WO1989000565A1

WO1989000565A1 - Cyclocarbonate compounds

Info

Publication number: WO1989000565A1
Application number: PCT/DE1988/000451
Authority: WO
Inventors: Gerwald Grahe; Artur Lachowicz
Original assignee: Dainippon Ink & Chemicals, Inc.; Dic Berlin Gmbh & Co.
Priority date: 1987-07-16
Filing date: 1988-07-15
Publication date: 1989-01-26
Also published as: EP0390777A1; DE3723782A1; JPH10251405A; JP2854298B2; DE3723782C2; JP2831671B2; JP3072075B2; JPH10265470A; JPH03501121A

Abstract

Cyclocarbonate compounds, process for manufacturing them by conversion of halogen hydrins with an alkali metal bicarbonate in the presence of a polar aprotic organic solvent, and their use in the manufacture of the corresponding urethanes.

Description

Cyclocarbonate compounds

The invention relates to cyclocarbonate compounds, processes for their preparation by reacting alkali metal hydrogen carbonates with vicinal halohydrins and their use for the preparation of the corresponding urethanes.

Cyclocarbonate compounds play an important role in many areas of the chemical industry both as solvents and as versatile intermediates. Numerous methods for the production of cyclocarbonates have been described ("Houben-Weyl" Methods of Organic Chemistry, Volume E 4, Georg Thieme Verlag, 1983). Probably the oldest method is based on the action of phosgene on glycols. A related process involves the reaction of glycols with chloroformic acid esters. The simplest laboratory process for the production of cyclocarbonate compounds is the transesterification of simple open-chain carbonic acid esters (advantageously diethyl carbonate) with glycols. An elegant process for the synthesis of cyclocarbonates is based on the reaction of corresponding epoxy derivatives with carbon dioxide, which is, however, carried out under increased pressure. Vicinal halohydrins have also been used to synthesize cyclocarbonates. For example, ethylene or propylene chlorohydrin could be reacted with bicarbonates of the alkali metals at elevated temperature, cyclic carbonic diesters being obtained (DE-PS 516 281). Only the simplest cyclocarbonates can be produced by this process. The Yields of ethylene carbonate were good, but that of propylene carbonate was poor, which underlines the importance of the substitution of the chlorohydrins used as starting compounds. The known method is unsuitable for cyclocarbonates with a total of more than 4 carbon atoms.

Ethylene carbonate could be obtained in low yields by reacting ethylene chlorohydrin with sodium methyl carbonate (US Pat. No. 2,784,201).

Simple alkylene carbonates are formed in the reaction of halohydrins with alkali metal carbonates in the presence of halogenated hydrocarbons as a diluent (US Pat. No. 2,766,258). Similar to the earlier method (DE-PS 516 281), this procedure can only be used for the production of ethylene and less advantageously propylene carbonate.

Vicinal halohydrins react under pressure with carbon dioxide to form cyclic carbonates (US Pat. No. 3,923,842). Vicinale can be used under mild conditions

Halohydrins in cyclic carbonates in acetonitrile as

Transfer solvent. Bicarbonate salts of quaternary ammonium compounds (EP

4 942). This procedure is only for the production of

Suitable cyclocarbonate compounds containing 2 to 4 carbon atoms in the chain.

All known processes for the preparation of cyclocarbonates from halohydrins and alkali metal carbonates restrict themselves to connections of the type

where R ^{4 represents} either a hydrogen atom or a methyl group. These compounds therefore contain no functional groups other than the cyclocarbonate function.

For the preparation of cyclocarbonate compounds with other sensitive functional groups, such as. B. the ester or. Ether group or a polymerizable double bond, these methods are unsuitable because in these cases problems arise that cannot be solved with the known methods: - The solubility of the carbonates or the bicarbonates of the alkali metals in the halohydrins is only sufficient for the reaction in the case of the simplest compounds, especially in ethylene chlorohydrin, less so in propylene chlorohydrin, - substitution of the halohydrins leads to an inevitable steric hindrance which significantly slows down or completely prevents the cyclization reaction. This decrease in reactivity is already very clear during the transition from ethylene to propylene chlorohydrin. Another substitution makes an additional one inhibit the cyclization reaction,

- The intrinsic reactivity of the functional groups which may be present is often so high that the cyclization of the substituted halohydrins with alkali metal carbonates to cyclocarbonates may only take place under very gentle conditions, since otherwise troublesome side reactions come to the fore, e.g. B. alkaline hydrolysis, saponification, polymerization, etc.

The object of the invention is to develop a process for the preparation of functionally substituted cyclocarbonate compounds from functional groups having halohydrins and alkali metal carbonates, in which the disadvantages of the known processes do not occur and which can also be used for the preparation of polymeric cyclocarbonate compounds.

The characterizing parts of claims 1, 2 and 3 contain the solution to the problem.

The present invention relates to a process for the preparation of cyclocarbonate compounds of the general formula

from vicinal halohydrins and alkali metal bicarbonates and the preparation of polymeric cyclocarbonate compounds.

