CS195379B1 - Process for preparing polyolefinic waxes conaining oxygen - Google Patents

Abstract

1429012 Oxidized polyolefins LEUNAWERKE WALTER ULBRICHT VEB 24 Aug 1973 [8 Sept 1972] 40318/73 Heading C3P Oxidized polyolefin waxes having an acid number up to 150 mg KOH/g and an ester number up to 150 mg KOH/g are prepared by oxidizing saturated branched polyolefins of molecular weight 800 to 10,000 in the melt at 120‹ to 170‹ C. with oxygen, ozone or an oxygencontaining gas, in the presence of 0À10 to 3% by weight of the polyolefin of a mixture of (a) 0À09 to 2À99 weight per cent of a salt of a Group VII(a) or VIII metal and (b) 0À01 to 1À0 weight per cent of a salt of a Group IV(b) metal. The polyolefin may be a polyethylene, polypropylene or ethylene/α-olefin copolymer. The metal salts may be (a) manganese, iron and cobalt stearates, and (b) tin and lead salts of carboxylic acids with over 8 carbon atoms, e.g. tin oleate, octoate and stearate. The process may be effected in the presence of inert liquid media, e.g. water and carboxylic acids, and the products may be used in textile and paper treating agents and polishes. Examples describe the oxidation of (1-6) polyethylene (7) ethylene/ vinyl acetate copolymer.

Description

The invention relates to a process for the production of oxygen-containing polyolefin waxes by oxidation of saturated polyolefins having a molecular weight of 800 to 10,000.

The polyolefin wax's oxidability is considerably less than that of paraffin hydrocarbons. A simple transfer of reaction conditions for paraffin oxidation is therefore not possible. Unless special precautions are taken, long reaction times must be envisaged and products having significantly altered properties, such as lower hardness, yellow to brown color, pungent odor, and a significantly increased melt viscosity, are obtained for the starting materials, further processing unusable.

These deficiencies are attempted to bypass several known methods with special technological conditions.

For example, it is known that polyethylene waxes can be oxidized in the molten state by oxygen or oxygen-containing gases under appropriate temperature control up to an acid number of 50 without the aforementioned drawbacks, but this process requires temperatures from 130 to 190 ° C.

Further, it is known to obtain oxidized polyolefin waxes with acid numbers of up to 100 and to perform oxygen oxidation in the liquid phase at relatively low temperatures of max. 130 ° C. However, this process assumes low melt viscosities, which are generally only available for low molecular weight polyolefins. The viscosity of the reaction mixture must be maintained by controlling the oxygen supply at a value which does not exceed the viscosity of the polyolefin wax used. Although products with good emulsifying properties can be obtained in this way, the reaction rate at temperatures below 130 ° C is so low that a reaction time of 12 to 20 hours is required to achieve an acid number of 20 to 30.

It is further known to carry out reactions at temperatures between 130 and 250 ° C under increased pressure and vigorous stirring to increase oxygen uptake and thereby oxidize at higher reaction rates and without increasing viscosity. Reaction rates of 2 to 4 kg O 2/100 kg wax / hour are achieved, with stirring powers below 1 kW / 100 kg wax resulting in yellow products, longer reaction times and high melt viscosities. In addition, high energy consumption, costly safety technology and a low degree of energy efficiency are achievable. Much of the electrical energy is converted into heat via a stirrer, which must be removed from the reaction vessel again by additional cooling.

Catalysts are known to rapidly overcome the induction period and to accelerate the oxidation process. Suitable catalysts are, for example, peroxide compounds, azo compounds and freshly oxidized polyolefins. A drawback of these methods is that the additives used adversely affect the product properties ^{of the} product since they provide low molecular weight cleavage products and thereby facilitate cross-linking reactions.

Further useful as catalysts are compounds known from the oxidation of paraffins, such as certain heavy metal compounds of manganese or cobalt, or their alkali195379

95379 or alkaline-earth compounds, for example in the form of potassium permanganate. While these catalysts accelerate oxidation reactions, they do not prevent various operating deficiencies such as product coloring, crosslinking, and fragrance deterioration. The formation of crosslinked products is manifested, for example, by the fact that the viscosity of the oxidation melt is gradually or very suddenly increased according to the conditions and, usually, at relatively lower oxidation stages, the viscosity of the oxidation melt is increased to high values. not fusible, insoluble and unusable.

In order to keep the formation of the crosslinked fractions low, these methods can only be applied to low wax waxes, and it is often necessary to keep the melt viscosity of the lyolefins low by adding hydrocarbon waxes. In view of the cross-linking tendency with post-gassing oxidation, only relatively low oxidation stages are achieved in practice.

