DE1669303A1 - Process for producing gloss-stable wax-copolymer mixtures - Google Patents

Description

DR. ELISABETH JUNG AND DR. VOLKER VOSSIUS

PATENT ADVOCATE 1 6 S 9 3 O

t MÖNCHEN 23 · · IE Q E C ST R ASSC 2 «. TELEPHONE · 4 «β · Τ · TELEQIIAMM-AOIIEtSE: INVCNT / MONCHEN

19 Jan 1 £ 37

P 7532 / Bu / kä

SHELL IHTiäiiNATIOWALE HESEARCH MAATSCHAPP1J, N.V. The Hague / Holland

"Process for the production of gloss-stable Vlaoh · -

Copolymer ~ Gemisohen "

Priority: January 21, 1966, Y, St.A. Registration Mr .: 522 071

The present invention relates to a process for the production of gloss-stable wax copolymer mixtures.

Polymers are mixed with waxes with varying degrees of success been. When mixing copolymers with waxes can however, a phase separation both in the liquid and in the solid phases occur. This phase instability can lead to abnormalities in the solid Phaat * lead? those on the surface

109833/1519 ^ _{0 0R | G | NAL}

deo feston mixture appears as a dust-like coating occur ,, This instability is called "blooming".

The subject of the invention is a process for the production of gloss-stable waehe-copolymer-GeEiischen "which is characterized" that the Gemiooh (a) at least 0.1 see about 0.05 to 5p5 ⁰ Ci above the freezing point (according to ASTM D-938) holds the wax and (b) then cools the mixture below its hardening temperature.

Can surprisingly been found that _it's the blooming of WaöhS'Oopolymer-Qeffiischen largely prevented if the inventive Gemisch'dem refund procedure subjects *

Sttfiiaela- and solidification points of the V / axis mean in this Description the same.

In process step (a), stability is achieved without that the procedure would be limited in time. the The selected time period for this process step is therefore exclusive Economically determined, periods of a few seconds are the most weekly periods of more than an hour «, on the other hand, is unsuitable.

In practice, the wax-copolymer mixture can be in molten Condition applied to a base and attached. can the coated base according to the invention on the desired tempera «» tu ?: be held <, ode: »· but one proceeds in such a way that the solid wax-copolymer-Gemisoh already on the base ©

"109833/1519

^; ^ ^{; Λί;} BATH

heated and then treated in accordance with step (a). lis is also possible, a base with a wax-copolyuer mixture to overlay, which on the at the next stage of the procedure (a) the temperature used is maintained.

In process step (b) is the way the mixture is is cooled, not critical. For example, a base coated with a wax / copolymer mixture can be coated with cold Quenching the water «According to another embodiment, one lets the coated substrate slowly to the solidification temperature cool the mixture.

Uus wax can be a petroleum wax, which is obtained by refining a waxy base oil for lubricating oils * It can be a distillate wax obtained by caffining a distillate lubricating oil. Distillate waxes are generally paraffinic in nature. In them, the ratio of normal paraffins to isoparaffins is inversely proportional to their molecular weight. Another example of a petroleum wax is a cuckoo wax, ie a wax that was obtained from refining a residual oil, for example from refining a "bright stock". Residue waxes can contain microcrystalline waxes and / or high-temperature paraffin waxes. Practically all residue waxes are genes of microcrystalline and paraffinic waxes. They can be divided into half-axis fractions, which are usually microcrystalline, i.e., amorphous, or mainly 'p / .r-'fiiiiiseh, i.e., crystalline,

109833/1519

8AD ORIGINAL

As the melting point rises and, to a certain extent, as the molecular weight of the wax rises, the blooming is generally less pronounced.For example, paraffin waxes from lighter distillates have a strong tendency to bloom, while waxes from heavy distillates are divided into two parts, microcrystalline waxes and residual waxes mixtures, the relatively blooming little, compared to mixtures of copolymers and distillate grow "Therefore, the present invention is particularly ■ -> if not aüsschliesslich - to" make mixtures of distillate paraffin waxes and Copolyraerisaten gloss stable, and indeed especially those that paraffin »Contains waxes from lighter distillates.

