WO2006075954A1

WO2006075954A1 - Water and solvent free process for alkoxylation

Info

Publication number: WO2006075954A1
Application number: PCT/SE2006/000040
Authority: WO
Inventors: Göran BERGWALL
Original assignee: Perstorp, Specialty Chemicals Ab
Priority date: 2005-01-13
Filing date: 2006-01-10
Publication date: 2006-07-20

Abstract

A water and solvent free process for alkoxylation of mixed polyhydric compounds comprising at least two different polyhydric compounds each having at least 3 hydroxyl groups is disclosed. The process comprises that at least one polyhydric compound (I) has a melting point exceeding applied alkoxylation temperature and that at least one polyhydric compound (II) has a melting point below said alkoxylation temperature. Compound (II) is used as solution medium and/or as carrier for said compound (I). Yielded mixed polyhydric alkoxylate has a combined monoalkylene, dialkylene and trialkylene glycol content of less than 0.5% by weight.

Description

WATER AND SOLVENT FREE PROCESS FOR ALKOXYLATION

The present invention refers to a water and solvent free process for alkoxylation of mixed polyhydric compounds of which at least one polyhydric compound has a melting point exceeding applied alkoxylation temperature, hi a further aspect the present invention refers to the use of a mixed polyhydric alkoxylate, obtained in said process, for acrylation.

Alkoxylates are in this context reaction products between polyhydric compounds, such as polyalcohols, and alkylene oxides yielding polyethers with controlled molecular weights and functionalities and having primary and/or secondary hydroxyl groups.

Alkoxylated polyhydric compounds, such as alkoxylated pentaerythritol, di-pentaerythriol, tri-pentaerythritol, trimethylolethane, di-trimethylolethane, trimethylolpropane and di-trimethylolpropane, are versatile chemical intermediates and building blocks. Said alkoxylated polyalcohols are for instance important raw materials in the production of radiation curing acrylic monomers, oligomers and polymers. Alkoxylated polyalcohols are used in increasing amounts since they combine good technical and hygienic properties and provides easy processing due to their liquid state.

Melting points exceeding the temperature range for typical alkoxylation procedures is a well known problem in the production of especially ethoxylates and propoxylates of for instance polyhydric alcohols. Alkoxylation of polyhydric compounds having melting points exceeding the alkoxylation temperature is traditionally carried out with water and/or other polar solvents present in order to allow the reaction to take place in a one phase system. Another approach has been to use inert solvents, such as aromatic or aliphatic solvents, as carriers for the polyhydric material.

The above described approaches have serious disadvantages, such as by-product formation and/or need to remove the inert solvent added. Glycols are formed as by-products when using water to facilitate said alkoxylation. Glycols not only reduce functionality but also in acrylate esters form toxic or skin irritating products and are difficult and costly to remove by for instance vacuum distillation and/or other operations. Alkoxylation by-products, such as mono, di and/or triethylene glycols, are very difficult to remove due to their low volatility, formation of azeotropic mixtures and their strong affinity to the main product. In practice it is very difficult to for instance go below 0.4% by weight of diethylene glycol.

The presence of for instance ethylene glycols in alkoxylated polyhydric alcohols results during production of acrylic monomers in formation of corresponding acrylates, such as mono, di and Methylene glycol mono and diacrylates. These acrylates, especially diethylene glycol diacrylate, have negative effects, such as toxicity, skin irritation and reduced functionality.

US 3,291,845 disclose a process for alkoxylation of high melting polyols, such as polyols having melting points in the range of 200-270°C, by pre-dissolving said high melting polyols in a low melting or normally liquid polyol, such as a glycerol or an ethylene or a propylene glycol. Disclosed process is subjected to a number of limitations. In order to achieve full benefits of the invention, it is necessary that (a) the mixture of the high melting polyol(s) and the normally liquid polyol forms an entirely liquid and clear solution at a temperature of less than 170°C, (b) the alkoxylation is performed at a temperature of less than 170°C, (c) the alkoxylation agent is added gradually and (d) the alkoxylation agent is added in an amount resulting in a polyol alkoxylate being liquid at room temperature. Furthermore, dissolving a high melting polyol in a glycol, such as an ethylene and/or propylene glycol, will result in increased amounts of undesired glycols as discussed in for instance above paragraph.