For this reason, known methods allow for the production of readily emissible, relatively hard polyolefin waxes, but with melt viscosities not higher than those of the starting products. In addition, the products have only low or no ester numbers and thus poor technical characteristics, or their production is associated with long periods or energy consumption.

The purpose of the invention is to produce easily emulsifiable polyolefin waxes having a higher oxygen content than known emulsifiable waxes, with large yields per volume and time unit.

SUMMARY OF THE INVENTION It is an object of the present invention to provide emulsifiable polyolefin waxes having a molar spherical molar mass of from 800 to 10,000 and an acid number of up to about 150 and an ateo number of up to 150. freezing point, unfavorably unchanged.

According to the invention, this object is achieved in that the oxidation is carried out in an amount of 0.01 to 2 wt.%, Based on the low-molecular-weight pooyo-olefin polymer used, mixtures of 0.01 to 0.9 wt. 0.01 to 1.0 moles of Group IVb metal salt of the periodic system. _O

The heavy metal salt of the VHa group of the periodic system is preferably an octoate or mannitol stearate. Preferred tin or lead salts of carboxylic acids with more than 8 carbon atoms are used as the Group IVb metal salts of the periodic system, for example, stannous octoate and lead.

According to the process of the invention, the oxide is formed into lyolefin waxes, in particular polyethylene waxes, obtained by the polymerization of ethylene. In addition, polypropylene or copolymers of ethylene with β-ω-efins having a molar spheroid of 800 to 10,000 can be oxidized by the process of the invention.

Aforementioned op and frictions are zapoořebí o ^ ¹ ^ ^{<^} oti art at nearly the same temperature profile substantially shorter · reaction time and. Can be obtained from well emuUggžote1né pólysllfinsvé · waxes numbers KYSE! Ooti from 1-50 and ester numbers HD 1 to 200, for example, at a reaction time of less than 5 hours, t0.0 kg of wax and a flow rate of 0.05 Nm ^ 02 / h have an acid value above 100. It has proven expedient to adjust the wax to number ratio in the emulsifiable polyolefin produced ky s; eioo to an eso number from 1.0 to 2.0, preferably 1.1 to 1.6.

The process according to the invention allows production. Mild polyolene waxes in which the melt viscosity does not rise during the reaction, but still decreases, and are thus easy to process. Furthermore, the process according to the invention has the advantage that the hardness of the products up to the number 50 does not decrease substantially, but is freely adjustable.

The oxidation according to the invention can also be carried out at a pressure of between 0 and 10 MPa in the presence of oxygen-inert sintering agents, for example in the presence of water, or of suitable carboxylic acids, using low molecular weight wax polyolefins having a molecular weight of between 10,000 and 20,000 or higher polyolefins having the nature of a plastic having a moocular mass of between about 20,000 and 2,000,000.

The properties of the polyolefinic oxidation products produced by the process of the present invention are determined by the tightened oxidation state, structure, and molecular weight of the starting polyolefin. Taking into account these specialty features, it is possible to produce products which, due to their excellent tax properties, are widely used in industrial applications, e.g. as sat, part of textile finishing, in the form of aqueous. The use of paper treatment and coating compositions for use in the construction industry, leather industry, in the plastics and metal-industrial industry, and as base materials for polishing, waxing and waxes. The products obtained are adapted to the various requirements of practice. ,

The process according to the invention is explained in more detail in the following examples. The definition of the starting and end products is given by the following parameters:.

eIoo ti number TGL 8418 (mgK0H / g wax) number TGL 8418 (mgK0H / g wax) vi-goat melt TGL 0-51 562 at 140 [deg.] C penetration TGL 12,622 / 10 ^_1 mm / 500 p / 20 ° C / 30 sec

Example!

350 g of a polyethylene trolley having a melt vitosity of 275 cSt, measured at 140 DEG, produced by the free-radical polymerization of ethylene at high pressures, are melted in a honeycomb column (45 mm, height 500 mm) at 160 DEG. After the addition of 0.35 g of manganese theamine and 0.35 g of manganese octoate, molar oxygen is introduced into the polyethylene wax melt through a filter candle at a rate of 50 l / h at 160-165 ° C. .

Samples are taken at the time intervals indicated in the table and analyzed. The results are shown in Table 1.

