CS416091A3 - Modified polyethylene glycols - Google Patents

Description

115 PRAGUE 1, 2 n. 25

Modified polyethylene glycols

Technology '- ·

The present invention relates to modified polyethylene glycols having a low, freezing point and, in other properties, to polyethylene glycols of conventional types.

Background Art

As. It is known that polyethylene glycols adducts of ethylene oxide with a hydroxy group are always at the end of the ethylene oxide chain ^ corresponding to the general formula

HO / CK2C2O / nH based on the number of ethylene oxide units, in the ethylene oxide chain - according to the polymerization stage - are liquid viscous solids, the preparation of which is generally in the reaction of gaseous or liquid ethylene oxide with water, ethylene glycol or diethylene glycol in the presence of ethoxylation catalysts. Depending on the properties they have, polyethylene glycol has various applications, for example in cosmetics, textiles, leather, rubber and plastics, lubricants, metal and wood, adhesives and heat transfer agents. . Preferred properties of these substances include, in particular, their water solubility, bioavailability, non-volatility, high temperature stability, and health hazards.

In addition to the numerous advantageous properties, however, the known polyethylene glycols also exhibit one very unfavorable property, namely a relatively high freezing point, resulting in processing difficulties. The freezing point of polyethylene glycols with a mean molecular weight of about: 2.00-approximately -SO ° C. For polyethylene glycol with an average molecular weight of okiO 300 of about -12 ° C, for polyethylene glycols with an average molecular weight of about 400 to 600, it is +4 to + 20 ° G and for polyethylene glycol with an average molecular weight of about 700 to 1500 is about 25 to 45 ° C · Due to these high temperatures, the products need to be stored at higher temperatures to maintain the liquid state or to be heated before use. This implies time and energy, and more frequent heating may deteriorate the color quality of the product. oxidation reactions. In addition, in some applications, for example, lubricants or metalworking agents, failure-free operation cannot be guaranteed by heating, as solidification may occur under certain conditions, and reaction products having high freezing points are formed from known polyethylene glycols.

In addition to pure polyethylene glycols, polyethylene-polypropylene glycols are known. These include substances with statistical, partitioning, ethylene oxide and propylene oxide units in the chain molecule, as well as block polymers from ethylene oxide and propylene oxide. Among the block polymers are those of the general formula

HO / CH 2 CH 2 O / and / CH 9 CHO / b / CH 2 CH 2 O / cH wherein a, b, and c are the number of ethylene oxide and propylene oxide groups. They contain a considerable amount of propylene oxide and differ from pure polyethylene glycols, among others, in that, unlike them, they are surface active and are not biodegradable (see U.S. Pat. No. 2,674,519 and DE-OS1,815,362). In the Journal of the Chemical Society, Chemical Communications nt. 12/1978, pp. 504 and 505 disclose a process for preparing crown ethers in which polyethylene glycol is reacted with ulfonochloronucleotides used in the presence of alkali hydroxides to form crown ether. the starting material is also the polyethylene glycol of the formula

H0 / GH9GH2O / m / CH9CHR10 / CH9CH2O / nH where R6 is methyl and m + n = 5. 0 the properties of the polyethylene glycols used are not " discussed in the publication. EP-A-0 062 807 discloses radiation-esters of acrylic acid curable by the reaction of acrylic acid with a diol which is ethoxylated and / or propoxylated with 1,6-hexanediol , a relatively low alkoxylation degree of neopentyl glycol or tripropylene glycol, a compound which is formed by the reaction of neopentyl- up to 6 moles of ethylene oxide, is also disclosed by the use of other glycol / 1 mol / s 2-diols.