Formation of the most toxic ethylene glycols can be reduced or avoided by the use of a stepwise process as disclosed in EP 0 537 260 Bl and US 5,543,557 A. The process comprises that propylene oxide first is added to a polyhydric alcohol followed by addition of ethylene oxide. There is, however, still a formation of propylene glycols and mixed ethylene/propylene glycols as well as the disadvantage of a two step process.

Alkoxylation of mixed polyalcohols is disclosed in German patent application 1996 2274 suggesting addition of 0.5% of water in the alkoxylation process. This facilitates the process, but, however, results in formation of much more glycols than the proportion of added water. Should 0.5% by weight of water be added in an ethoxylation wherein for instance one mole of ethylene oxide is added to one mole of trimethylolpropane, the result will be an alkoxylate with about 1.3% of glycol. For example:

^• 1 mole of trimethylopropane (molecular weight 135) + 1 mole of ethylene oxide (molecular weight 44) -» 1 mole of trimethylolpropane ethoxylate (molecular weight 179) and 1 mole of water (molecular weight 18) + 1 mole of ethylene oxide (molecular weight 44) -> 1 mole of ethylene glycol (molecular weight 62).

A further process facilitating alkoxylation of high melting materials is disclosed in US 5,625,045 A, wherein sucrose based ethers for polyurethane foams are prepared by alkoxylation of a sucrose suspended in a pre-produced sucrose alkoxylate and/or a low molecular weight alcohol.

International patent application WO 03/027054 discloses a process for water and/or solvent free alkoxylation of high melting polyhydric compounds. The process comprises that a high melting polyalcohol, such as pentaerythritol, in a first step is coated with a catalytically effective amount of at least one alkoxylation catalyst and then subjected to alkoxylation under effective stirring yielding an alkoxylated alcohol oligomer or polymer being liquid at applied alkoxylation temperature. Said liquid oligomer or polymer is then subjected to further alkoxylation.

The present invention quite unexpectedly provides a new and improved process for alkoxylation of polyhydric compounds having melting points exceeding the temperature range of typical alkoxylation procedures. The process of the present invention refers to a water and solvent free process for alkoxylation of mixed polyhydric compounds of which at least one polyhydric compound has a melting point exceeding the range of applied alkoxylation temperature.

It has been found that combining a high melting polyhydric compound, such as, but not limited to, pentaerythritol and di-pentaerythritol, with a low melting polyhydric compound, such as, but not limited, to trimethylolpropane or di-trimethylolpropane, has enabled production of alkoxylates, such as ethoxylates, propoxylates and/or butoxylates, in a simple one step process without pre-dissolving said high melting polyhydric compound in water, alcohols, glycols and/or inert products and without addition, before or during said alkoxylation, of water, alcohols, glycols and/or inert products to facilitate the alkoxylation reaction. The process of the present invention yields alkoxylates with eliminated or substantially reduced amounts of annoying by-product glycols. A further advantage obtained by the process of the present invention is that the need to remove carrier materials, such as reactive or inert solvents, is avoided. The present invention also gives, compared to prior art processes, an improved combination of properties and simpler and hence less costly production procedures. The process of the present invention yields mixed polyhydric alkoxylates combing favourable technical and hygienic properties without complexing production and/or increasing production costs.

The present invention accordingly refers to a water and solvent free process for alkoxylation of mixed polyhydric compounds comprising at least two different polyhydric compounds each having at least 3 hydroxyl groups, whereby at least one polyhydric compound (I) has a melting point exceeding applied alkoxylation temperature, such as a melting point of at least 130°C or preferably at least 16O⁰C, and at least one polyhydric compound (II) has a melting point below applied alkoxylation temperature, such as a melting point of less than 130°C or preferably less than 110⁰C. Compound (I) and compound (II) is subjected to alkoxylation at a weight ratio compound (I) to compound (II) of between 80:20 and 20:80, such as 75:25, 25:75 or 50:50, by reaction with at least one alkylene oxide. The alkoxylation temperature is at least 110⁰C, such as 130-160⁰C. Compound (H) is in the process of the present invention used as solution medium and/or as carrier for compound (I). The mixed polyhydric alkoxylate, yielded in the present process, has a combined monoalkylene, dialkylene and trialkylene glycol content of less than 0.5% by weight.