In wax-Copolynier Gemiseh the Cöpolymergehalt generally does not exceed 50 GeV / _e ~ y £ p preferably 35 wt · ^, based on the Gesanitgeniisch ₀ The copolymer may ethylene units and units of a terminal Äthylenbindun _e s having unsaturated organic compound with 3 contain up to 6 carbon atoms. The ethylene copolymer preferably contains (^ monomer units of an of-olefin _P of esters of terminally unsaturated monocarboxylic acids and saturated aliphatic alcohols or of esters of saturated conocarboxylic acids and unsaturated aliphatic alcohols having terminal ethylene bonds lower olefins, e.g. propylene, butene-1 and pentene-1, vinyl acetate, methyl and ethyl aylate.

109833/1 5 1 9

BATH ORIGINAL

Esters, the ethylene and vinyl acetate units, are particularly suitable contain · They have the formula ■

H H ι m H H I. I.
___ ft I. I. ■ - ■ · u - "ν j I. I. I. H H H O
I.

in general the average number of ethylene units per vinyl acetate unit is in the molecule and has a value from about 6.5 to about 30, preferably from about 8 to about 14, and η is an integer from about 15 to about 250 on average.

Ethylene-GT-olefin copolymers are also preferred. They have the formula

(CH ₉ )

2'n

in which η is an integer of on average about 10 to about 50, preferably 10 to 40 ₈ and H is a hydrocarbon radical with 1 to 3 carbon atoms »The unit (CHg) _n eats an unbranched hydrocarbon chain. The mean molecular weight of the copolymers is about 20 C) CO to 800,000, preferably 200,000 to 400 OCO. The molar ratio of ethylene to the higher (K-olefin can be about 60 to about 95 mol- #. Copolymers with about 80 to about 95 mol- # ethylene units are particularly suitable because they are more crystalline and less sticky

10 9 8 3 3/1519 BAD ORiGJNAl.

preferably has a viscosity number (intrinsic viscosity) of about "1 (determined at 15O ⁰ C in decalin) to 3 dl / g .The density of the Copolyaerisates is between 0.85 to I ₁₁ O g / ccn. copolymers with a low density. are those with a density between 0.85 to about 0.91 g / cca; copolymers with a high density are those with a density between about 0.91 to about 1.0 g / ccm.Mixtures of different copolymer seeds with high and low density can provide a desirable improvement in low temperature properties without a corresponding increase in brittleness.

The invention is illustrated by the following examples:

- ■ - r

A 22.86 cm wide sulfite paper pad was used for testing Coated on both sides with a wax-copolymer-Genisch · Das über-ζίββςη the. The support was done in such a way that the support was placed in a constant temperature bath made of a molten Uaoha-Copolyraer mixture dipped and then let the pad run between rollers to remove the excess Waohs copolymer mixture to squeeze out * The tests were carried out twice. On the first try, the mixture became quick in the usual way to below the solidification temperature of the wax-copolymer chamber deterred. In the other experiment, the 3-axis copolymer mixture was used at least 0.1 second for 0.05 to 5 »5 ° C above the solidification point (according to ASOSI-D 938) of the wax in the wax-copolymer mixture used, and then below the freezing temperature cooled down. Blooming occurs in wax-copolymer greens ach quickly in the course of minutes, but at the latest after a few hours. The results lines, rte.ss the invention

109833/1519

BATH ORIGINAL

Ancestors leads to advantages in terms of glana stability.

Jäuia coating of the base was a Haida-BeüchichtmigBinaacnine in the tests · A mixture of BO <} ew .- / i of a distillate paraffin wax with a melting point was used of about 60 ° C and 20% by weight, -5 = of an Ethylon "> Vinylaoetat-Gopolyaeriscit-es, the 72 hol ~ $ £ ethylene and 28 ool · ^ vinyl acetate

and had a shell indsx: of 15 g / 10 min (Fliessgeim Extruaionsplaetometier)

Table I.

conditions

rapid cooling

62.78 ⁰ C.
O _t 5 see

AU8-

bloom

no

Water permeability g / 100 in .2 / 24_h

37.7H ^{0 O.95}

Relative.
Feet moisture

2 _P 92
O ₁ , 0δ

I = S ViI ι U | iU <

22.78 ° C, 50 relative. humidity

0..28 0 _t 03

The example is performed by the method according to the invention

and an improved water vapor permeability of the pact or 10 at 22.78 ° G and around the Paktor 50 at ⁰ C 37.78

