DE2341873A1 - Butadiene monoxide and ethylene glycol reaction prods. - as additives in bright copper plating baths - Google Patents

Abstract

New 2-(2-hydroxyethoxy)-3-buten-1-ol nIII) and 1,2-di-(1-hydroxy-3-buten-2-oxy)-ethane (IV) are prepd. by (a) allowing butadiene monoxide (I) to reat, at 0-40 degrees C with excess ethylene glycol (II), in mol. ratio of (I):(II) of 1:2 to 1:10 (1:3 to 1:6) in the presence of acid catalysts, to form (III) and (b) further reaction of (I), under the same reaction conditions, with (III) obtd. in a mole ratio of (I):(III) of 1:2 to 1:10 (1:3 to 1:6) to form (IV). (III) and (IV) are used as additives in acid Cu electrodeposition baths, in concns. of 0.1-10(0.5-2)g/l. (II) and (IV) are obtd. in high yields. Their addn. to Cu electroplating baths improve bath efficiency and the working time can be prolonged up to the onset of first cloudiness, which sets in later, thereby delaying filtration and saving filter renewal costs.

Description

Düsseldorf,: · 5.8 1973 Henkel & CieGmbH

Henke Is tr. 67 patent department

Z / Br

Godfather n-tanme ldung

D 4723

New reaction products as butadiene monoxide and ethylene glycol, their production and use in galvanic copper baths

The invention relates to 2- (2-hydroxyethoxy) -3-buten-l-ol, 1,2 bis (1-hydroxy-3-buten-'2-oxy) ethane, their production made of butadiene monoxide and ethylene glycol as well as use in acidic galvanic copper baths.

It has been found that new reaction products of butadiene monoxide and ethylene glycol by the action of Butadiene monoxide at temperatures of 0 - 40 ° C to excess ethylene glycol in a molar ratio of 1: 2 to 1:10, preferably 1: 3 to 1: 6 in the presence of acidic Catalysts and further reaction of butadiene monoxide under the same reaction conditions with the formed 2- (2-Hydroxyethoxy) -j5-buten-1-ol in a molar ratio of 1: 2 to 1:10, preferably 1: 3 to 1: 6 in high yields receives.

Acid catalysts for the production process according to the invention are, for example, Lewis acids such as Boron trifluoride etherate, antimony pentachloride, tin-IV-chloride, also tertiary oxonium salts of boron trifluoride and antimony pentachloride, for example of epichlorohydrin, such as them E.g. after H. Meerwein can easily be represented, as well as strong acids such as sulfuric acid, perchloric acid and acidic ion exchangers are suitable.

509809/1183

Henkel & CIe GmbH s «h · 2 m raunhmmtidiin« d

From a publication by R.O. Kadesch in the Journal of the American Chemical Society 68, 44 (1946) is known to that butadiene monoxide (3i4 - epoxy-1-butene) in the reaction yields 2-methoxy-3-buten-l-ol with methanol in the presence of sulfuric acid as a catalyst.

When this reaction was transferred to the reaction of butadiene monoxide with polyhydric alcohols, it was too expect that a mixture of the most varied of reaction products will change according to the respective conditions forms. Already with a dihydric alcohol there is initially the possibility of the formation of mono- and disubstitution products. Furthermore, the butadiene monoxide can with the 1-hydroxyl group formed in the reaction The resulting 2-alkoxy; 5-butene-1-oils react. the The same reaction possibilities also exist with the hydroxyl groups formed in the disubstitution products, so that a large number of reaction products are already obtained when reacting with a dihydric alcohol results.

With the method according to the invention, the Possibility created through targeted implementation of To produce butadiene monoxide with ethylene glycol in high yield 2- (2-hydroxyethoxy) -3-buten-l-ol. In continuation the reaction it was also possible to obtain 2- (2-hydroxyethoxy) -3-buten-1-ol among the same Reacting reaction conditions with butadiene monoxide in high yield to 1,2-bis (1-hydroxy-3-buten-2-oxy) ethane. This possibility of producing the two new ether alcohols 2- (2-hydroxyethoxy) -3-buten-1-ol and 1,2-BIs- (I-hydroxy-j5-buten-2-oxy) ethane in high yield

509809/1183

Henkel & CIe GmbH "see below 3" "M.monm.idum d t-723

from butadiene monoxide and ethylene glycol through a simple one Distillation process was completely surprising.

