DE1443774A1 - Process for the preparation of 2,2-dimethylalkanoic acid esters, 2,2-dimethylalkanols and 2,2-dimethylalkanoic acids - Google Patents

Description

The invention relates to the production of a number of new, aliphatic esters, namely in individual the production of 2,2-dimethylalkanoic acid esters after a telomerization process, as well as the Akb carried out subsequently Production of 2,2-dimethylalkanols and 2,2-dimethylalkanoic acids from the relevant 2,2-dimethylalkanoic acid esters.

2,2-Dimethylalkanoic acid esters are important Compounds »because they are particularly extremely resistant to hydrolysis and oxidation are «These materials are therefore

809810/1292

Application in the manufacture of, for example Plastlfiziexrongsmitteln, lubricants, surface-»active agents, etc. compared with the verzeweigten of unbranched and other compounds prepared _f much more resistant to hydrolysis, oxidation and against Wärmeeinflüsee ₉ (LIE. ₉ For this reason and because of their excellent compatibility are the particularly high molecular weight. ,, 2,2-Dimethylalkanoesäureester suitable as additives in greases, textile (slide) forward waxes _t ,, polyolefin blends, and the like. these "2 _r 2 Dimethylalkanoesäureester are valuable intermediates for the preparation of 2 _s 2 -JDimethylalkanols, 2,2-dimethylalkanoic acids and, if necessary, 2,2 ~ dimethylalkylnitriles and 2,2-dimethyläkylamines. Finally, the 2,2-diethylalkanoic acids and the 2,2-methylalkanols are useful for the preparation of monomers which can be used to produce highly crystalline (stereoregular) crystalline polymers with high softening points ellen.

33a, however, has not hitherto been a commercially useful process for the preparation of 2,2-dimethylalkanoic acid esters The present type has become known, & the invention was based on the object of a method for the production of 2,2-dimethylalkanoic acid esters to develop, especially the technical one

8098 10/1292

viable production of these esters from readily available reap, should enable cheap raw materials «

It has now been found that the desired 2 _t 2 Dimethylalkanoesäuree8ter can be easily obtained by a Telomerisationeverfahren ·

As discussed in US Pat. No. 2,440,800, the term "telomerization" is used as a. Understood the type of reaction that takes place according to the following equation:

IY + b (CH ¹ R ² -CrV) X (CR ¹ R ² CE ³ R ⁴ ) _n Y (Te) .ogen) (Taxogen) (Telomeres)

The compound XY which supplies the end groups of the product is referred to as "telogen" and the polymeric

sable, monomeric olefin called "taxogen" · The

P k
formed reaction product (jtroduftt) is a mixture of

"Telomeres" of various chain lengths. To further

and
Information / regarding a compilation of the relevant literature, see the publication "Telomerisation, A Review of the Literature", US Department of Commerce, Office of Technical Services, PB 131930 of November 19, 1958,

There are already numerous compounds, including carboxylic acids and carboxylic acid esters, as telogens

809810/1292

* »4- * ■

In felomerisatlonsreaktlonsii aie olefin, such as xthylene as flew * - suggested The known proposals have serious disadvantages # In particular, the braokes required for the reactions in question are generally very weak, fi »h» sia liegssa e> ei over? about S19 afm? far®! * saü.ss@a di @ as f © I # g @ n® and Saxogeae iidC'ß Äsgaiigsmaterialisa © isiea aolisß lein “show”, ims sehXi @ lslle! You fall as haapt-? including Matasialissi iron überaiäSig esteUejaä sm & Solyolefiaeii and s amgkattiges Selosieresi _f am »

Di © ls? Fimfiimg Ta ^ riaht on äes · (Hbsrraaeneades

aa © SsofeuttssPeSareester 3.
e 2 ©! © g®aei £ ajaderen esters land whose

iä imea ^ waits deliberately

in the case of it imter? © 2f «j @ 2cii, mig from in particular

al © Telogeae © ntwekelte «new

in this respect, you do away with important ones

e, ALSs for only vernaltnismä @ ig 'low or moderate Seaktionsdrueke are erforderlisli, DA8 the einausetsendea Reaktioasteilnelimer not particularly pure z% \ be' need ₅ and tHe AUSER high yields of short-chain telomeres other products "in particular Eoiyolefine will not get"

In one, according to the invention, is a Telomeriea- 8098 10/1292

extraction process is provided in which a the taxogene component forming olefin having endstäridiger Boppelbindung using a Carbonsäureesters as telogen component in the presence of ^x olyaierisationskatalyeators at elevated temperature and under pressure polymerized resp · is telopoiymerisiert "and which is characterized in that the Carbonsäureester from a isobutyric consists*

According to the invention, therefore, an isobutyric acid ester is reacted with a taxogen, such as ethylene or propylene, in the presence of a polymerization catalyst which can act effectively via free radicals or ions, at a relatively low pressure with heating «,

Which are mainly in the method according to the invention The reaction taking place is essentially a telomerization reaction and flows through the represent the following equationί

O CH, O CH

«T J I! t

EOC-CH + n (CH ₂ = CH ₂ ) - ~~>

8 0 9 8 10/1292

in which the substituent S is primarily methyl, ethyl, propyl, xsopropyl, butyl * sec, butyl, tert-butyl, amyl, xsoamyl, cyclohexyl, benzyl, phenyl and tolyl and η is a whole number from 1 to 16.

The inventive method gives excellent yields of low molecular weight telomer products such as 1 ί 1, 1 ι 2 and 1: 3 adducts, ie Dimethyliälkaaoesäureester with 1 to 3 olefin units per molecule, whereas polyolefins, such as polyethylene, polypropylene, etc., are not formed, and gröiBere amounts of high molecular weight products do not arise »Home the reaction conditions are adjusted within the according to the invention preferred limits properly matched, is as Haup'tproduk-t a Chemically of low molecular weight telomeric esters" namely, esters with 1 to 3 tsxogenen a. ';. nits obtained per molecule "

An essential, feature of the erfindungegeraäßsn g traversing sas "be tehtv vile ₉ already said the use of a IsobuttejLg.äureesters as telogen" The '/ A out, -for h & .upx-eäalilieh for the telomerization of τοη ittsruäuröffioiioestem- Syps ROOOCH (CH ^) ^ beniitsi; «vroriri the rust R is a monohydric alcohol _{radical f} , including radicals such as alkyl,, cycloalkyl, aralkyl or aryl» However, the applicability of the invention is