SUMMARY OF THE INVENTION

SUMMARY OF THE INVENTION It is an object of the present invention to provide polyethylene glycols in a modified manner such that they exhibit a substantially lower freezing point compared to conventional poly (ethylene glycol) glycols, while retaining their other beneficial properties. -, -

wherein R is an alkenyl radical substituted with one or more times, preferably once or twice, with an alkyl group, with methyl, ethyl, propyl or isopropyl. The alkenyl chain has 2 to 4 carbon atoms, y is 1 to 2, preferably 1, the sum of x + z is 5 to 30, preferably 10 to 20, x; i z are numbers different from zero. in this case, the compounds, where -R-is -CH 2 GH / CH 2 A, -y-1-1-fl-Zlt-z, R is -CH 2 C / CH 3/2 CH 2 -, y = lax + z = 5 or 6 are excluded. R is according to the invention a branched alkylene group consisting of 2 to 4, preferably 2 or 3, carbon atoms in the alkylene chain and carrying as branching alkyl groups having 1 to 3 carbon atoms, preferably methyl. The alkyl substituents may be the same or different, may be present once or multiple times. The alkylene chain is preferably substituted once or twice. Preferred polyethylene glycols of formula I are also those in which the alkenyl moiety is once or twice substituted, "Ϊ is 1 and the sum of x + y is 10 to 20. Preferred Cy-alkyl substituted alkenyl moieties corresponding to R are as follows:

Formula CH, I 3 -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH , CH, I / 3 -CHO; G-CHCH-CH 3 Name 1-methyl-ethyl / isopropylene moiety / 1-methylpropylene moiety 2-methylpropylene moiety 2-methylbutylene moiety 2.2-dimethylpropylene moiety 2,2-dimethylbutylene moiety 2,2,3 The tertiarybutylene radical of the above alkyl groups has the most preferred properties of an isopropylene radical and a 2,2-dimethylpropenyl radical.

For the sake of clarity, glycols / diols or dihydroxy compounds (corresponding to the above-mentioned alkyl radicals from which the radical R @ 1 of formula I is derived from which the polyethylene glycols according to the invention are derived) are listed below.

Formula CH, I 3 H0GH2CH0H-

CHCH 2 CH 2 CH 2 CH 3 I 3

HOCH2CHCH2OH CH, Name 1-Methylethylene glycol / 1,2-propylene glycol [1-methylpropylene glycol] butanediol-1,3 / 2-methylpropylene glycol. H0CH2CHCH2'CH2'OH 2-methylbutylene glycol πττ | 3 CH 2 CH, 3 HOCH, CCH, CH, OH 2 2 -2,2-di-methylpropylene glycol - / neopentylglycol / 2,2-dimethylbutylene glycol

CH CH, CH-

I 3 L HCHCH 2 C - CH 2 2,2,3-trimethylbutylglycol

Especially preferred are modified polyethylene glycols corresponding to formulas II and III below:

K0 / GH2'3H2O / X / CH3GHO / V / CH9GH50 / 7H / 11 / OH, IO HO / CH3O / C / Tg-C-CHgO / CH9CH20 / zH / 111 / CH3 where y is Number 1 to 2, preferably 1, and the sum of x + z is 5 to 30, preferably 10 to 20, wherein xiz are numbers different from zero and the above rule is true. the preparation of modified polyethylene glycols according to the invention is carried out essentially according to known procedures for the addition of ethylene oxide to glycols. therefore, for such a reaction, a glycol corresponding to the corresponding moiety in formula I, that is, the selected branched monoalkylene glycol (γ = 1) or dialkylene glycol (γ2), is used. up to 30 moles of ethylene oxide, preferably 1-10 moles of ethylene oxide per 1 mol of alkylene or di-alkylene glycol. the process is carried out by introducing into the pressure vessel equipped with a stirrer a branched glycol compound and an alkaline catalyst, then "inert" the atmosphere by flushing with nitrogen or other inert gas to remove water, which may come from e.g. heating under vacuum (using a water pump) is carried out in an appropriate manner from an alkaline catalyst introduced into the vessel or formed by the formation of alkali glycollate and / or solvents such as methanol, which may also come from the introduced alkaline catalyst. when the water and / or solvents are removed, then, at a temperature of 10 ° C to 17 ° C, preferably at a temperature of 120 to 160 ° C, feeds the ethylene oxide in a liquid or gaseous state, the pressure being maintained at 30 to 400 kP. a. End of addition of ethylene oxide with pressure reduction, which remains substantially constant.

