WO2001014300A1

WO2001014300A1 - Process for production of an etheralcohol

Info

Publication number: WO2001014300A1
Application number: PCT/SE2000/001558
Authority: WO
Inventors: Ulf Annby; Nicola Rehnberg
Original assignee: Perstorp Ab
Priority date: 1999-08-20
Filing date: 2000-08-09
Publication date: 2001-03-01
Also published as: SE9902954L; AU6487600A; SE520971C2; SE9902954D0

Abstract

A process for manufacture of an etheralcohol consisting of two monomer units of which at least one is derived from an oxetane of a trimethylol C1-C8 alkane or alkoxylated trimethylol C1-C8 alkane, such as trimethylolpropane, trimethylolethane or alkoxylated, such as ethoxylated and/or propoxylated, trimethylolpropane or trimethylolethane. The process comprises subjecting an oxetane of said trimethylol C1-C8 alkane to a ring opening reaction by addition of at least one alcohol having one, preferably two, or more hydroxyl groups. The reaction is performed at a molar ratio said oxetane to said alcohol of 1:10 to 1:2 and is performed in the presence of a catalytically effective amount of at least one acidic catalyst.

Description

PROCESS FOR PRODUCTION OF AN ETHERALCOHOL

The present invention refers to a process for production of an etheralcohol consisting of two monomer units of which one is derived from a trimethylol Cj-Cs alkane or alkoxylated trimethylol C]-C₈ alkane, such as trimethylolpropane, trimethylolethane and/or alkoxylated trimethylolpropane. The process comprises subjecting in the presence of at least one acidic catalyst at least one oxetane of a trimethylol C Cs alkane and/or alkoxylated trimethylol

Ci-Cs alkane to a ring opening reaction by addition of at least one alcohol having one, preferably two, or more hydroxyl groups.

Oligomeric and polymeric etheralcohols such as dimers, trimers and polymers of for instance glycerol, neopentyl glycol, trimethylolethane, trimethylolpropane and pentaerythritol are commonly used as raw materials and monomers in the production of various resins and compounds used as drying or curing binders, lubricants, toughenerers, reactive diluents, viscosity modifiers etc. within for instance the coating, glue, moulding and chemical industry in general. Said resins and compounds include monomeric, oligomeric and polymeric reaction products such as linear, branched and dendritic esters, polyesters, ethers, polyethers, polyurethanes and the like. Further important applications areas include paper milling, surface treatment of pigments and fillers and of course as raw material or intermediate product in various chemical reactions and syntheses. Oligomeric etheralcohols consisting of two monomer units derived from for instance one or two diols, triols, tetrols or polyols normally exhibit, compared to included monomer or monomers, properties being much different and normally much improved. The demand for said etheralcohols are accordingly high and during the last decades ever increasing, while the supply is limited for reasons set forth below.

Known and commercially available methods of producing etheralcohols consisting of two or more monomer units include recovery of by-products yielded in the syntheses of alcohols, such as 1,3-propanediols having a 2- or 2,2-substitution being for instance alkyl, hydroxyalkyl and/or hydroxyalkoxyalkyl, for instance dimers of neopentyl glycol, trimethylolethane, trimethylolpropane, pentaerythritol, and/or various etherifications of mono, di, tri and polyalcohols alcohols. Di-trimethylolpropane is for instance in general yielded and recovered from the reaction between formaldehyde and M-butyric aldehyde. Dimers and other oligomeric alcohols consisting of two monomer units are also produced in reactions wherein one or two of for instance said 1,3-propanediols or derivatives thereof is/are subjected to direct or indirect etherification, such as disclosed in for instance the International Patent Application WO 92/05134.

Further species of dimeric, oligomeric and polymeric alcohols not contemplated by the present invention are esteralcohols obtained by esterifying alcohols and hydroxyfunctional carboxylic acids. These esteralcohols can be exemplified by the commonly used neopentyl glycol hydroxypivalate.

Presently commercially available methods for manufacture of etheralcohols consisting of two monomer units, of which at least one is derived from a trimethylol Cj-Cs alkane and/or alkoxylated trimethylol Cj-Cs alkane, are subject to a number of drawbacks, such as limited quantities available as said by-products, low yields in for instance etherifications and complex chemical processes and/or recovery, for instance multiple reaction and/or recovery steps.