809810/1292

η η telomerization that can be carried out under moderate »pressure

The process is not limited to leobutyric acid esters of monoalcohols; rather, esters of isobutyric acid in general can be used for the invention, including isobutyric acid monoesters of Polyolem, such as trimethylpentanediol monoisobutyrate, ! • opentyl glycol monoisobutyrate etc., isobutyric acid / diund-trieteters of diols and triols, such as trimethylpentanediol diisobutyrate, neopentylglycol diiaobutyrate, Trimethylolpropane triisobutyrate, etc. and various less common meobutyric acid tea ^ like sucroee-

aoetatlsobutyrat, sucroseoctaisobutyrat, isobutyroxytrimethylhexylieobutyroxytrimethylhexoaten such as is.B. 6-isobutyrpacy-315 »S-trimethylhexyl-e-isobutyroxy-J, 5» 5-trimethylhexoate * and the like.

Accordingly, for the method according to the invention even

wherein B of the above formula is an acyl oxy-

alkyl or an oxyalkyl reet is useful «

But preferably esters of lower aliphatic monoalcohols Although iet useful in calibrating each isobutyric _f used because of the lower boiling points of the resulting telomeric esters and the consequently easier separation of the reaction products. A particularly suitable setter is isobutyl isobutyrate, which is known by

* ((JH ₅ ) ₂ CHC0CH ₂ C (CH ₃ ) gCHgCH (GH ₃ ) CH ₂ CH ₂ OCCH ₂ CH (CH ₃ ) CH ₂ C <CH ₅ ) ₂ CH ₂ OCCH (CH ₃ ) ₂

809810/1292

Condensation of isobutyraldehyde with itself, in Presence of a suitable catalyst produced

also will. Except isobutylisobutyrate are Masat methyl, ithyl-, isopropyl, propyl, sec "butyl and tert butyl isobutyrate _e been used with success for the erfindungsgeinäße Verfehren. A special purification of the esters in question is not necessary, rather the commercially available isobutyric acid esters can be used directly for the process.

The process of the invention finds its main application with catalysts and taxogens which are suitable for telomerization by means of free radicals. Ethylene and propylene are preferred as taxogenic materials, although other 1-olefins of the formula CH ₂ = CH ¹ E ² , where R each represents a hydrogen atom or a lower alkyl group, can also be used. Such olefins are known to be easily accessible industrially and, moreover, no special purification is required here either. In the preferred embodiment of the method according to the invention are the polymerization catalysts used free-radical in nature, with any compound or combination of compounds that generate free radicals, can be used as a catalyst "Examples of suitable catalysts include _e Bi-tert.Butylperoxyd, hydrogen peroxide and Cümolhydroperoxyde

^ BATH ORIGINAL

809810/1292

Oxygen and air are also suitable. Organic peroxides are preferred as catalysts used. A suitable concentration of catalyst

Usually about $ 0.1 to $ 4 based on that

is weight of the leobutyric acid ester »and / the optimal Concentration generally around 0.2 to 2 percent by weight,

However, the process according to the invention can be carried out just as well with ionic telomerization catalysts, which is why the invention also relates to the use of various catalysts and taxogens "*"

extends that for the kaekLonisehe and anionic

t telomerization are suitable. The one for a canonical Catalysts suitable for telomerization are strong Lewis acids, i.e. strong electron acceptors; the suitable taxogens are olefin monomers terminated with Double bond that have electron-loosening substituents, such as compounds of the type CHp =

wherein
OBH, 8DOUBBc Ry can be hydrogen and at least one of the R substituents from alkyenyl · "alkoxy alkyl"? Aralkyl groups or the like exists, for example in vinyl ethers, iJI isobutylene, gC-methylstyrene, isoprene, etc. present. I. E. the expression ^M 01efinHionoaeres ^{n with a} terminal double bond is not only understood here to mean 1-olefins,

BATH ORIGINAL 809810/1292

but generally acyclic and cyclic compounds of the type CH ₂ = CRR, in which R each denotes a hydrogen atom or various organic radicals

The catalysts suitable for anionic telomerization are Lewis bases, such as metal alkyls, Alkali metal hydroxides. The taxogens suitable for this type of reaction are terminal olefinic ones Monomers that have electron-withdrawing substituents

contain, including compounds such as axkyl-

nitrile, methacrylonitrile, methyl methacrylate, etc.

The reaction temperature depends on the catalyst used. Useful temperatures are in the temperature range from about 5O ° C to 400 ^0, is however generally preferred to a temperature in the range of about 50 ° to 300 ⁰ C. The optimum temperature ranges for the individual catalysts can be seen in the following table:

Catalysts at optimal temperature

range in ⁰ C

Ethyl peroxide 50-80

Benzoyl, butyl, lauroyl.

or propyl peroxide x 60-100

Diethyl or dimethylphenyl oxide * 120-160

Cumyl or di-t-butyl peroxide * 130-180

Hydrazine salts, cummol hydroperoxides 200-300

Perhalogen compounds., Oxygen * _{RAn nR1PfM} ..

Hypohalides 175-300 ^BAD ORIGINAL

8098 10/1292

Virtually reaction temperatures are zv / iselien about 10 ^ü ° to 30O ⁰ C preferred for satisfactory conversions and reaction rates to achieve · For best results, it is important to select a catalyst that has a reasonable half-life in the occupied working temperature "

The printing conditions for the process according to the invention are of great importance. The partial pressure of the Olefins must be in the range of about 28 to 210 atmospheres, m «i (400 to 3,000 psig). Greater pressures than about 210 atmospheres result in waxy products, while pressures lower than about 28 atmospheres Provide conversions too low to be economical · When using a lower alkyl ester of isobutyric acid as telogen, ethylene or propylene

and
as a taxogen / an organic peroxide as a catalyst, the preferred pressure range is about 35 to 140 atmospheres. If isobutyl isobutyerate is used as telogen and di-tert-butyl peroxide is used as catalyst, particularly good results are obtained with a pressure of about 56 atmospheres. ”Therein. That excellent results can be obtained with the process of the invention at such moderate overprints is a valuable feature

in the
of the procedure. The / Individual ^ Preferred Prints

fluctuate within the specified range with the

BATH. ORIGINAL 809810/1292

Reaction temperature and the particular catalyst used. At higher temperatures it is necessary use a higher pressure to obtain equivalent molar concentrations of the olefin to maintain in the reaction mixture.