Said polyhydric compound (I) is in preferred embodiments of the present invention a 2-alkyl-2-hydroxyalkyl-l,3-propanediol, a 2,2-dihydroxyalkyl-l,3-propanediol and/or a dimer, trimer or polymer of a said 1,3-propanediol having a melting point of at least 160°C. Said polyhydric compound (T) is in its most preferred embodiments trimethylolethane, di-trimethylolethane, pentaerythritol, di-pentaerythritol, tri-pentaerythritol and/or combinations thereof.

Said polyhydric compound (II) is in likewise preferred embodiments of the present invention a 2-alkyl-2-hydroxyalkyl- 1,3-propanediol, a 2,2-dihydroxyalkyl-l,3-propanediol and/or a dimer, trimer or polymer of a said 1,3-propanediol having a melting point of less than 110⁰C, such as less than 100⁰C. Said polyhydric compound (II) is suitably exemplified by trimethylolpropane and di-trimethylolpropane. Further suitable and preferred polyhydric compound are for instance glycerol, di-glycerol and dendritic polyester and/or polyether polyols. Suitable dendritic polyester and/or polyether polyols are disclosed in for instance the International patent applications WO 93/17060, WO 93/18079, WO 96/07688, WO 96/12754, WO 99/00439, WO 99/00440, WO 00/56802 and WO 02/40572, which by reference are herein included.

Said dendritic polyester and/or polyether polyols are most preferably obtained by addition of at least one di, tri or polyhydric monocarboxylic acid to a di, tri or polyhydric core molecule at a molar ratio yielding a polyhydric dendritic polymer comprising a core molecule and at least one branching generation bonded to said di, tri or polyhydric core molecule or are obtained by ring opening addition of at least one oxetane of a di, tri or polyhydric compound to a di, tri or polyhydric core molecule at a molar ratio yielding a polyhydric dendritic polymer comprising a core molecule and at least one branching generation bonded to said di, tri or polyhydric core molecule.

Products unsuitable as polyhydric compound (H) include ethylene glycols, propylene glycols, neopentyl glycol and other aliphatic glycols as well as monofunctional alcohols. These products will reduce functionality and/or lead to formation of potentially hazardous products when further processed, such as subjected to acrylation.

Combinations of two or more polyhydric compounds (T) or (II) as disclosed above are of course possible and in certain cases even favourable from for instance a technical point of view. Said at least one alkylene oxide is preferably ethylene oxide, propylene oxide, butylene oxide, butadiene monoxide, cyclohexene oxide and/or phenylethylene oxide and said allcoxylation is in preferred embodiments of the present invention performed at a molar ratio hydroxyl groups to alkylene oxide of between 1:0.5 and 1:20.

The most preferred embodiments of the process of the present invention comprise pentaerythritol and/or di-pentaerythritol as said polyhydric compound (I), trimethylolpropane and/or di-trimethylolpropane as said polyhydric compound (II) and ethylene oxide and/or propylene oxide as said at least one alkylene oxide.

In a further aspect the present invention refers to the use of a mixed polyhydric alkoxylate, yielded in the process of the present invention, as raw material and/or intermediate product in the production of acrylic acid esters, acrylic oligomers and acrylic polymers, such as polyester acrylates, acrylic modified fumarate esters, urethane acrylates, epoxy acrylates and/or glycidyl acrylates. Acrylic and acrylate are in the following to be interpreted as including compounds wherein the acrylic double bonds are derived from for instance acrylic acid, methacrylic and/or β-methyl acrylic acid (crotonic/isocrotonic acid) and/or from other routes, such as from a halide corresponding to a said acid. Said acrylic monomers, oligomers and polymers are in preferred embodiments accordingly acrylates, mefhacrylates and/or β-methyl acrylates.