In order to remove any volatiles present, it is desirable to heat the polyethylene glycols of the present invention under reduced pressure of 2 to 100 ° C for 0.3 to 1 hour at about 30 to 120 ° C.

Suitable catalysts are alkali hydroxides, carbonates and alcoholates having 1 to 3 carbon atoms, preferably sodium and potassium compounds. Most preferred are hydroxy acid, sodium carbonate, sodium acetylate, and corresponding potassium compounds. The amount of catalyst is generally 0.1 to 5% by weight, preferably 0.3 to 3% by weight. based on the amount of seeded glycol. * r

Modified polyethylene glycols of the present invention present, as known pure polyethylene glycols, liquid viscous to solid products by molecular weight. Compared to pure polyethylene glycols, the novel substances have surprisingly and do not have a substantially lower freezing point, while other important properties have the same. Based on this interesting fact. the new polyethylene glycols are more advantageous in processing and storage than the known materials. For all uses; where it is necessary to maintain the liquid state in a relatively wide range of temperatures, the new modified polyethylene glycols are substantially less susceptible and have no problems characterizing the substances used. Further, it has been suggested that the reaction products of the novel poly (glycol) polyols, such as those etherified, also have a lower solid temperature, which is another important advantage of the novel compounds of the invention. EXAMPLE 1 In a reaction vessel equipped with a stirrer, 104 g of moles of neopentyl glycol and 2 of FWMW of sodium methoxide, methanol in solution (0.6 wt%) were introduced. sodium methylate based on neopent-glycol after purging with nitrogen to remove oxygen, heated to a temperature of 120-125 ° C, and at this temperature was swelled for 2 hours under reduced pressure using a water-pump to remove the methanol present. after the vacuum was removed, the mixture was heated to 130-140 ° C and ethylene oxide gas at 502 g (11.4 mol) was metered in at this temperature over a period of about 3 hours.

Pressure ranging from 100 to 400 kpa was achieved. The end of ethylene oxide addition resulted in a reduction in the pressure that remained constant. The reaction product was purified by removing any volatiles present by heating to about 80 ° C under vacuum for about 2 kpa. Examples 2 to 8 Examples 2 to 8 were carried out analogously to Example 1. The presented glycols, alkaline catalysts and the amount of ethylsoxide metered at the reaction temperature and at the reaction pressure are summarized in Table 1, which follows. For clarity, this table also includes the corresponding values from Example 1 .. V? the following table 2 shows the values for y and x. + from the formula I resp. from Formulas II and III for products prepared according to Examples 1-8. 2 shows the solidification temperatures of the products and their other properties, the average molecular weight, the viscosity at 25 ° C. and solubility in water. Values given for x, y and z represent statistical mean values. - - - ~ ........-

In order to compare the modified polyethylene glycols of the invention with the known pure polyethylene glycols of the same average molecular weight, the values for the known polyethylene glycols of the same molecular weight are given in the "freezing point" column in Table 2, the same values being true for the two properties for the other properties.

As exemplified, the novel modified polyethylene glycols exhibit unexpected low freezing temperatures compared to the known pure polyethylene glycols. Another advantage is the fact that in other properties the new polyethylene glycols do not differ from the known ones. (0 44 73 rd + »Μ> S ¢ 5 44 IX03 44φβ Φ • Ρ * * ° 8 ° ° C0 β + », +> 'Β Οο αχο Ν 3¾. >> +» © -44 3ι 3βΌ Η Γ —ΓΓ * Η, χ Ο -β— —ι — Iρ * ϊ-Ρ Φ 00 γ4 Ο and Η Ο 44> s ¢ 4 00 Ό- © Η 44 Μ> β · o 44> s

pH 00

H

J ο ο ο ο ο ο ο ο ο ο ο ο ο m 1 1 1 I 1 ο II ο ο ο ο ο ο ο Ο ο ο ΙΓ . ο. . ο .. ο. LP Ο LP LP Λ Λ LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP LP)))))))))))))))))))) L xt rd Η Η γΗ (Η γΗ γΗ ΛΡ · ..00, .. ... ο... Ο. .... ΙΡ .Ο -Ο t- -: -.. ** * CM I CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM § § § § § © © © © © © © © * * * Σ ο ο ο σ σ σ σ — — — — — — — tt tt tt tt tt tt tt tt tt CM CM CM CM CM * 00 CM CM ο 00 CM CM CM CM CM CM CM CM CM CM 0 0 CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM CM κ f — 1 Μ. >>> 5 "> 5 •> 5 Μ W ο γ4 ο Η Η κ Η Η Η Η Ή" Η 44 Η 'oo

r-H 2)