The reaction time or the contact time in the method according to the invention can largely can be changed, namely from a few minutes to several hours, otherwise the contact time the least influence on the product distribution, compared with the other reaction parameters such as the reaction temperature and the partial pressure of the olefin used. However, generally leads a long contact time with products of higher molecular weight, while with shorter contact- « times a more uniform yield of low molecular weight product, albeit at a lower degree of conversion, is achieved. A contact time of about 0.5 to 4 hours is usually the optimum.

The formation of the higher esters appears to be inversely influenced by the reaction temperature will. As the temperature rises, the formation of the higher esters is reduced »As in the The following examples show »for high yields of higher esters a higher partial pressure of the Olefins and a low temperature chosen while

809810/1292

vice versa for low /, usbut at higher Telomers a high temperature and a low partial pressure of the olefin in question can be selected.

The method according to the invention can both Batch-wise as if carried out continuously «When carrying out batch-wise, proceed as follows: First of all, this is lied to, i. E. an ester of isobutyric acid, and the catalyst in one appropriate high pressure autoclave introduced, then the air in the autoclave with the taxogen, such as Ethylene or propylene, displaced, in front of the contents of the autoclave according to the one used Catalyst and the desired product distribution selected temperature is heated. If the chosen Working temperature is reached, ethylene is forced into the autoclave until the pressure is in the range of 28 to 210 atmospheres, the pressure chosen and maintained being a puncture of the desired Product distribution is. For a more precise regulation of the product distribution, i.e. the product distribution at If the reaction is carried out in batches, the autoclave is preferred with the telogen, i.e. an ester the isobutyric acid charged, the air in the autoclave with the taxogen, such as ethylene or propylene, displaced, and then the contents of the autoclave heated to the desired temperature, whereupon the

809810/1292

-H-

Taxogen is admitted up to the desired working pressure. Only then is the catalyst, either as such or dissolved in a small amount of the telogen, injected into the autoclave in order to initiate the telomerization reaction. In this type of work it is very important that adequate cooling is provided so that the reaction temperature can be controlled if necessary. After the reaction has ended

± x ± then the Autoelav emptied »The crude product contains 10 to 70 percent by weight of 2 _r 2-Dimethylaklkanoesäureestern) depending on the catalyst concentration + ^u f in the partial pressure of the olefin used. The esters in question can moreover easily be isolated by distillation in a column having 15 plates at a reflux ratio of 3 ϊ 1. Reduced pressures are used in the distillation of the higher esters.

If this is carried out continuously, this will be lied to, i. h _# is an ester of isobutyric acid and the taxogen, such as ethylene or propylene, continuously fed into a stirring devices exhibiting system, the system in question may consist of a Sührautoclaven or one of the conventional systems with mlaiifpuS8§Ä ^ü ». In addition, a suitable catalyst is continuously used, either as such or in the form of its solution ^

BATHROOM OBIGINAL 809810/1282

in the telogen fed into the system at such a rate that the desired Conversion is achieved or maintained * Connected to the reaction system is a

Gae * -

continuously operating liquid separation

direction where the ethylene or propylene is separated and returned to the reaction system * Das liquid reaction product is continuously withdrawn and transferred to a distillation tract, where the unreacted isobutyric acid ester is separated and then also into the reaction system is returned. That of the isobutyric acid ester stripped product is then further fractionated to recover the individual components. The method according to the invention is further described below

Examples 1 to 6

These examples teach the experimental _results

the ethylene telomerization of methyl ^ -isobutyric acid-

tmter
ester ram different conditions were obtained,

the conditions involved being chosen to regulate the amounts of higher lelomers produced. The methyl isobutyrate was used in each case to · 98 to 99 · 1 ° purely The ethylene besafi di · normal purity without possibly on "impurities present such as water, carbon dioxide, and the like

809810/1292

Particular attention was paid to »In each case the methyl isobutyrate was mixed with the catalyst

11 and inserted into a 2 liter stirred autoclave The autoclave was first rinsed with ethylene and then heated to the selected reaction temperature heated to the selected reaction pressure. These conditions were maintained for the selected reaction time, whereupon the autoclave was cooled and the pressure released. The contents of the autoclave were comatographiech in each case analyzed and then separated by distillation.

The reaction conditions selected in detail and the test results obtained are summarized in the following table. The heading ^M Cg acid ester ⁿ in the table relates to an ester in which the acid part of the molecule contains a total of 6 carbon atoms, namely methyl-2,2 dimethyl butyrate. Correspondingly relates

en the heading "Cg acid ester" on an / ester in which the acid portion of the molecule contains a total of 8 carbon atoms, namely on methyl 2 _f 2-dimethylhexanoate.

Further, the term "C _1n acid ester" relates to

en ^ιυ

an / ester in which the acid portion of the molecule contains a total of 10 carbon atoms, while the term ⁰ C ₁ 2 ** G22 * " ^s & ^urees ' * ^{; er} " slck refers to those esters in which the acid portion of the molecule contains more than 10 carbon atoms. f> has material atoms, ' ^r

809810/1292

Table I.

MethyliBobutyrate-Ethylene TelomeriBations

Weight

Product. S-ewiohteprozente

Catalyst > Ketaly- Ethylene- Reaction- Reaction- C _g acid- Coöäure- C ^ acid- C ₁₉ -C ₉₉ -

... 4th - v.- ₀ . aruck temperature time _ester ^^ _Β ^ _βρ g ^.

Eater ■. ^Ester

1 Di-tert.-
butyl peroxide 1.0 00
O 2 Di-tert -
butyl peroxide 1.8 φ
00
—K
O
ro 3
4th Dift-tert.-
butyl peroxide
Di-tert -
butyl peroxide 1.0
1.0 CD 5 Dicumylper "
oxide 1.0 6th Cumene hydro
peroxide 1.8

35
(400) 140 56
(800) 140 56
(800) 120 84
(1200) 140 (8O ⁵ O) 110 (800) 230

20.0 37.4 22.2 5.4 30.0 20.0 19.0 19.0 12.4 49.6 90.0 10.5 13.2 11.7 64.6 22.5 9.2 11.6 10.4 68.8 10.0 13.1 14.1 15.0 57.8 20.0 39.0 24.6 16.6 20.8

Values in brackets mean psig values

Example 7 shows the ethylene telomerization of

with
Isobutyl sobutyrate / DI-terte-butyl peroxide as a catalyst.