Protective and decorative paints and lacquers, inks, glues and other drying and curing compositions based on acrylic, methacrylic and/or β-methyl acrylic (crotonic/isocrotonic) oligomers and polymers meet with an increasing importance within a large number of applications. The increasing importance is substantially due to the utility and unique properties of said products, such as short curing times, excellent film properties, low or no amounts of solvents. Acrylic compositions for said and other applications often comprise a number of various components, such as one or more polyester acrylates, acrylic modified fumarate esters, urethane acrylates, epoxy acrylates and/or glycidyl acrylates and one or more functional monomers, for example esters of di, tri and polyhydric alcohols, preferably alkoxylated polyhydric alcohols, and an acrylic acid. Functional monomers work, besides being monomers, also as viscosity reducing diluents for said oligomers and polymers. The properties of an acrylate, such as film forming, curing, drying and the like, are determined by for instance the molecular weight and molecular structure as well as the chemical and physical structure of said acrylate.

A basic problem in producing low molecular weight raw materials for radiation curing is, due to the nature of the acrylic double bond, the difficulty to combine high reactivity and low viscosity with low toxicity. The present invention shows steps to achieve this in a novel way by alkoxylation giving suitable raw materials for acrylation.

Starting molecules for highly reactive acrylate monomers normally have a hydroxyl functionality of three or more, preferably four or more. The starting molecules are often based on ethoxylates and/or propoxylates of solid polyalcohols, such as trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, di-trimethylolethane, di-trimethylolpropane, di-pentaerythritol and the like. Modification for improvements in one aspect of normally used products typically imparts other properties. Adding for instance more ethylene oxide will reduce viscosity and toxicity but also reduce reactivity, hardness and chemical resistance of the cured film. The mixed polyhydric alkoxylate yielded in the process of the present invention will, however, due to low glycol content and high hydroxyl functionality in the alkoxylate intended for acrylation combine low toxicity with high reactivity and high crosslinking density.

The composition and technology of radiation curable systems and acrylic products are further disclosed in for instance ⁿ Chemistry & Technology of OV and EB Formulations for Coatings, Inks and Paints" - Volume 2: "Prepolymers and Reactive Diluents for UV and EB Curable Formulations" by N.S. Allen, M.S. Johnson, P.K.T. Oldring and S. Salim, 1991 Selective Industrial Training Associates Ltd. London, U.K.

Without further elaboration, it is believed that one skilled in the art can, using the preceding description, utilise the present invention to its fullest extent. The following preferred specific embodiments are, therefore, to be construed as merely illustrative and'not limitative of the remainder of the disclosure in any way whatsoever.

hi the following, Examples 1-10 refer to alkoxylations of mixed polyalcohols in accordance with embodiments of the present invention. Examples 11 and 12 are reference examples showing the high amounts of glycols yielded in prior art alkoxylation processes. Examples 13-15 show the use, according to embodiments of the present invention, of alkoxylates obtained in Examples 1, 2 and 11 (reference) for acrylation. Examples 16 and 17 refer to evaluations of acrylates obtained in Examples 13 and 14. Tables 1-3 give results from said acrylations and said evaluations.

Example 1

250 g of pentaerythritol was in an autoclave dissolved in 250 g of molten trimethylolpropane and 0.56 g of KOH was added. The mix was at a pressure of 4-5 bar heated to 160°C under stirring and inert atmosphere. 500 g of ethylene oxide was during 3 hours added followed by a post reaction for 30 minutes. Obtained product was neutralised with glacial acetic acid to a pH of approx. 6. Stripping or other means for removing volatile compounds such as water and glycols were not used. Obtained product was a clear liquid with a hydroxyl value of 630 mg KOH/g and a viscosity of 1300 mPas at 23°C. GC analyses show a content of ethylene, diethylene and Methylene glycols of less than 0.5% by weight.

Example 2

375 g of pentaerythritol was in an autoclave dissolved in 125 g of molten trimethylolpropane and 0.56 g of KOH was added. The mix was at a pressure of 4-5 bar heated to 160⁰C under stirring and inert atmosphere. 50O g of ethylene oxide was during 3 hours added followed by a post reaction for 30 minutes. Obtained product was neutralised with glacial acetic acid to a pH of approx. 6. Stripping or other means for removing volatile compounds such as water and glycols were not used.

The final product was a clear liquid with a hydroxyl value of 630 mg KOH/g and a viscosity of 1600 mPas at 23°C. GC analyses show a content of ethylene, diethylene and Methylene glycols of less than 0.5% by weight.