The present invention quite surprisingly provides a process for manufacture of an etheralcohol consisting of two monomer units of which at least one is derived from a trimethylol Cj-Cs alkane and/or alkoxylated trimethylol Cj-Cs alkane, such as an ethoxylate and/or propoxylate obtained from a reaction between for instance trimethylolpropane or trimethylolethane and ethylene oxide and/or propylene oxide at a molar ratio said trimethylol Cj-Cs alkane to said oxide of 1 : 1 to 1 :50, such as 1 :3 to 1 :20.

The process of the present invention comprises the step of subjecting at least one oxetane of a trimethylol Ci-Cs alkane or alkoxylated trimethylol Cj-Cs alkane, such as an oxetane of trimethylolpropane, trimethylolethane or said ethoxylate and/or propoxylate of trimethylolpropane or trimethylolethane, to a ring opening reaction by addition of at least one alcohol having one, preferably two, or more hydroxyl groups. The ring opening reaction is performed at a molar ratio said oxetane to said alcohol of 1 : 10 to 1 :2, such as 1 :8 to 1 :4, 1 :6 to

1 :3 or 1 :5 to 1 :2, and in the presence of a catalytically effective amount of at least one acidic catalyst.

Said alcohol is in certain preferred embodiments of the process suitably a 2- or 2,2-substituted 1 ,3-propanediol, such as a 2-alkyl, a 2-hydroxyalkyl, a 2-hydroxyalkoxyalkyl, a 2,2-dialkyl, a 2,2-dihydroxyalkyl, a 2,2-dihydroxyalkoxyalkyl, a 2-alkyl-2-hydroxyalkyl or a 2-alkyl-2-hydroxyalkoxyalkyl substituted 1,3-propanediol. Alkoxy is here preferably ethoxy having 2 to 50 carbon atoms, propoxy having 3 to 60 carbon atoms or propoxyethoxy having 5 to 50 carbon atoms and alkyl is preferably alkyl is C_\ - CJS, such as Cj - Cι₂ or Cj - Cs, alkanyl.

Preferred species of said 1,3-propanediols are suitably exemplified by for instance 2-methyl- 1,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl- 1,3-propanediol, trimethylolethane, trimethylolpropane, trimethylolpropane triethoxylate and pentaerythritol. Further prefened embodiments of the process include diols, such as mono, di, tri and polyethylene or propylene glycols, as well as monoalcohols, such as methanol, ethanol and other lower alcohols.

The etheralcohol yielded in the process of the present invention is most preferably di-trimethylolpropane, that is the dimer of trimethylolpropane, whereby said oxetane is an oxetane of trimethylolpropane and said 1,3-propanediol is trimethylolpropane (2-ethyl-2-hydroxymethyl- 1,3-propanediol).

The ring opening reaction of the process of the present invention is preferably performed at a temperature of 25-150°C, such as 50-125°C, using at least one Brønsted acid, such as a sulphuric acid and/or a sulphonic acid, such as methane sulphonic acid and/or ?-toluene sulphonic acid and/or using at least one Lewis acid, such as BF₃, A1C1 and/or SnCl₄, as acidic catalyst. Brønsted acids are most preferably used when said alcohol is selected among di, tri and polyalcohols. Advantageously used acidic catalysts include for instance sulphonates, such as alkanesulphonate and haloalkanesulphonate. Said sulphonates can be exemplified by the group of alkylsilyl fluoroalkanesulphonates, such as trimethylsilyl trifluoromethanesulphonate.

Sulphonates are preferably used when said alcohol is a monoalcohol.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilize the present invention to its fullest extent. The following specific embodiments are, therefore, to be construed as merely illustrative and not limitative of the remainder of the disclosure in any way whatsoever. In the following, Examples 1-9 refer to embodiments of the present invention wherein etheralcohols having two monomer units, of which one is derived from trimethylolpropane oxetane, optionally with smaller amounts of oligomers having three monomer units as by-products are synthesised.

Example 1

2.00 moles of trimethylolpropane oxetane (TMPO) and 5.65 moles of trimethylolpropane (TMP) were charged in a reaction flask and mixed at 90°C. The temperature was then adjusted to 70°C. A catalytic amount (1% by weight) of concentrated sulphuric acid was added. The mixtures were kept at 70°C for 1.5 hour and then analysed by GLC. Products in obtained reaction mixture included 3.82 moles of trimethylolpropane, 0.58 mole of di-trimethylolpropane and 0.07 mole of tri-trimethylolpropane. Example 2

1.13 mole of trimethylolpropane oxetane (TMPO) and 6.34 moles of trimethylolpropane (TMP) were charged in a reaction flask and mixed at 90°C. The temperature was then adjusted to 70°C. A catalytic amount (1% by weight) of concentrated sulphuric acid was added. The mixtures were kept at 70°C for 1.5 hour and then analysed by GLC. Products in obtained reaction mixture included 4.11 moles of trimethylolpropane and 0.34 mole of di -trimethy lolprop ane .