Example 7

98 pounds

Into a 2 liter ~ Rührautoclaven v / ere 864- g'Isobutylisobutyrat (6 moles) and 4.68 g of di-tert filled _e -butylperoxyd (0.036 mol). The autoclave was purged with ethylene and then heated under stirring for 20 hours under 63 atmospheres ethylene pressure at 14O ⁰ C. After the autoclave had cooled and relaxed, it was emptied and the crude product was distilled. A total of 310 g of telomeric product was obtained. The analysis and calculation indicated that 5.8 weight percent of the Isabutylisobutyrats in isobutyl- 2,2-diniethyl- butyrate, further 5.9 weight percent of the Isobutylisobutyrats in Isobuty2r-2 _f-2 Biraethylhexanoat, 4.0 weight percent of the Isobutyiisobutyrats in isobutyl-2 , 2-dimethyl octanoate and the "2% by weight of the isobutyl isobutyrate had been converted into esters with more than 10 carbon atoms in the acid unit of the product molecule"

Example 8 below shows ethylene telomerization. of isobutyl isobutyrate with cumal hydroperoxide as a catalyst *

Example β

In a 2-liter autoclave a maximum of 576 g

809810/1292 ^BÄD

Purified isobutyl isobutyrate (4 mol) (with about 0.002 fi water) and 5.1 g cumene hydroperoxide (0.024 mol) were added. Ber autoclave was purged with ethylene and with stirring under 63 atmospheres ethylene pressure (dry) for 10 hours at 268 ⁰ C heated. After cooling and releasing the pressure, the reaction product was removed from the autoclave and analyzed. It contained β 1.1 percent by weight of low-boiling fractions, 85.0 percent by weight of isobutyl isobutyrate, 5.7 percent by weight of isobutyl 2,2-dimethylbutyrate,

4.1 percent by weight isobutyl 2,2-dimethylhexanoate, 1.7 percent by weight isobutyl 2,2-dimethyl octanoate,

1.2 percent by weight of 18obutyl-2,2-dimethyld4eanoate and 0.5 weight percent isobutyl 2,2-dimethyldodecanoate.

Examples 9-15

In these examples a number of esters were found that were similar in chemical structure were telomerized with ethylene, including methyl isobutyrate and isobutylobutyrate a 300 ml stirred autoclave was used in each case. The catalyst consisted of di-tert-butyl peroxide Comparable amounts of ester were used, with the molar ratio of ester to catalyst in each individual case about 1: 0.006 was> ber esters in each case with the catalyst mixed and placed in the autoclave, whereupon the

BATH ORIGINAL 809810/1292

Rinsed the autoclave with ethylene and then on heated to a selected reaction temperature and at this temperature under a selected ethylene pressure the autoclave was heated for a certain (selected) time after cooling and releasing the pressure the crude product was emptied from this and the material analyzed »from the following table show the reaction conditions used in detail and the test results obtained.

809810/1292

Tabel

Example ester

fempe- print time rature atm "hrs. o-

9 10 11 OO O 12th (D 00 13th O 14th ro 1b co

Xethyl isobutyrate 151

Isobutyl isobutyrate 148

Isobutyl isobutyrate 153

sec-butyl acetate 148

Methyl n-butyrate 147

Isobutyl formate 14f

Diethyl malonate 149

55

54.

56 56 ca 53 56

55

"Content of the raw product in percent by weight am

liquid
product

20.2

27.8

21.3

0.0

1.7

0.7

5.4

solid product

ca «0.2 ca« 0.2 approx. 0.2

1.3 1.0 4.7 1.2

to

This shows that esters other than isobutyric acid esters with relatively moderate excess pressure with Ethylenes cannot be telomerized to any appreciable extent, and that a large part of what is actually formed Product consists of waxes,

Examples 16 to 21

^ These examples bring experimental results obtained at the Ithylenlelomerisation of isobutyl isobutyrate under conditions that were chosen so that the formation of the Isabutylestern 0g-, Cg, CLq- and C was ₁₂ -2,2-Dimethylalkanoesäuren as high as possible .

and

In each case the isobutyl isobutyrate / the catalyst was placed in a 2 liter stirred autoclave, whereupon the autoclave is rinsed with ethylene and adjusted to the selected reaction temperature at the selected reaction pressure was heated. These conditions were made during the

following
the times given in / Table II were maintained, whereupon the autoclave was cooled and let down. tmx distillation separately. The table shows that, under the conditions preferred according to the invention, the main conversion product consists of a mixture of the lower telomers. In fact, more than 85 percent by weight of the telomers obtained in Examples 16 to 21 consisted of esters of Cg-BCj2 ~ * ^acids »

809810/1292

which corresponds to telomeric esters with 1 to 4 taxogen (ethylene) units per molecule.

809810/1292

-P

φ ta ο

A. CQ

• Η

-P

• 3

• ο

FM

VO

τ- O

CM O

O O

VO O

■ Ρ · • Η-CJ φ + »

NCQ

3 - Ζ ZZ A

S-P

© W

fr ι Cj

I 1 I Ή

CQ> »Φ £

O -P «4 Π U Ή <β O Φ Φ £ Μ-Ρ« β-Ρ Φ CO O SB O pc)

O CM

CM O

VO CM

VO CM

in O

O O

O »Λ

τ- r »-cn vo * - ^ -

CVJ

CM CM

CM CM

cn

CM QO

in

co cn

vo in

CVl

vo

tr \

CM CM

CM

OO

00

cn

in τ

CM

CM CM

vo

CM

in

in

CM CM

in

CM

VO CM

O O

CM

τ - CM

CM

VO CM

O O

O O

vooo mm vooo

cn

κ \ in

vo τ- cn

O T-

cn

VO

in

• P

ce α

+ »Ββ M

Φ AO U • β

rl

O O

• Ρ H
O M. U ι φ A. -PtI
U t> » • ρ I. • Η pi

• Ρ

-P

-Pf * + »« rf

BM Φ M

4 * O -PO -PO

IM IU I U

• Η 9 -H 9 -H Φ

^ A RA RA

• p «tf ^ * ιβ

■ Ρ

• Η Φ

£ 3 Ω |

• Ή A CQ vo t * - co cn ο * -

* - .ν χ- τ- CM CM

809810/1292

Examples 22 to 26

These examples bring test results of the ethylene telomerization of various esters of isobutyric acid. All experiments were carried out as indicated for Examples 1 to 6 and 16 to 21 and the products obtained were separated by distillation. The test results show that the size (value) Ton E in the formula BOOCCH (CH ^) _{2 has} no influence on the telomerization of isobutyric acid esters. In each case, 1 & tert-butyl peroxide was used as a catalyst for the experiments.