X >> >> >> β ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο ο. (Φ (/ (X IX * b (X * β. Χί- (X Τ 1 ΜΟ 1 Μ0 LD ΜΟ ο Ο ο Ο σι [> CM «Μ t ((Μ 0 φ Η φ rf« • ι « · >> Η s s s s s >> >> >> >> >> >> >> >> >> >> >> >> >> >> >> >> >> >> >> >>

CM

CP thi 00

OJ

Table

»O O O P P P O O O O O O O O O J J J J J J J J J J J J J O O O

<—I - CO <35 IO P • É É «« «« «« W W OH OH OH OH OH OH OH OH OH VI VI VI VI VI VI VI VI VI VI VI? M β Γ P P M M M M M M M M M M M M HP HP HP HP HP HP Λ Λ 0 Λ Λ P. P P O O O O O O O O O O O O O O O O

Λ1 O ω and O bOa + jΜ Wa o • a sω + >> td o Ό oj

H Λί

VI 'l "d *

F4 fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd fd ii rl rl -rl Ή • rl • H XJ XJ XJ XJ> O XJ K> £ 0 Λ)

-P

- - -P - - * OJ- -T T -. , O_ O O — 1 m O CM O O O O o -to m HH O H o C rH H Ρ- ω o * p - o md r- o o m oj oj xj- + + + + + +

O

Ol + o

OJ +. O o t * - y h io m-h 01 m oj

1 + I + + + 1 J

O o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o \ t Ch O i-1 HHH OJ OJ iH H i-1 H rM HH r-1 i-1 OJ HO) m IO VD-CO CO industrial applicability

Polyethylene glycols according to the invention have applications in many industrial sectors such as cosmetics, textile, leather, rubber, plastics, lubricants, metalworking and metalworking, adhesives, and can be used as heat transfer agents. A significant advantageous property is that, compared to the known polyethylene glycols, they have a substantially lower freezing point, which greatly influences the scope and application possibilities.

Claims (6)

12 1 - · 'ο, · f í ^ ei <~ - j PATENTOVÝ ŘL ÁR; O -v - Modified polyethylene glycols of general formula I HO / CH 2 OH 2 O (R) / R (y) (CK 2 CO 2 O / zH / 1) wherein R is an alkylene radical having 2 to 4 carbon atoms, which is substituted by alkyl on the alkenyl chain one or more times, namely methyl , ethyl, propyl or isopropyl, y is 1 to 2, the sum of x + z is 5 to 30, with xiz being numbers different from zero, except that when R is -CH 2 CH / CH 3 / -, y = lax + z. = 5a when R 1 = -C 1 -C 4 / CH 2 CH 2 -y = lax + z = 5 or 6, these compounds are excluded. Polyethylene glycols according to claim 1, characterized in that the alkenyl radical R is substituted once or twice with alkyl. 3. polyethylene glycols according to claim 1, characterized in that y is a number 1. 4. "polyethylene glycols" as claimed in claim 1, characterized in that - the sum of x + z is between 10 and 20 · Polyethylene glycols according to claim 1, characterized in that the alkenyl radical R is singly or twice substituted by alkyl, y is 1 and the sum of x + z is from 10 to 20 · Polyethylene glycols according to claim 1, characterized in that they correspond to one of the following general formulas (II) and (III) ch3 ΗΟ / σΗ2ΟΗ20 / χ / ΟίΓ2ΟΗΟ / γ / ΟΗ2αΗ2Ό / ζΗ / 11 / GH H0 / GH9CHo0 / x / Gn <C-CH 0 0 / GH 2 CH 2 O / zH / m / 3 where y is the number 1 and the sum of x + z is from 10 to 20.