Example 3

250 g of pentaerythritol was in an autoclave mixed with 250 g of di-trirnethylolpropane and 0.56 g of KOH was added. The mix was at a pressure of 4-5 bar heated to 16O⁰C under stirring and inert atmosphere. 500 g of ethylene oxide was during 3 hours added followed by a post reaction for 30 minutes. The yielded product was neutralised with glacial acetic acid to a pH of approx. 6.

The final product was a clear liquid with a glycol content of less than 0.5% by weight.

Example 4

165 g of di-pentaerythritol was in an autoclave mixed with 335 g of di-trimethylolpropane and 0.56 g of KOH was added. The mix was at a pressure of 4-5 bar heated to 160⁰C under stirring and inert atmosphere. 500 g of ethylene oxide was during 3 hours added followed by a post reaction for 30 minutes. The yielded product was neutralised with glacial acetic acid to a pH of approx. 6.

The final product was a clear liquid with a glycol content of less than 0.5% by weight. Example 5

250 g of pentaerythritol was in an autoclave dissolved in 250 g of glycerol and 0.56 g of KOH was added. The mix was at a pressure of 4-5 bar heated to 160⁰C under stirring and inert atmosphere. 500 g of ethylene oxide was during 3 hours added followed by a post reaction for 30 minutes. The yielded product was neutralised with glacial acetic acid to a pH of approx. 6.

Example 6

Example 1 was repeated with the difference that 500 g of propylene oxide was added during 5 hours instead of 500 g of ethylene oxide during 3 hours.

The final product was a clear liquid with a viscosity of 2500 mPas at 23°C and a glycol content of less than 0.5% by weight.

Example 7

Example 1 was repeated with the difference that 50O g of propylene oxide was added during 5 hours instead of 500 g of ethylene oxide during 3 hours.

The final product was a clear liquid with a viscosity of 3000 mPas at 23°C and a glycol content of less than 0.5% by weight.

Example 8

Example 3 was repeated with the difference that 500 g of propylene oxide was added during 5 hours instead of 500 g of ethylene oxide during 3 hours.

Example 9

Example 4 was repeated with the difference that 500 g of propylene oxide was added during 5 hours instead of 500 g of ethylene oxide during 3 hours.

The final product was a clear liquid with a glycol content of less than 0.5% by weight Example 10

Example 5 was repeated with the difference that 50O g of propylene oxide was added during 5 hours instead of 500 g of ethylene oxide during 3 hours.

Example 11 (Reference)

136 g of pentaerythritol, xx g powdered KOH and 70 g distilled water were charged in an autoclave. The mixture was heated to 150⁰C under stirring and inert gas. 58 g of propylene oxide was added during 1 hour at said 150⁰C and a pressure of 3-4 bar followed by a post reaction for 30 min. Remaining water was now evaporated at 150⁰C and a vacuum of less than 0.01 bar until a water content of less than 0.2% was reached. 168.2 g of ethylene oxide was subsequently under inert atmosphere charged for 2 hours at 150⁰C and a pressure of 3-4 bar. Post reaction for 30 minutes followed to complete reaction and unreacted eo removed by vacuum. Obtained product was neutralised with glacial acetic acid to apH of approx. 6.

The final product was a clear liquid with viscosity of 1600 mPas had a hydroxyl value of 629 KOH/g and contained by weight according to GC analysis 0.03% monoethylene, 0.05% diethylene, 0.06% triethylene, <0.6% monopropylene, 0.7% diethylene, 0.3% tripropylene glycol and 3.85% mixed ethylene/propylene glycols.

Example 12 (Reference)

Example 11 was repeated with the difference that 57.2 g of ethylene oxide was charged in stead of 58 g of propylene oxide.

The final product was a clear liquid with viscosity of 1100 mPas had a hydroxyl value of 630 mg KOH/g and contained by weight according to GC analysis 0.1% monoethylene, 0.9% diethylene and 2.6% triethylene glycol.