Isobutyrate
eater Temp.
⁰ C Tabel III Product, ⁰ IO Weight percent ⁰ H ^C 16 Ethyl 210 ^C 8 27 ^C 12 2 1 example Propyl 212 pressure
Atm.
(psiic.) 33 22nd 6th 1 3 22nd Cycloheayl 206 84-98
(1200-1400) 31 26th 31 11 5 2 23 Benzyl 235 84-104
(1200-1490) 37 28 18th 5 1 3 24 ffaenyl- 223 94-105
(1350-1500) 29 29 23 8th 7th 3 25th 84-95
(1200-1325) 41 22nd 9 26th 84-90 36

Example 27 shows the propylene release of isofeutyl isobutyrate with M-tert-butyl peroxide as a catalyst

Example 27 864 S isobutyl-

809810/1292

isobutyrate and 4.6 g of di-tert-butyl peroxide were added, the Autoelav was rinsed out with propylene and ^{heated to HO 0} C (with stirring) for 5 hours under a propylene pressure of 56 atmospheres. After cooling down and

Blowing off the excess propylene, the reaction

(the telem, product) product separated by distillation. It was made of

64 percent by weight of isobutyl esters of C ₇ , C ₁₀ and C ₁ acids and 36 percent by weight of higher, liquid telomers.

shows
The following example 28 / the propylene telomerization of methyl isobutyrate with di-tert-butyl peroxide as a catalyst »

Example 28

In a 2-Idter-Rührautoelaven 929 g methyl isobutyrate and 3 »2 g of di-tert _e -butylperoxyd given by 84 atm propylene were pressed and heated for 3 hours at 178 ° C * After cooling and venting of excess propylene, the autoclave emptied and the product separated by distillation «33 56 of the methyl ester of 2,2-dimethylpentanoe

at together. ,;

acid / sack 88 $> methyl esters of C ,, -, Cjq- and G -.-- acids.

The following example 29 'shows a continuous Process for the ethylene telomerization of isobmtyl

809810/1292

butyrate,
Example 29

The reaction system used is shown in the accompanying drawing in the diagram. The reactor 10 consists from a cylindrical steel vessel 35.6 cm in diameter. The entire volume of the system, including the steam-heated exchanger 12 and the five-stage Centrifugal pump 14 is approximately 318 liters. That introduced into the feed vessel 16 through lines 18 and 20 Isobutyl isobutyrate is continuously in an amount of 95.3 leg by means of a controllable feed pump 22 fed hourly or 2 270 kg daily (into the reactor) · The di-tert-butyl peroxide used as a catalyst is fed via a line 24 to a catalyst mixing tank 26, where it is continuously with a small hatchet of the isobutylisobutyrate stroas removed from line 18 through line 28 is mixed becomes »A 20-year solution of the catalyst in isobutyl isobutyrate is fed through a separate metering pump 30 into a line 32 in such a way that 0.4 to 1.31 percent by weight thereof, based on the laobutylisobutyrate main stream, come from line 34

To facilitate temperature control, a stream of liquid is drawn from the bottom of the reactor Withdrawn via a line 36 and by means of the pump 14

809810/1292

¹ 28

- 28 - »

through a line 38, the WärSMeamstausher 12 and

0 in the reactor
a line 4Ä / "led back _c from © in a gas container

by means of a compressor 46 m & / a line 48

Ethylene with a pressure of about 50 to 58 atm "

The ethylene atom, the catalyst atom of the

one
Reactor * /

The circulation stream and the leobutylisobutyratro »misohtn ■ generally the solution 58 mnä form the ice entering the hair actuator via the exchanger 12 and the outlet 40. HeaktofeaseMöfeungsetroBi 3 ⁰ G held » U ₁ , ii" se the BsscMclcungeetrom, 4 * naoMeai as required, heated or cooled *

The bulk of the product flows from the reactor through a line 50 into a steam-liquid separating device 55 (from which ethylene which has not entered into action is withdrawn through lines 5+ and 56 in the "Gaab" filter 44, but is withdrawn through a line 58 ·, Liquid product runs through a container 60, a · Piunpe € 2 and a line 64 to a distillation column € 6, which has a Durohaeeawr of? 0 _# 5 om and a · height of 9 _# 14 * «and a yüllköryerkolonne if "Sa" did not react · XeobutyliÄobutrrJit is stripped here and cleaned by «in» Leitang 68 ohn · Wolter «in d« n! «obutylieobutyrrnt ·

'· ■ BAD ORiGINAL

809810/1292

epeisebehäler 16 returned «The telomere products are finally withdrawn through a line 70 for the purpose of separation by distillation «

In the drawing the abbreviations mean ⁿ PG ^"M and FtB.G ^'s pressure regulator and writing pressure regulator of known type"

The individual average conditions observed, degrees of conversion, yields and product distributions in the course of an experiment extending over 15 days after the continuous one Procedures of Example 2 are given in Table IV

809810/1292

809810/1292

Safcelle IT

1 185 56 »5 0.6 2.4 17th 2 184 56 0.4 2.4 13th 3 186 57 0.55 2.5 16 4th 188 56 , 5 0.95 2.5 24 5 188 57 , 5 1.24 2.5 25th 6th 186 50 1.24 2.7 16 7th 186 57 »5 1.08 2.4 19th 8th 188 57 1.07 2.4 20th 9 188 57 1.24 2.5 26th 10 188 58 1.22 2.45 25th 11 188 58 1.22 2.5 21 12th 186 57 1.3 2.5 24 13th 187 56 1 »42 2.5 21 14th 188 58 1 »1 2.5 19th

97

Day temp. Pressure weight · contact mole percent conversion weight a no. ο «Atm · percent time in l unff pro ,! Dur ch hang pro ζ ent