19537 9

Table 1

Oxidation time / min / Numbers with s 10 s 1ti / mgK0H / g Esther number / mgK0H / g Color according to • j 0 s tupnice / TGL 8418 / Viskooitr melt / cSt / 0 0 0 0 275 30 9.54 8.1 -. 192.3 50 22.17 24.13 1 .125,4 70 26.65 22.3 - 115.1 1 00 50.79 51, 63 3 100.2 1 1 5 61.73 56.12 - 94.9 175 90.60 72.5 - 235 101.4 83.2 -. 265 130.9 107.61 4 93.6 She said d 2 (comparative experiment) heavy metal salts IV. main groups periodic system, show e below Oxidation of the same polyethylene wax Table 2. under the above conditions but without ^- Table 2

Time Čslo Es terové Color by Vis k o. Ita oxidation acidity to you number j odové melting, ny scale ‘ / min / (mgKOH / g). / mgK0H / g / TGL 8418 / / c.S t / 0 0 0 . 0 275 30 6.73 - - - 40 14.31 8.84 - 132.0 70 23.01 1 8,10 '- 1 27,3 100 ALIGN! 23.62 23.99 4 142.2 130 33.39 29.04 - 151.9 1 60 37.59 32.0 5 - 1 90 4 3.77 36.90 10 253.8 220 47.40 41, 5 - 240 51.07 50.56 15 Dec 635, 1

Example 3

7.0 kg of polyethylene wax as in Example 1 was melted in a 10-liter beaker heated by two 2200 W extruder heaters.

After the addition of 3.5 g of magnesium stearate and 10.5 g of stannous stearate, the melt of the ethylene wax poles is heated to 160 ° C and introduced into it by a filter candle / pore size of 5 to 15 µm / 250 liters of 02 / hour at 160 to 165 [deg.] C. Reaction heat is removed through a suspended hairpin water cooler. The oxidation process is shown in Table 3.

Tab Street · 3

Oxidation time / min /

20 May

180

210

270

Acid number / mgKOH / g /

Estheres. Penn trace Visko ozta number melt / mgKOH / g / / cSt /

3.09

21.32

37.6

69.03

82.78

99.89

116.41

- 14.2 275 2.5 17.0 205.1 17.96 20.4 . 138.6 29.74 27.7 99.6 64.26 41.5 99.3 68.74 74.0 99.0 75.49 91.0 99.2 104.67 105 99.6

Example 4

In a jacketed column (0 45 mm, height 500 mm), 300 g of polyethylene wax as in Example 1 is melted at 140 ° C. After addition of 0.30 g of mannan stearate and 0.60 g of stannous octoate, it is introduced into the tavenigas. polyethylene wax filter candle 50 l / h molecular oxygen at 130 ° C and 140 to 140 ° C

145 ° C. At the intervals indicated in Tables 4a and 4b, samples shall be taken and analyzed. The results are shown in these tables. '

Corresponding comparative experiments without the addition of certain heavy metal salts are shown in Tables 4c and 4d.

Tables 4a to 4d

Oxidative Time Number Es terové Viscosity Penetration temperature oxidation yeast los you number melt 101 mm at 500 p , ° C / / min / / mgKOH / g / / mgK0H / g / cSt / 20 ° C, 30 p and/ 0 0 . 0 2 7 5.0 14.2 '30 7.5 7.1 - - 60 19.08 13, 1 9 112.8 19.8 90 32 19.3 7 9.9 22.1 140 to 1 20 46.02 29.5 70.9 26.4 1 50 58.91 - 62.0 27.3 145 ° C 1 80 74.92 37.32 50.2 55.8 210 95.93 - ’ 45.4 92.0 240 120.3 79.20 36.6 101 270 132 103.5 · 35.0 105 '

Ooídační Time Number Estheres Viskozi ta P ^ i ^ ttrace temperature oxidation acidity number melt 10 ~ 1 mm at 500 p / ° C / / min / / mgK0H / g / mgK0H / g / cSt / 20 ° C, 30 p b / 0 0 0 27 5,0 14.2 30 2.52 - - -  - 60 5.89 - - - 90 7.86 7.5. 177.0 17.3 130 [deg.] C 1 20 11.2 - . - 150 15.4.  <- - - · 1 80 19.6 12.36 134.6 19.3 210 25, 95 - - - 240 ' 33,. 95 20.7 85.6 22.6 270 46.2 41, 32 65.0 25.3