Example 3

0.67 mole of trimethylolpropane oxetane (TMPO) and 6.56 moles of trimethylolpropane (TMP) were charged in a reaction flask and mixed at 90°C. The temperature was then adjusted to 70°C. A catalytic amount (1% by weight) of concentrated sulphuric acid was added. The mixtures were kept at 70°C for 1.5 hour and then analysed by GLC. Products in obtained reaction mixture included 5.45 moles of trimethylolpropane and 0.24 mole of di-trimethylolpropane.

Example 4

1.48 mole of trimethylolpropane oxetane (TMPO) and 6.10 moles of trimethylolpropane (TMP) were charged in a reaction flask and mixed at 90°C. The temperature was then adjusted to 23°C. A catalytic amount (1% by weight) of concentrated sulphuric acid was added. The mixtures were kept at 23°C for 2 hours and then analysed by GLC. Products in obtained reaction mixture included 5.01 moles of trimethylolpropane, 0.44 mole of di-trimethylolpropane and 0.03 mole of tri -trimethylolpropane.

Example 5

609 mmoles of TMP was melted at 90°C. The temperature was then adjusted to 70°C and a catalytic amount (0.7 mole%) of concentrated sulphuric acid was added. 153 mmoles TMPO was added dropwise in two portions with vigorous stirring within the time of one hour. After a total time of 1.5 hour the stirred mixture was allowed to cool and was then subjected to GLC analysis.

Products in obtained reaction mixture included 494 mmoles of trimethylolpropane, 51 mmoles of di-trimethylolpropane and 34 mmoles of tri-trimethylolpropane. Example 6

609 mmoles of TMP was melted at 90°C. The temperature was then adjusted to 70°C and a catalytic amount trimethylsilyl trifluoromethanesulfonate (0.4 mole%,TMSO₃SCF₃) was added. 151 mmole TMPO was added dropwise in two portions with vigorous stirring within the time of one hour. After a total time of 1.5 hour the stirred mixture was allowed to cool and was then subjected to GLC analysis.

Products in obtained reaction mixture included 471 mmoles of trimethylolpropane, 78 mmoles of di-trimethylolpropane and 32 mmoles of tri-trimethylolpropane.

Example 7

34.6 mmoles of neopentylglycol was melted at 135°C. A catalytic amount (0.5 mole%) of trimethylsilyl trifluoromethanesulphonate was then added. 8.6 mmoles of TMPO were added dropwise in two portions with vigourous stirring within the time of one hour. After a total time of 2.5 hours the stined mixture was allowed to cool and was then subjected to GC-MS(CI) analysis.

Products in obtained reaction mixture included (area-%) 79% of neopentylglycol, 14% of neopentylglycol-trimethylolpropane ether and 4.9% of two different trimeric neopentyl glycol/trirhethylolpropane ethers.

Example 8

80 mg of trimethylsilyl trifluoromethylsulfonate was added to 5 ml of methanol. The temperature was raised until gentle reflux and 1.0 g of TMPO was added dropwise in two portions with vigourous stirring within the time of one hour. After a total time of 2 hours, the stined mixture was allowed to cool and was concentrated in vacuo. 1.1 g of methyl-trimethylolpropane ether (1.1 g) was obtained having a purity (GLC) of more than 85%.

Result from NMR analyses: 1H NMR(DMSO-_/(₅): δ(ppm) 4.2 (br, OH, 2Η); 3.22 (s, CH₂OH, 4H); 3.18(s, eO-, 3H);

3.10 (s, CH₂O-, 2H); 1.19 (q, 2H); 0.75 (t, 3H)

¹³C NMR MSO-^): δ(ppm) 73.46; 62.34; 59.46; 44.09; 22.52; 8.27

Example 9

30 mg of trimethylsilyl trifluoromethylsulfonate was added to 2.15 g of monoethylene glycol. The temperature was raised to 70° C and 1.0 g of TMPO was added dropwise in two portions with vigourous stirring within the time of one hour. After a total time of 2 hours, the stirred mixture was allowed to cool and was concentrated in vacuo.