Katalyea · »Std» _Te , "i- V ₊ -U," Telomeres

Beechätoc ieobutyrat _d ⁿ _m JJJ ^ lung tor from

kicking

material

gelomer distribution, weight percentage

30th

97 26.4 96 27.5 97 36.7 98 35 97 29 96 31 97 33 97 35.5 97 34 97 31 96 35 95 32 96 30th

G C

^{10 12}

^G 14 "" ° 22

'16

23 21 16 10

> 1 31 20th 17th 9 24 34 25th 12th 3 18th 33 33 6th 7th 20th 31 34 9 5 25th 26th 24 10 12th 26th 29 27 8th 10 20th 29 35 8th 5 18th 37 31 9 3 18th 32 34 12th 2 17th 41 31 4th 6th 20th 39 24 11 4th 20th 36 35 2 5 2o 34 24 11 9

15 189 57i5 1.31

2.5

24

96

35 29 33 10

On the various characteristics discussed above, the The fact that erf imdungagem & ee Terf ahreniron differ from the known telomerization processes is different inventive method ron these in a further important feature when isobutyl isobutyrate is used as a felogen, i.e. it occurs alongside the main reaction, whereby daa olefin «η da« carbon atom Ir. 2 of the Xeobutteraavre unit of the Seter · is added, also addition of the olefin to da «lohlenatoffatcm Vr. 2 of the isobutyl alcohol unit a · Accordingly, according to the method according to the invention, products of the following type can be obtained "where as «UBLtML listed product rom Type X the main product forms and in a molar ratio ron about 10ti sn the likewise formed products of type II and III arise ”.

01. 0 CH,

¹ l ²

Ttp I I (OI ₂ -Cl ¹ l ² ) _a -0

«, Ο οι,

ψη 11 »J-O_J3 ~ O-OH ₂ -C- (CH _2T OR ¹ l ² ) _n I

οι. ο οι-

01 «

809810/1292

1 2

In the above formulas, E and E denote hydrogen atoms or lower alkyl groups and η is a whole number iron 1 to, 1β _β

^ As already mentioned, the 2.2-Dimethylalkanoesäureestei'g which can be produced by the inventive process, \? Ertvolle intermediates for the preparation of 2 _t 2 Dimethylalkanoesäuren and 2 _f 2 ~ 3) iinethylalkanolaisowie various derivative of such acids and alcohols © Compounds of the above-armored type I, which "as I said, form the main" product of the process according to the invention, as well as compounds of the type III kdaneii söfcaüdESSk below? @ w & TgiBek®m, HydrolysebiliaguBgesi to 2,2-dimethylalkenoic acids of the type

OH- 0

'S *) ~ G C-OE

η ι

1 2

are hydrolyzed, in which R, S and -η are given above © Have meaning *

Connections of fyps XI and. des fyps III can under vigorous hydrolysis conditions in 2,2-ΦΙϊε «·» thylElkanole des fypβ

309810/1292

? 3
H (CH ₀ -CR ¹ R ² ) -C CH ₀ -OH

1 2
be converted, in which R, R and η are also the

have the meaning given above. In addition, the

Lr *

Esters of all three types mentioned y in 2,2-Dimeth.yltlkanoIe (converted by reduction or hydrogenation will"

in

Another / beyond the scope of the present invention Another valuable process involves the acidolysis of the Type I ester with isobutyric acid to give 2,2-dimethylalkanoic acids according to the following equations:

H (CH, H ² ), CH,
♦ 3 0
-COR + CH, 0
♦ ⁵ «H ₉ SUN. Γ?
C. CH ₃ H (CH, Λ CH- O
t 3 η
• * C C-OH
* ι Isobutyric acid , -CR ¹ CH, 0
HC - COR , -CR ¹

CH, CH,

2,2-Dimethylalkanoic acid isobutyric acid & ter

809810/1292

The reaction is else performed in the "V / that the telomere ester type I in · presence of an acid catalysis ^ to & rs, such as sulfuric acid, is heated with Iaobuttersäure _e An important advantage of this method is _s that the original

Isobutyric acid ester, which is used for the production of the telomer

one
Esters is used as / the reaction products are formed

can be and returned naturally in the telomerization reaction "Another cyclic process according to the invention is the ester of type II in the presence of a catalyst such as an alkali metal, such as Natriumisobutylat, with isobutyl alcohol to alcoholysis to unterwerf en _g being obtained * a product that from the 2,2 «-dimethyl <?> alkanol of the type

HO-CH ₀ -C- (CH ₉ -CR ¹ R) JH

GH

and the isobutyric acid atar as it is used for the preparation of the telomeric ester ₉ . Here, too, the isobutyric acid ester in question is then returned to the telomerization reaction «

Although those formed by the method according to the invention Ester decomposed under vigorous conditions by hydrolysis to the acid and alcohol components concerned

809810/1292

can be, as has just been explained, so these esters can be compared to one Very resistant to hydrolysis. Therefore, in preferred methods according to the invention telomeric esters prepared in a first stage by the new telomerization process according to the invention

■ expand and in a subsequent / graduate these esters ▼ crack or by hydrogenation in 2,2-Dimethylalkanoesäurqnbzw. 2,2-Diraethylalkanols transferred "

The process, according to which the esters are converted into 2,2-Diinethylalkahole, comprises a reduction stage, wherein the esters over a hydrogenation catalyst at higher temperature, namely at a temperature of 200 to 400 ⁰ C, preferablyy about 250 ⁰ C, and under a hydrogen pressure from about 210 to 420 atmospheres. Suitable catalysts include copper-chromite, barium copper-ohromite, Raney nickel, platinum, palladium and the like, the catalysts in question being used either alone or on a suitable carrier material. A catalyst which is particularly preferred for the hydrogenation of 2,2-dimethylalkanoic acid esters is a barium copper chromite type catalyst, such as, for example, a catalyst which contains about 33 percent by weight per cent of copper in the form of copper oxide and about 38 percent by weight of chromium in the form of Cr ₂ O ,, about 10 Jt of barium in the form of BaO and the remainder essentially

809810/1292

Silicium dioxide contains "

The following example is a 2 ~ step process described according to the invention, the esters obtained in the first telomerization stage then being reduced by hydrogenation to 2,2-dimethylalkanols will »The one used in this example for the 1st stage Ester material consisted of a mixture of isobutylobutyrate and isobutyl ~ 2,2-dimethylbutyrate, the latter of which had previously been produced by telomerization "