Example 2

In the following years a distillate paraffin wax with a melting point of about 51-67 ° C and an ethylene-vinylt: -i; at Copolymerieiit were vesweuded as in Figure 1. The proportions of the erinfi1;!? A ± m 'rfaene vmrcteR x ^ riiort do featausstelliii ¹ »^ ob

ne vmrcteR x ^ riiort do 109833/1519

BATH ORIGINAL

the critical temperature range due to the copolymer concentration of blooming is changed "

Table IX

Composition in wt .- ^ 10 $> Copoly-
merisat «Γ. for> 0, l see on
Φ held cooled quickly
Ton 93.33 ⁰ C to
below the
Freezing temp
temperature 90 p 20th i> copoly-
merisat 54.44 no blooming Blooming 80 s 30th $> Copoly
mer! sat 54p44 no blooming Blooming 70 y 53.89 . no blooming Blooming 6 wax, 6 wax ρ ί wax ρ

The results above show that the copolymer content in the mixture has no noticeable influence on the critical tempering temperature.

Example 3

The procedure was as in Example 2 with the difference that a distillate paraffin wax with a melting point of approximately 60 ° C. was used in the wax-copolymer mixture. Bas Copolymer! Eat stayed the same.

10.98 33/1519

BATH

Table III

Composition in Gew _e = $ ^c /> wax 8 5 56 copoly-
merisat i » Copoly»
merisat Temp.,
⁰ C for X) ₉ I see on
T held Eohnell cooled down
of 93.33 ⁰ C to
below the
Solidified
temperature 95 $ 5> wax , 7.5 * Oo «
polymer $> Copoly «
merisat 62> 22 -
64.44 no blooming Blooming 92 _s io wax, 10 ? C Copoly "
merisat 62.22 -
64.44 no blooming Blooming 90 i> wax, 20th 64 "44 no blooming Blooming 80 i> wax, 30th 62.22 no blooming Blooming 70 64 »44 no blooming Blooming

The results of this example confirm those of Example 2, that namely at tempering temperatures within the critical Temperature range no blooming occurs and that the addition of different amounts of polymer to the tempering temperature without Influence remains.

Example A.

A vachs Oopolymer-Oemioch, which consisted of 70 Gew "~ # of a distillate paraffin wax with a melting point of about 60 ⁰ G and 30 Gew." 56 of an ethylene vinyl acetate copolymer analogous to Example 1, was combined with other petroleum oils in order to reduce the influence of different Wachae to determine the critical tempering temperature.

109833/1519

ORIGINAL

. - 10 -Table IY

Composition in weight-96 Temp.,
⁰ C fürjO, l seo on
T held cooled quickly
from 93.33 C to
below the
Cretaceous tem-
temperature $ 90> 70/30 wax polymer.
sat + 10 4t distillate wax
Pp. 71.11 ö
(Fp, of the combined
Wax 61.67 "C)
90 # 70/30 wax polymer
sat + 10 $ arrears
wax pp 58.33
(Fp. Of the combined
Wax 60 C)
90 $> 70/30 Waohspolymer-
sat and 10 # ßügkstands-
wax pp. 82.22 C
(Pp of the combined
Wax 62.78 ^Ü C) 66.11
64.44
65.56 . no blooming
no blooming
no blooming Blooming
Blooming
Blooming

These tests show that the temperature used depends on the
Depends on the wax base and that no blooming occurs,
if wax ~ PοlyraerGemische be compensated at least 0 _r l second within the specific temperature range.

Example 5

For portions of a 70/30 wax-polymer mixture from Example 4 became 1% by weight of anti-blooming agents or gloss stabilizers added. As shown below, these additives have no visible effect on the aging temperature of the Wax-polymer mixtures.