The new ether alcohols produced according to the invention are particularly suitable for their performance to improve modern acid galvanic high-performance copper plating baths. In such baths that are used as brighteners organic sulfonic acids whose sulfonic acid group has an aliphatic radical and a sulfur atom on is bonded exclusively by heteroatoms, can be contained by the addition of the new ether alcohols the operating time until the onset of the first cloudiness and thus the time until the required Extend filtration many times over. In addition to saving costs for the filtration, this also results also a saving in filter material, which no longer has to be replaced as often.

The new ether alcohols according to the invention are used in the acidic electroplating copper baths in an amount of 0.1-10 g, preferably in an amount of 0.5 - 2 g per liter of bath liquid.

The following examples are intended to explain the subject matter of the invention in greater detail without, however, referring to it restrict.

509809/1183

Henkel & CIe GmbH «.η * 4« r p <.i.xtonm.id »ni d 472?

Examples

1) Production of the reaction products from butadiene monoxide and Ethylene glycol

a) 2- (2-Hydroxyethoxy) -3-butene-1-oil

To a mixture of 186.2 g (5 mol) of ethylene glycol and 1.4 g of boron trifluoride etherate (5 mol ^) as a catalyst, 70.1 g (1 mol) of butadiene monoxide (j5,4-epoxy-1 - butene) dripped. The rate of addition was regulated in such a way that the temperature of the exothermic mixture was kept at 10.degree. After the butadiene monoxide had been added, the cooling bath was removed and the temperature of the mixture was allowed to rise slowly to room temperature. To complete the reaction, stirring was continued for a further 1/2 hour at room temperature. The catalyst was then neutralized with sodium methylate solution, the precipitated salt was filtered off and the reaction product was fractionally distilled in vacuo. After the excess ethylene glycol had been distilled off, 94.5 g (71.6 % of theory) of 2- (2-hydroxyethoxy) -j5-buten-1-ol with a boiling point of bp ₀ ° Q1 = 70-72 ° C. were obtained. The ether alcohol obtained was gaschromato-

PO

graphically pure and had the refraction exponent nr = 1.4611.

b) 1,2-bls- (l-hydroxy-2-buten-2-oxy) -ethane

To a mixture of 59 * 1 g (0.5 mol) of the under a) prepared 2- (2-hydroxyethoxy) -3-buten-l-ols and

509809/1183

Henkel Λ CIe GmbH s * t »5 _m ρ.« «· ...»! «* Ο 4723

0.1 g of boron trifluoride etherate (5 mol %) as a catalyst were added dropwise with stirring and cooling with ice 7 * 0 g (0.1 mol) of butadiene monoxide. The rate of addition was regulated in such a way that the temperature of the exothermic mixture was kept at 10.degree. After the butadiene monoxide had been added, the cooling bath was removed and the temperature of the mixture was allowed to rise slowly to room temperature. To complete the reaction, the mixture was stirred for a further 1/2 hour at room temperature. The catalyst was then neutralized with sodium methylate solution, the precipitated salt was filtered off and the reaction product was fractionally distilled in vacuo. After the excess 2- (2-hydroxyethoxy) -3-buten-l-ol had been distilled off in vacuo, 13.2 g (66 $> of the theory) of 1,2-bis (1-hydroxy-j3- buten-2-oxy) -athane with boiling point Sdp- "= 105-110 ° C

Uji mm

obtain. The ether alcohol obtained was pure according to gas chromatography and had the refraction exponent τξ ° = 1.4726.

There is also the possibility of producing the 1,2-bis (l-hydroxy-3-buten-2-oxy) -ethane without a intermediate purification of 2- (2-hydroxyethoxy) -3-buten-l-ol by following the process described under b) to the production under a) after distilling off the excess ethylene glycol, but without distilling the 2- (2-hydroxyethoxy) -3-buten-1-ol, connects.