Example 50

A mixture of 2,540 kg of isobutyl isobutyrate and 19 96 kg of isobutyl 2,2-dimethylbutyrate was fed into a 318 liter steel reactor over a period of 24 hours. 418.2 kg of ethylene and 14.06 kg of di -tert-butyl peroxide (DTBP), Kontaktaelt the average was 2.5 hours and the catalyst concentration is 0.55 kg DTBP / kg isobutyl isobutyrate "the Heaktortemperatur was maintained at 186 ⁰ C and the pressure was about 57.5 atm" the reactor leaving material consisted of 2 08? isobutyl isobutyrate kg and 810 kg · igelomerenjprodukten on the analysis enthlit the Telomerenfraktion 23 * 4 $ leobutyl-Gg-ester, 21.4 i> isobutyl "* 0 _8" eeter _# Ht 3 'f> Ieobutyl-C. "ester, 10 , 7 $ isobutyl ** C ₁ "" eeter _f

10
5 _f 5 i » isobutyl'-Ci. -Ester, 41 % 0% isobutyl-Cjg-eBter

and 20 _t 7 $ leobutyl-C, jg-ester bia C * ₀ * -ester « The Eohprodukt

ORIGINAL BATHROOM 809810/1292

was first transferred to a stripping column for the isobutyl isobutyrate, from which 2,041 kg of the same were distilled off at the opf and returned to the process.
172.4 kg isobutyl-2 _t 2-dimethylhexanoate, 113.4 kg IBQ ~ butyl-2,2-dimethyloctanoate, 86.2 kg isobutyl-2,2-dimethyldecanoat, 45.4 kg isobutyl-2,2-dimethyldodecanoat, 31.8 kg of 18obutyl-2,2-dimethyltetradecanoate and 166 kg of ieobutyl-2,2-dimethylliexadecanoate were separated off until the isobutyl-2,2-dioethylootacosanoate. were transferred while the other telomeric hedgehog sequentially into a hydrogenation unit, where they in contact with a Bariumkupferehromitkatalysator at about 250 ⁰ C and
a hydrogen pressure of about 210 to 420 atm. in
2.2 »Dimethylalkanols and isobutanol were converted. After the isobutanol was separated off by distillation, the pure alcohols were obtained, their individual
Singe and properties in the following table T
are listed.

309810/1292

»Ρ

I- IO O co CO t- to O T- CM IO "* ■ "ti"

ιη

to

J) O • OCM

fcO PiOCM

σ »
co

CM

co

O GO CM

co

IO

T-Kv CO

VO

co

to

co

IO

co o "

O O

CQ O

CM

in

10

co

CM

VO

O VO

vo ί-

Ο VO O vo

Ο VO I—

Pi-H «·

«Ο

• HOVO

CQO H

VO

•O

IO CM

CM

CM CM

l-CM

IO

CM

OQ

CQ

T-CM

ΟΛΟ

Ο "* τ- CM

CM

CM

VOCO f-VO

4 “O O

CM CM

Jbct η .ο

ΙΟΗΙ VOlO

HO

CM CM

lO ^ Q t-H

IO H CM T-

{Γχ-χί · OCM10

rTw 9 ^W

QO 9> ■ Ö

o co

O tH

■ d + *

ο ο

■ d + »

I ^H

I I

CM CM

CM CM

ORIQIMAL INSPECTED

10/12

Alcohols such as those listed in Table V, the

that is, by hydrogenation of those obtained according to the invention

here
teloaeren ester obtained by the / indicated method

are characterized by their exceptional thermal and hydrolytic resistance. You can do this can be used to make esters which have the same properties and which are compatible with many polymers as well as being valuable as lubricants and plasticizers. Also these are alcohols useful as intermediate products for the manufacture of detergents,

The preferred process according to the invention for the preparation of 2,2-dimethylalkanoic acids comprises a 1st stage, in which 2,2-dimethylalkanoic acid esters are prepared by telomerization, and a subsequent 2nd stage, in which the telomeric esters obtained in the 1st stage are converted to the corresponding 2,2-Dimethylalkanoic acids are cracked The preferred method consists in the thermal cracking of the esters in question at a temperature of above 40O ⁰ C and preferably below about 700 ⁰ C. However, the esters in question can also be suitable in the presence of voa

809810/1292

• - 40 -

Cracking catalysts such as ix different synthetic or natural catalysts, such as silica-alumina, silica-zirconoxy *, Silicon dioxide-magnesium oxide, etc. are cracked »

The following example describes a process for the preparation of 2,2-dimethylalkanoic acids by cracking according to US Pat Invention.

Example 51

In a stainless steel reaction vessel suitable for working under pressure was placed 48.25 kg of isobutyl isobutyrate

and 0.289 kg of di-tert-butyl peroxide introduced »It happened

also

this became continuous and the reaction product became continuous carried away during the experiment, which lasted a total of 96 hours it was necessary, in order to keep the total pressure at about 54 atmospheres, ethylene added, and also one slight, positive ethylene purging maintained by the system »The reaction vessel itself consisted of one 76.2 mm thick, stainless steel tube, which is 6 liter grabbed. The collected reaction product weighed 53 x 9

The average reaction conditions were 169 ° C _t

pressure
about 54 atmj / and 12 hours of contact time while 0.6 g

Di-tert-butyl peroxide / 100 g of isobutyl isobutyrate added were «purposes tracing back to that

BATH ORIGINAL 809810/1292 '

Beaktionsgefäß 31 kg IsobutyÜBobutyrat were stripped from the reaction product · The distillation and chromatography analysis carried out showed that 18.1 i "of telomeric product of isobutyl-2,2-dimethylbutyrate, 16.6 $> from isobutyl-2,2-dimethylhexanoate, 12.7 £ from isobutyl-2,2-dimethyloctanoate, 9.4 5t dimetliyldecanoat 2.2 from isobutyl ~ 26.6 56 Isobutylö-j-ieobutyl-Cg-5elomeren and 16.6 $> from isobutyl CPQ -ieobutyl-O »0-Teloiaeren passed · Some of the isobutyl-Cg-, Ieobutyl-Cg and isobutyl-CjQ telomers were converted into the corresponding acids according to the following formula: Cg, Cg etc. denote the number of carbon atoms in the acid part of the concerned seters