GC-MS(CI) showed that yielded reaction mixture consisted of (area %) 61 % monoethylene glycol, 20-25% monoethylene glycol-trimethylolpropane ether and 8.5 and 3.1 % of two trimeric ethers.

Claims

1. A process for manufacture of an etheralcohol comprising two monomer units of which one is derived from at least one trimethylol Cj-Cs alkane or alkoxylated trimethylol

Cj-Cg alkane ch a racte rised in, that said process comprises the step of subjecting at least one oxetane of a trimethylol Cj-Cs alkane or alkoxylated trimethylol

C Cβ alkane to a ring opening reaction by addition of at least one alcohol having one, preferably two or hydroxyl groups, said reaction being performed at a molar ratio said oxetane to said alcohol of 1:10 to 1:2, such as 1:8 to 1:4, 1:6 to 1:3 or 1:5 to 1:2, and said reaction being performed in the presence of a catalytically effective amount of at least one acidic catalyst.

2. A process according to Claim 1 characterised in, that said trimethylol Cj-Cs alkane is trimethylolpropane or trimethylolethane.

3. A process according to Claim 1 or 2 characterised in, that said alcohol is a 2- or 2,2-substituted 1,3-propanediol.

4. A process according to Claim 3 c h a r a c t e r i s e d i n, that said 2- or 2,2-substituted 1,3-propanediol is a 2-alkyl, a 2-hydroxyalkyl, a 2-hydroxyalkoxyalkyl, a 2,2-dialkyl, a 2,2-dihydroxyalkyl, a 2,2-dihydroxyalkoxyalkyl, a 2-alkyl-2-hydroxyalkyl or a 2-alkyl-2-hydroxyalkoxyalkyl substituted 1,3-propanediol.

5. A process according to Claim 4 characterised in, that alkoxy is ethoxy having 2 to 50 carbon atoms, propoxy having 3 to 60 carbon atoms or propoxyethoxy having 5 to 50 carbon atoms.

6. A process according to Claim 4 or 5 characterised in, that alkyl is Ci - s, such as C] - C]₂ or C] - Cβ, alkanyl.

7. A process according to Claim 3 or 4 ch a racteri s ed i n, that said 2- or 2,2-substituted 1,3-propanediol is 2-methyl-l,3-propanediol, neopentyl glycol, 2-butyl-2-ethyl- 1,3-propanediol, trimethylolethane, trimethylolpropane or pentaerythritol.

8. A process according to Claim 1 or 2 characterised in, that said alkoxylated trimethylol Cj-Cg alkane is an ethoxylate and/or propoxylate obtained from a reaction between trimethylolpropane or trimethylolethane and ethylene oxide and/or propylene oxide at a molar ratio trimethylol Cj-Cs alkane to said oxide of 1:1 to 1:50, preferably 1:3 to 1:20.

9. A process according to Claim 1 or 2 characterised in, that said alcohol is a mono, di, tri or polyethylene or propylene glycol.

10. A process according to any of the Claims 1-9 characterised in, that said ring opening reaction is performed at a temperature of 25-150°C, preferably 50-125°C.

11. A process according to any of the Claims 1-10 characterised in, that said at least one acidic catalyst is at least one Brønsted acid and that said alcohol is a di, tri or polyalcohol.

12. A process according to Claim 11 characterised in, that said at least one Brønsted acid is sulphuric acid or at least one sulphonic acid, such as methane sulphonic acid and/or -toluene sulphonic acid.

13. A process according to any of the Claims 1-12 characterised in, that said at least one acidic catalyst is at least one sulphonate, such as at least one alkanesulphonate and/or haloalkanesulphonate.

14. A process according to Claim 13 characterised in, that said at least one sulphonate is an alkylsilyl fluoroalkanesulphonate, such as trimethylsilyl trifluoromethanesulphonate.

15. A process according to any of the Claims 1-12 characterised in, that said at least one acidic catalyst is at least one Lewis acid.

16. A process according to Claim 15 characterised in, that said at least one Lewis acid is BF₃, A1C1₃ and/or SnCl₄.

17. A process according to Claim 1 characterised in, that said oxetane is an oxetane of trimethylolpropane, that said alcohol is trimethylolpropane and that said etheralcohol is di-trimethylolpropane.