C/ 0 0 0 27 5,0 14.2 30 7.6 3.9 179 16.1 Mp 140-145 ° C 60 15.4 10.9 155 19.7 comparative t 90 20.8 17.1 1 1 9 24.2 try 1 20 27.49 25.0 1 10 28.0 / without additive 150 32.26 30.4 92  3 1,0 Tin / 180 37.04 33, 1 89 36.5 Oxidative Time Čslo Es terové. ViskozZta Penntrace temperature oxidation yeast los you number melt 10 “1 mm at 500 p / ° c / . / min / / mgKOH / g / / mgK0H / g / cSt / 20 ° C, 30 p d / 0 0 0 ’275.0 14.2 '30 0.28 0.30 - _ - 130 ° C be- 90 0.42 0.51 - - heavy additives 1 50 0.56 0.68 260 - of metals 210 1, 68 1.9 - - 270 3.64 3.9 231 15.5

Example 5

350 g of polyethylene wax as in Example 1 was melted in a honeycomb column (0 45 mm, height 500 mm) at 160 ° C. After addition of 0.35 g of manganese stearate and 0.70 g of lead octoate, molecular oxygen is introduced into the melt of the polyethylene wax through a filter candle / pore size of 5 to 15 [mu] m at a temperature of 140 to 145 [deg.] C.

Samples are taken at the time intervals indicated in Table 5. The results are shown in Table 5.

Table 5

Dob a Number Estheres Viskozi ta Penetration oxidation kyse1oo ti number melt 500 p, 20 C / min / / mgKOH / g / • / mgKOH / g / / cSt / 30 p 0 · 0 0 275 14.2 30 7.29 8.14 ‘-  -. 60 17.12 17.96 154.4 16.8 90 33.39 22.73 110.2 19.5 1 20 54.44 39.56 79.6 28.3 1 50 74.64 51.63 67.4 45.8 180 95.12 57.81 49.2 - 66.9 210 109.43 55.95 41.8 100.0

195379.

Example 6

After 359 g of polyethylene wax produced by free-radical polymerization of ethylene at high pressures of different molecular weights, it was melted in separate coatings according to Example 1 at 140 ° C. After addition of 0.35 g of manganese stearate and 35 g of stannous octoate, it is introduced into the melt of polyethylene wax through filter candles / pore size of 5 to 15 µm / 30 liters of O 2 / h at 140 to 145 ° C. Samples are taken at the time intervals indicated in Table 6 and analyzed. The test results are also shown in Table 6.

Tables 6a to 6c

Time Number Estheres Viscosity Penetration oxidation. acidity number melt 50 °, 20 ° C at 140 ° C 30 p / min / / mgKOH / g / / mgKOH / g / / cSt / a / _r - 0 0 0 409 14.5 30 4.07 - 363 13.9 60 7.15 - 301 15.0 90 14.59 - 224 17.0 1 20 25.54 16.55 1JD7, 7 20.6 150 47, 98 26.38 76.2 27, 1 180 60.03 3 1,0 63.5 33.7 210 76.88 36.76 56.9 43.9 240 92.57 54.3 46.6 57.3 270 100.45 60.91 45.8 68.9 Dob a Number Es terové Viscosity Penetration oxidation kýselos ti number melt 500 µ, 20 ° C at 140 ° C 30 p / min / / mgKOH / g / / mgKOH / g / / cŠt / b / 0 0 0 570 11.1 60 7.01 9,82 334.5 13,7 ' 90 15.15 12.91 201.2 14.5 1 20 25.93 22.69 137.1 17.2 1 50 32.55 24.97 115.0 18.7 180 43.21 3Z, 55 88.0 20.5 210 53.59 39.01 80.7 23.9 240 - - - - 270 72.39 52.48 62.8 32.6 с / 0 0 0 7 7 2.7 10.7 30 0.70 - - - 60 0.98 - - - 90 3.79 - - - 1 20 9.54 7.29 356.4 12.8 1 50 16.83 9,82 234.7 14.3  180 22.45 16.83 215.9 17.4 210 30.02 20.49 138.7 17.5 240 43.21 25.54 100.4 20.2 Example 1 a d 7 oxidation is introduced into the melt by filtration Candles molecular oxygen in quantity Po 350 g ethylene-vinyl acetate wax 50 liters / hour at 140-145 ° C. % vinyl acetate content 15.08 wt. viscosity ta At the time intervals specified in the table melt at 140 ° C 521.6 cSt /, produced 7, samples are taken and analyzed. You- radical copolymerization of ethylene and vinyl- the results are given in Table 7b and 7c. acetate at high pressures will melt Comparative experiment at 140 ° C without additive in mantle column according to Example 1 1 at oxidation accelerators from capture results 140 [deg.] C. After addition of various accelerators in Table 7a.