109833/1519

BATH

- 11 Table Y

stabilizer Temp., ⁰ C for> 0.1 seconds at Ϊ ge
keep Low density polyethylene 64.44 no blooming Al-etearate 64.44 no blooming IIa ~ stearate 65.00 no blooming K-stearate 64.44 no blooming Zn stearate 65.56 no blooming Polyvinyl stearate 65.00 no blooming Stearic acid amide 62.78 no blooming

A mixture containing 70 Sew.-5 & auo a distillate paraffin wax having a melting point van about 60 ⁰ C and consisted of 30 weight ""# from an ethylene-vinyl acetate Copolyiaerisat containing units containing 15 mol ~ # vinyl acetate and a melt index of 6 g / 10 min, 2 samples had a s * s ^ ne base applied. The coating temperature was over? 6 _f 67 ⁰ C, the one sample was quickly quenched with cold water below the freezing point of the mixture and showed strong blooming "The other sample at least one second was maintained at about ⁰ C and 62.78 · then quenched with cold water The mixture of this sample was polished stably.

Example 7

All of the following mixtures consisted of 70 wt. ~? 6 from a distillate paraffin wax with a melting point of about 60 ⁰ C and 30 wt. ~ # From a Copolyiaeren. It should be determined what influence the various copolymers on the guard

ö with regard to the tempering temperature. With everyone 109833/1519

ORIGlNAL BATHROOM

2 tests were carried out. The samples yurden 95ι33 at about ⁰ C to a backing applied · The first sample was rapidly quenched with cold water, the second sample was held for more than 0.1 second to about 63 * 89 ⁰ C '

! Table VI

Copolymer deterred at
93.33 ⁰ O remunerated at
63.89 ⁰ O Ethylene methyl acrylate
Ethylene-ethyl acrylate
(20 mol $ ethyl acrylate
- Melt index 2 _P 5g / 10 min)
Eti ^ len-isobutyl erylate
(20 moles # isobutyl acrylate
- melt index 20g / 10 min) Blooming
Blooming
Blooming no blooming
no blooming
no blooming

Results similar to those above are obtained when the copolymer from ethylene units and units of a "'-olefin, at =" for example polypropylene.

Example 8

The mixtures were checked for their carbon dioxide permeability Room temperature (22.78 ° C) examined. The permeability was determined on a mixture that was quickly quenched from over 93 »33 ° C to below its solidification temperature, and also on a mixture that was tempered for more than 0.1 second between 62.78 to 63 »89 ° C and then quenched. The permeability

was determined in ml / sec / om / cm / cm Hg.

deterred remunerated

0.9 0.6

........... ,,, 109833/1519

■ ■ - ' _BAD OBlGlNAL

Compared to the quickly quenched mixture, the tempered mixture shows a decrease in G0 ₂ ^ I> permeability of 33 $>,

Claims

10 9 8 3 3/1519

Claims (11)

Claims 1. A method for producing gloss-stable wax-copolymer ™ mixtures, characterized in that w * the mixture (a) is at least 0.1 second about 0.05 to 5.5 ^° C. above the solidification point (according to AST !! D-938 ) holds the wax and (b) then cools the mixture below its solidification temperature, 2. The method according to claim 1, characterized in that the Waohs-Copolyjaer mixture in molten Brings state to a base and treats the coated base according to claim 1 « 3 * Method according to claim 1, characterized in that » draws that the wax-copolymer-mixture, which is already in a solid state on the base, is heated and then afterwards treated according to claim 1. 4 »The method according to claims 1 to 3 _f, characterized in that the copolymer content in the mixture is not more than 50 wt · - ^, based on the total amount. 5. The method according to claim 1 to 3, characterized in that that the copolymer content is not more than 35% by weight, based on the total mixture 6. The method according to claim 1 to 5, characterized draws that an ethylene copolymer is used. 109833/1519 BATH ORIGINAL 7 * The method according to claim 6, characterized in that that the ethylene copolymer units of an unsaturated compound having terminal ethylene bonds containing 3 to 6 carbon atoms. 8, The method according to claim 6, characterized in that the ethylene Oopolymer units of one csi -olefins, of esters from terminally unsaturated monocarboxylic acids and saturated aliphatic alcohols or monocarboxylic acids saturated with esters and terminal ethylene bonds containing unsaturated aliphatic alcohols « 9 «Method according to claim 6, characterized in that that the ethylene copolymer contains vinyl acetate units. 10. The method according to claim 6, characterized in that the ethylene copolymer is propylene units contains. 11. The method according to claim 1 to 3, characterized in that the wax is a distillate paraffin wax is used. 109833/1519 ΒΑΌ ORIGINAL