Example 13

The mixed polyhydric alkoxylate obtained in Example 1, acrylic acid and toluene as azeotropic solvent (raw materials : azeotrop 1:1 by weight) was charged in a laboratory autoclave at a molar ratio hydroxyl groups to acrylic acid of 1:1.2. 1400 ppm of 4-methoxyphenol and 140 ppm of nitrobenzene, calculated on said alkoxylate and acrylic acid was added and agitation and heating to 55°C was commenced. 0.9% by weight (calculated on alkoxylate and acrylic acid) of methane sulphonic acid was when a clear solution is obtained charged. Air was allowed to bubble through the reaction mixture and heating to reflux and water separation was commenced and maintained until a minimum of 98% of the theoretical amount of esterification water was collected - temperature range 105-115⁰C. Obtained product was now cooled to room temperature and excess acrylic acid was removed by neutralisation to pH 7 with an aqueous solution of NaOH. Resulting water/salt phase was separated and removed and the organic phase was washed with alkaline (NaOH) water (pH « 11) until the amount of 4-methoxyphenol reached a suitable level. The water phase was between washings allowed to separate and was removed. Remaining toluene was finally vaporised at 40⁰C and < 10 mm Hg. Air was allowed to bubble through the product during the vaporisation.

Properties of obtained product are given in Table 1.

Example 14

Example 13 was repeated with the difference that the mixed polyhydric alkoxylate obtained in Example 2 was charged instead of the alkoxylate obtained in Example 1.

Properties of obtained product are given in Table 1.

Example 15 (Reference)

Example 13 was repeated with the difference that the alkoxylate obtained in Example 11 (Reference) was charged instead of the alkoxylate obtained in Example 1.

Properties of obtained product are given in Table 1.

Example 16

Urethane acrylate compositions were prepared using following formulation in parts by weight:

Urethane acrylate ⁿ 25

Tripropylene glycol diacrylate 25

Acrylate ace. to Examples 13, 14 or 16 50 ϊrgacure^® 500 ^*2 4

*1: CN963B80, Sartomer Europe, France.

*2: Photoinitiator, Ciba Specialty Chemicals, Switzerland. References were prepared using acrylates based on Polyol TP 30^™ (ethoxylated trimethylolpropane nominally having an alkoxylation degree of 3, Perstorp Specialty Chemicals AB, Sweden) and Polyol PP 50S^™ (ethoxylated pentaerythritol nominally having an alkoxylation degree of 5, Perstorp Specialty Chemicals AB, Sweden). The Polyol TP 30^™ and Polyol PP 5 OS^™ acrylates were produced in accordance with Example 13.

Curing results are given in Table 2 showing that acrylates according to embodiments of the present invention suitably can substitute traditionally used acrylated alkoxylates.

Example 17

Polyester acrylate compositions were prepared using following formulation in parts by weight:

Polyester acrylate ^*1 25

Tripropylene glycol diacrylate 25

Acrylate ace. to Examples 13, 14 or 16 50

Irgacure^® 500 ^*2 4

*1: EB851, Surface Specialties (UCB), Belgium.

*2: Photoinitiator, Ciba Specialty Chemicals, Switzerland.

References were prepared using acrylates based on Polyol TP 30^™ (ethoxylated trimethylolpropane nominally having an alkoxylation degree of 3, Perstorp Specialty Chemicals AB, Sweden) and Polyol PP 50S^™ (ethoxylated pentaerythritol nominally having an alkoxylation degree of 5, Perstorp Specialty Chemicals AB, Sweden). The Polyol TP 30^™ and Polyol PP 50S^™ acrylates were produced in accordance with Example 13.

Curing results are given in Table 3 showing that acrylates according to embodiments of the present invention suitably can substitute traditionally used acrylated alkoxylates.

Table 1

Table 2

*1 : Tack free, 80W/cm, UV dose 440 mJ/cm²

*2: 40 μm film on glass panels, 4 passes at 10 m/min, 80W/cm, UV dose 600 mJ/cm²

*3: 30 μm film on aluminium panels, 4 passes at 10 m/min, 80W/cm, UV dose 600 mJ/cm²

Table 3

*1: Tack free, 80W/cm, UV dose 250 mJ/cm²

*2: 40 μm film on glass panels, 4 pass at 10 m/min, 80 W/cm, UV dose 600 mJ/cm².

*3: 30 μm film on aluminium panels, 4 pass at 10 m/min, 80 W/cm, UV dose 600 mJ/cm².