In a heated, tubular cracking reactor, which was filled with "Vyeor glass chips", 1,085 ml of isobutyl-2,2-dimethylbutyrate were introduced, namely 169 ml per hour, the average reactor temperature being 57O ⁰ C. Basal reaction product was 4, 03 normal. 495 ml of 2,2-dimethylbutyric acid and 260 ml of isobutylene were obtained. The average contact time was 11.1 seconds. The ester-acid conversion was 65 i> and the yield 88 ^. Similarly were 1675 ml ¥ isobutyl-2,2-dimethylhexanoate and 1 410 ml Iaobutyl-2,2-dimethyloctanoate introduced into the cracking unit described the lined · to · ⁰ At 59 ° C and a contact time tone were 9.7 seconds at a yield of 84 » 68.5 of the 2,2-dimethylhexanoate converted into 2,2-dimethylhexanoic acid. At 570 ⁰ C in a Kontaktxeit of 9.6 seconds at a ward · · Auebeut τοη 88 £ ^ a 67 owned transfer

BATH ORIGINAL 809810/1292

reached by leobutyl 2 _> 2-dimethyloctanoate in 2 _t 2-dimethyloctanoic acid. Purified distillation «The boiling points and neutralization equivalents were determined and compared with known values»

The acids produced by the specified process are characterized by exceptional thermal stability characterized and can be used to prepare various esters, which are also excellent Have thermal and hydrolytic resistance and at the same time with a variety of polymers

and therefore
compatible admdc ψφρϊψ rnkst excellent plasticizers "tiffiffifKitbcaat are»

8 098 10/1292

Claims (1)

Claims 1. Telomerization process for the production of 2,2-dimethylalkanoic acid esters, 2,2-Dimethylalkanols and 2,2-Dimethylalkanoesauren, in which one is the taxogenic Component-forming olefin with a terminal double bond with a carboxylic acid ester as a telogen Component in the presence of a telomerization catalyst ™ lysators telomerized at elevated temperature and under pressure and the telomerizate is then optionally reduced or cracked, characterized in that that the carboxylic acid ester consists of an isobutyric acid ester. 2. The method according to claimi, characterized in that an olefin of the formula CH ₂ = CR R, wherein R and R each represent a hydrogen atom or a lower alkyl Λ radical and η an integer from 1 to 16, with an isobutyric acid ester of the formula ROOC-CH (CH,) _? , where R is a preferably lower alkyl radical, a cycloalkyl, aralkyl or aryl tea, in the presence of 0.1 to 4 percent by weight, based on the isobutyric acid ester, of a free radical catalyst at a temperature of about 50 to 400 ⁰ C, preferably 100 to 300 ⁰ C, under a pressure of about 28 to 210, preferably 35 to • 140 atmospheres to form a 2,2-dimethylalkanoic acid ester * ORIGINAL BATHROOM the formal 809810/1292 O OIL, 1 where R -, - R and R have the given meaning, telopeiynerized. 3. The method according to claim 2, characterized in that ethylene with a particularly lower isobutyric acid ester in J-xiM esenlieit of 0.2 to 2 % weight percent tines organic peroxide to an IJster of the lorrnel: 0 GH, ROGG- (GH ₂ -GH ₂ ) _n II 'OH,' will. 4. The method according to claim 5, characterized in that the peroxide consists of di-tert-butyl peroxide, ouriiolli hydroperoxide or dicuinol peroxide. 5. The method according to claim 2, characterized in that 'that propylene with a particularly lower isobutyric acid ester in the presence of 0.2 to 2 percent by weight of an organic peroxide to form an ester of the formula: BATH ORIQiMAL 809810/1292 O CH _x II t J J ₁ -OOO CH ₃ telOjw.'iymerä. is vird. 6. The method according to any one of claims 1 to 4, characterized. ,; elcenn ^ calibrates, that ^ .ethylene with isobutyl isobutyrate to one liquid Greiaisch from "Jstorn of Cornelia 0 0H _v Il I ■> ^ OGUUlI ₀ CH I, OIL, CII ,, CH, 0 CII _x J Il I -> HG-G 0-0-OH ₀ -U- (OH ₀ -GH ₀ ) II II and GH _x 0 CII _x I ■? Il Ϊ -> H (GH ₀ -GH ₀ ) -0 CU-CH ₀ -G- (GII ₀ -GH ₀ ) H III C. C. Li. Ι C. j C. C. Ti. with η = 1 to 16 telof ^ tyüiörisiort becomes. 7 · The method according to any one of claims 1 to 6, characterized characterized in that for continuous production BATH ORIGINAL 909810/1292 of a 2,2-dimethylalkanoic acid ester is a gaseous one Continuous flow of the olefin and the isobutyric acid ester together with the organic peroxide be fed to a moving reaction zone so that the reaction flowing out of the zone mixture is continuously transferred into a gas-liquid separation device that the separated, gaseous olefin is returned to the reaction zone, that the collected in the separation device, liquid product is distilled, and that the separated from the product, unreacted Isobutyric acid ester is returned to the reaction zone ο Process for the production of 2,2-dimethylalkanols, characterized in that an ester or ester mixture obtained according to one of Claims 1 to 7 the composition: 0 CH "» ir J ROCC- (GH ₂ -CH ₂ ) _n H CH, or _{c CH} ti ι 0 CH, 80 98 10/1292 in which R and η have the meaning given earlier, catalytically in a manner known per se to an alcohol or alcohol mixture of the composition: HO-CH ₂ -C- (CH ₂ -CH ₂ ) _n H or CH HO-CH ₂ -O- (C ₃ Hg) _n H is reduced, 9 «The method according to claim 8, characterized in that the reduction at a temperature of 200
to 400 ⁰ C and a hydrogen pressure of 210
is carried out up to 420 atmospheres «, 10. Process for the preparation of 2,2-dimethylalkanoic acids, characterized in that an ester or ester 'obtained according to one of claims 1 to 7 mix of composition 0 CH, ROCC- (CH ₂ -CH ₂ ) _n H OH, 809810/1292 or 0 CH »T f CH ₃ ) _n H where R and η have the meaning given earlier, ^{thermally cracked at a temperature of 400 to 700 0} C and an acid or an acid mixture of the composition from the reaction product 0 CH It I HO-CC-CCH ₂ -CH ₂ ) _n H O CH, It! - HO-CC- (ι
CH, will be separated " 809810/1292