2) The following example is intended to demonstrate the excellent usefulness of the ethereal

- 6 509809/1183

Henkel Λ CIe GmbH. ut * 6, ", ρ.". Μα · ιι..ΜΜ "ο 4-723

To illustrate alcohols for improving acidic galvanic copper baths. A copper bath was used for the experiments with the following additions:

210 g / l copper sulfate
60 g / l sulfuric acid
0.2 g / l Ν, Ν-diethyl-dithiocarbamldic acid-S-

propyl-w-sulfonic acid sodium 2.0 g / l adduct of 8 mol of ethylene oxide

to 1 mole of decyl alcohol

1.0 g / l jJ-diethylamino - ^ - hydroxy-propyl-diethyl-2,2-dihydroxy-propyl-ammonium chloride

This bath delivers pore-free, uniformly at a temperature of 25 ° C in the current density range of 1 to 8 A / dm high-gloss copper deposits. When operating the bath with an average load of 0.5 A / l The electrolyte starts to become cloudy after about 40 Ah / 1.

For comparison, a copper bath as described above was used, but with an additional 1 g / l 2- (2-Hydroxyethoxy) -2-buten-l-ol were added. That ' The bath delivered pore-free, uniformly at a temperature of 25 ° C in the current density range of 1-8 A / dm high-gloss copper deposits of the same good quality. The first signs of cloudiness appeared in one average load of 0.5 A / l only after about 200 Ah / l. That means the time up to the required Bath filtration can be extended to about five times and that the filter, normally 1-2 times per Exchanged week, now need to be renewed far less often.

- 7 -509809/1183

Henkel & CIe GmbH ut * 7 i »r ret.meni <ni <i» ni d ^ 725 _ ^. . « _O 17 λ

23418/3

If the acidic copper baths are operated with continuous filtration, the addition of 1 g / l 2- (2-hydroxyethoxy) -3-buten-l-ol the normal circulation of 1 to 2 bath volumes per hour to 0.25 to 0.5 bath volume per hour.

In a further comparative experiment, a copper bath as described above was used, in addition to the 1 g / l 1,2-bis (l-hydroxy-3-buten-2-oxy) -ethane were added. The. Quality of the deposited copper precipitates was the same as without addition. This bath showed the first signs of cloudiness in an average bath Load of 0.5 A / l only after about 180 Ah / l. This addition also made the time up to the required Bath filtration significantly extended.

509809/1 183

Claims (6)

Henkel & Cie GmbH s * n · 8 » _r fonmonm.iduni d 4-723 Claims Process for the production of new reaction products from butadiene monoxide and ethylene glycol by action from butadiene monoxide at temperatures of 0 - 40 ° C to excess ethylene glycol in a molar ratio 1: 2 to 1:10, preferably 1: 3 to 1: 6 in the presence of acidic catalysts and further reaction of butadiene monoxide under the same reaction conditions with the 2- (2-hydroxyethoxy) -3-buten-l-ol formed in a molar ratio of 1: 2 to 1:10, preferably 1: 3 to 1: 6. 2) 2- (2-hydroxyethoxy) -3-buten-1-ol. 3) 1,2-bis (1-hydroxy-3-buten-2-oxy) ethane. 4) Use of 2- (2-hydroxyethoxy) -3-buten-l-ol according to claim 1 and 2, as an additive in acidic electroplating copper baths in an amount of 0.1-10 g, preferably 0.5-2 g per Liters of bath liquid. 5) Use of l, 2-bis (l-hydroxy-3-buten-2-oxy) -ethane according to claim 1 and 3 as an additive in acidic galvanic copper baths in an amount of 0.1-10 g, preferably 0.5-2 g per liter of bath liquid. 6) Use of the Xtheralkohole according to claim 1 - 5 in acidic electroplating copper baths containing organic sulfonic acids as brighteners, the sulfonic acid group of which is bonded to a carbon atom surrounded exclusively by heteroatoms via an aliphatic radical and a sulfur atom. 509809/1183