Tables 7a to 7c

U oxidation accelerator

D ob a Number Es terové Viskozi ta Penetration oxidation acidity number melt 500 p, 20 ° C / min / / mgK0H / g / mgK0H / g / cSt / 30 p

and / or without

0 0 90 522 31.1 30 0.84 - - 60 1.40 - 90 2.52 - - 1 20 6.17 - - 1'50 9.54 180 18.79 - 210 27.78 90 138 4 7,6

12

Accelerator Time Number Es terové • Viscosity Penetration oxidation .oxidation acid sloo t i number melt 500 µ, 20 ° C at 140 ° C i 30 p / min / / mgKOH / g / / mgKOH / g / / cSt / b / 0 0 90 522 3.1 30 1, 96 O O -. ’ 0.1 wt. 60 2.24 O O '- with tearan 90 5.33 96.53 370.5 32.2 of manganese 1 20 7.0 1 O O O 1 50 11.22. 97.09 219.8 36.4 1 80 16.55 O O O 2 10 28.06 98.22 122.1 50.2 240 .41,81 106.91 88.2 75.4

C/ 0 0 90 522 31.1 0.1 W hmooi 30 1, 4 O 501 tteat ^ r ^ ou manga ~ 60 5.75 O O 'o natého  90 12.35 97.08 225, 1 37.6 1 20 21.04 O O O 0.1 W m o i 1 50 37.6 101, 3 100.2 67.4 octoan 1 80 55.28 101.85 73, 7 103 stannous 210 70.71 108.87 62.1 105

He said a. D 8

350 g of polypropylene wax (acid number = 0, melting point = 138 ° C, molar mass 4300) were melted in a jacketed column at 150 ° C according to Example 1. After the addition of 0.5 g of octoate, and 0.5 g of lead stearate,

Table 8 melt introduces oxygen (20 to 50) by means of a filter candle, according to Example 1. 1 (h / kg) and the heat of reaction is removed in part. After some time samples were taken and analyzed. The results of the tests are shown in the following table.

Oxidation time Number kyys Ioo ti Esther number. MoOekulová / min / / mgK0H / g / mgKOH / g / mass 0 0 0 4 300 1 5. 0.3 0.1 O 30 0.4 0.3 O 60 1.0. 1.5 O 90 2,0 4.0 O 1 20 3.8 6.3 O 1 50 7.7 8.1 2 '200 1 80 7, 8 9.7 O· 210 9.3 1-0,7 O 240  10.1  11.1 2 050

kg of polypropylene wax (acid number 138 ° C) was melted according to Example 1 -

155 ° Ci

The moocular mass was 4300, in a jacketed column, at 150 ° C

After the addition of 3.5 g of stannous and 3.5 g of stannous octoate and 4.0 g of lead sternum, oxygen is introduced into the melt by means of a candle, as described in Example 1, until the amount of 1 is reached. of oxygen is 10 to 25

Qa / kg / hr.

Table 9

Moment:

acid number:

Molecular hormone

300

Okami ik:

210 min

Number k ^ ye ^ el ^ oti:

8.4 mgKOH / g

Mooocular hmoOnc> ot:

Claims (4)

SUBJECT OF THE INVENTION CLAIMS 1. A process for the production of polyolefin waxes having an oxygen content of from 3 to 150 mg KH / g wax, preferably from 3 to 150 mg KOH / g wax, by oxidation of saturated polyolefins having a molecular weight between 800 and 10,000. with pure oxygen or oxygen-containing gases, optionally with the addition of ozone at temperatures of 120 to 170 ° C, preferably 130 to 150 ° C, in the melt in the presence of heavy metal salts, characterized in that the oxidation is carried out at about 0.01 Up to 2.0% by weight of the low-molecular-weight polyolefin polymer used may be from 0.01 to 0.9% by weight of the heavy metal salt of Group VIIa and from 0.01 to 1.0% by weight of the Group IVb metal salt. system. 2. The process according to claim 1, wherein the heavy metal salt of Group VIIa of the periodic system is octoate or manganese stearate. 3. The process according to claim 1, wherein the Group IVb metal salts of the periodic system are stannous or lead salts of carboxylic acids with more than 8 carbon atoms, for example stannous octoate and lead stearate. 4. The process according to claim 1, wherein the ratio of the acid number to the ester number is from 1.0 to 2.0, preferably from 1.1 to 1.6, in the emulsifiable polyol of the olefin wax produced.