Claims

1. A water and solvent free process for alkoxylation of mixed polyhydric compounds comprising at least two different polyhydric compounds each having at least 3 hydroxyl groups characterised in, that at least one polyhydric compound (I) has a melting point exceeding applied alkoxylation temperature, such as at least 130⁰C, preferably at least 160⁰C, that at least one polyhydric compound (H) has a melting point of less than 13O⁰C, preferably less than 110⁰C, that said compound (H) is used as solution medium and/or as carrier for said compound (I), that said compound (I) and said compound (H) in a weight ratio of between 80:20 and 20:80 is subjected to alkoxylation at a temperature of at least 110⁰C, such as 130-160⁰C, by reaction with at least one alkylene oxide, and that yielded mixed polyhydric alkoxylate has a combined monoalkylene, dialkylene and trialkylene glycol content of less than 0.5% by weight.

2. A process according to Claim 1 ch ar ac t eri s e d in, that said polyhydric compound (I) is a 2-alkyl-2-hydroxyalkyl-l,3-propanediol, a 2,2-dihydroxyalkyl- -1,3 -propanediol and/or a dimer, trimer or polymer of a said 1,3 -propanediol and that said polyhydric compound (I) has a melting point of at least 16O⁰C.

3. A process according to Claim I or2 characterised in, that said polyhydric compound (T) is trimethylolethane, di-trimethylolethane, pentaerythritol, di-pentaerythritol or tri-pentaerythritol.

4. A process according to any of the Claims 1-3 characteri sed in, that said polyhydric compound (II) is a 2-alkyl-2-hydroxyalkyl-l,3-propanediol, a 2,2-dihydroxyalkyl-l,3-propanediol and/or a dimer, trimer or polymer of a said 1,3 -propanediol and that said polyhydric compound (TT) has a melting point of less than 100⁰C.

5. A process according to any of the Claims 1-4 characteris ed in, that said polyhydric compound (II) is glycerol, trimethylolpropane or di-trimethylolpropane.

6. A process according to any of the Claims 1-4 characteri s ed in, that said polyhydric compound (H) is a dendritic polyester and/or polyether polyol.

7. A process according to any of the Claims 1-6 characteri s ed in, that said alkylene oxide is ethylene oxide, propylene oxide, butylene oxide, butadiene monoxide, cyclohexene oxide and/or phenylethylene oxide.

8. A process according to any of the Claims 1-7 c h a r a c t e r i s e d i n, that said alkoxylation is performed at a molar ratio hydroxyl groups to alkylene oxide of between 1:0.5 and 1:20.

9. A process according to any of the Claims 1-8 c h a r a c t e r i s e d i n, that said polyhydric compound (I) is pentaerythritol or di-pentaerythritol, that said polyhydric compound (H) is trimethylolpropane or di-trimethylolpropane and that said alkylene oxide is ethylene oxide and/or propylene oxide.

10. A process according to Claim 9 c h a r a c t e r i s e d i n, that said polyhydric compound (I) and said polyhydric compound (H) is alkoxylated at a weight ratio of between 75:25 and 25:75, such as 50:50.

11. Use of a mixed polyhydric alkoxylate according to any of the Claims 1-10 as raw material and/or intermediate product in production of a monomer, oligomer or polymer having at least one acrylic double bond.

12. Use according to Claims 11, wherein said monomer, oligomer or polymer is an acrylic, a methacrylic and/or a β-methyl acrylic monomer, oligomer or polymer.

13. Use according to Claim 11 or 12, wherein said monomer, oligomer or polymer is an acrylic, methacrylic and/or β-methyl acrylic acid ester; a polyester acrylate, methacrylate and/or β-methyl acrylate; an acrylic, methacrylic and/or β-methyl acrylic modified furαarate ester; a urethane acrylate, methacrylate and/or β-methyl acrylate, an epoxy acrylate, methacrylate and/or β-methyl acrylate; and/or a glycidyl acrylate, methacrylate and/or β-methyl acrylate.

14. Use according to any of the Claims 11-13, wherein said monomer, oligomer or polymer is included in a radiation curing composition.

15. Use according to Claim 14, wherein said radiation curing composition is a protective and/or decorative paint or lacquers, an ink or a glue.

16. Use according to Claim 14 or 15, wherein said radiation curing composition is a UV curing composition.