carried out in the presence of a wetting agent, a catalyst or a mixture thereof.

7. A process as claimed in claim 1, claim 2 or claim 3 in which 1 to 10% by weight, relative to the copolymer, of a previously oxidized ethylene copolymer is used as a catalyst in the oxidation process.

8. A process as claimed in claim 1, claim 2 or claim 3 in which the resultant product is subjected to an after-treatment which consists of partial or complete esterification, saponification, amidation, transesterification, hydrolysis or subsequent oxidation.

9. A hard, easily processable polar wax with a dropping point above 80 and below 110°C, a needle penetration index below 10:10-1 mm and an acid number of up to 200, whenever obtained according to a process as claimed in claim 1, claim 2 or claim 3.

10. A polish or paste comprising an oxidation product with an acid number of 10 to 50 and a melt viscosity at 120°C of 500 to 20,000 mPas, obtained by oxidation, in accordance with claim 2 from an ethylene/vinyl acetate copolymer with a vinyl acetate content of 1 to 30% by weight and a melt index of 0.1 to 200 g/10 minutes (determined in accordance with DIN
53,735 at 190°C and with a load of 2.16 kp [MFI 190/2], in association with water or an organic solvent.

11. A polish or paste as claimed in claim 10 in which the amount of oxidation product used is 0.01 to 50% by weight, relative to the finished polish or paste.

12. A polish or paste as claimed in claim 10 containing additional constituents which are customary in polar waxes.