R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an optionally substituted aliphatic, cycloaliphatic, aromatic or arylaliphatic hydrocarbon radical having 1 to 12 carbon atoms or the radicals are components of a 5- or 6-membered ring, where R ¹ , R ² , R ³ and R ⁴ can be identical or different from one another and at least one of the radicals R ¹ , R ² , R ³ and R ^{4 has} at least one functional group with at least one heteroatom from the IV to VII group of the Periodic Table of the Elements and / or carries at least one unsaturated C = C or / and C≡C function.

Starting materials for the process according to the invention are vicinal halohydrins of the type

(3)

where R ¹ , R ² , R ³ and R ^{4 have} the meaning already mentioned and X represents a halogen atom from the group Cl, Br, J, with an alkali metal bicarbonate MHCO3 (M = Na or K) in the presence of a polar aprotic solvent at temperatures between 50 ° C to 160 ° C, preferably between 80 ° C and 100 ° C according to the reaction equation (4):

Products which are obtained by the reaction of optionally substituted epihalohydrins (especially epichlorohydrin) with numerous H-active compounds according to the general reaction equation (5) are particularly favorable starting materials for the process according to the invention described here.

Reaction equation (5):

wobe i Z = z. B. R 'COO -

R 'O - R' S - R ' ₂ N - HO - CL - etc.

The substances used as starting compounds in the process according to the invention have one more than one occurring vicinal halohydrin structure, such as that in the reaction of epihalohydrin with corresponding polyfunctional compounds according to Eq. (6) emerging products is the case,

t

where Z (H) n = z. B. HIGH ₂ CH ₂ OH

HOOCCH ₂ COOH

HOOCCH = CHCOOH

R-NH ₂

H ₂ O, NH _3, etc., n> 1

for example, polyfunctional cyclocarbonates can also be prepared by the process according to the invention described here, which is illustrated by reaction equation (7):

where n≥2 and R ¹ , R ² , R ³ and R ^{4 have} the meaning already mentioned and R ¹ is additionally a bi- or polyfunctional, optionally substituted radical.

Alkali metal bicarbonates serve as cyclization partners for the halohydrins in the process according to the invention, it being possible advantageously to use both sodium and potassium carbonate.

Because of the poor solubility of the alkali metal bicarbonates in the substituted halohydrins, the process according to the invention is carried out in the presence of a solvent. Polar, aprotic solvents such as dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfone, N-methylformamide, N-methyl-2-pyrrolidinone, N, N-diethylformamide, trimethylurea, trimethylphosphate, 1,3-dimethylimidazolidion-2-one, acetonitrile are suitable. Dimethyl sulfoxide or nitromethane, with dimethyl sulfoxide being particularly effective.

In view of the prior art cited above, it must be described as extremely surprising that the process according to the invention allows the production of functionally substituted cyclocarbonates under mild conditions and in high yields. It should be particularly emphasized that, in contrast to the known processes, the process according to the invention is applied to a large number of very differently structured halohydrins that can. This is particularly surprising because according to the previously described processes for the preparation of cyclocarbonates (DE-PS 516 281, US-PS 2 766 258 and EP 4 942), high yields of cyclocarbonates can only be obtained if you use short-chain halohydrins without further uses functional groups as starting compounds, especially ethylene halohydrins, but also, with restrictions, propylene or butylene halohydrins.

The possibility of also being able to produce functionally substituted cyclocarbonates or polymeric cyclocarbonates in the process according to the invention therefore means a considerable advantage over the previously known processes of the prior art.

The invention thus also includes processes for the preparation of polymeric cyclocarbonate compounds per

Macromolecule contain at least one cyclocarbonate group,

characterized in that

a polymer which has at least one vicinal halohydrin of the general formula

or the general formula

where R ² , R ³ and R k ⁴ each represent a hydrogen atom or an optionally substituted aliphatic, cycloaliphatic, aromatic or arylaliphatic hydrocarbon radical having 1 to 12 carbon atoms or the radicals R ² and R ³ or R ^{4 are} components of a 5- or 6- membered carbocyclic ring, wherein R ² , R ³ and

R ⁴ can be identical or different from one another and optionally one of the radicals R ² , R ³ and R ⁴ , optionally a heteroatom from the IV to VII group of the Periodic Table of the Elements and / or at least one unsaturated C = C or / and C≡ C function and X is a halogen, is reacted with an alkali metal bicarbonate in the presence of an aprotic organic solvent at temperatures between 50 ° - 160 ° C.

All polymeric groups which can be prepared by polymerization, polyaddition and polycondensation reactions are suitable as the remaining polymer.

Of particular note are the polymeric hydrocarbons (such as polyethylene, polystyrenes), the polymeric hydrogen halides (such as Teflone, polyvinylchloride), the polyacrylates, the polymethacrylates, the polyesters, the polyimides, the polyamides, the phenoplasts, the aminoplastics, the polyurethanes, the polysilicones and the polymers of epoxides. The polymeric compounds mentioned can have been prepared either by homo- or by copolymerization.

A particularly interesting field is the use of the cyclocarbonates obtained by the process according to the invention for the production of urethanes. The corresponding reaction with primary or secondary amines proceeds according to equation (8).

(8th)

If polyfunctional cyclocarbonates are reacted with polyfunctional amines in reaction (8), polyurethanes can be obtained which are usually prepared from the highly toxic isocyanates. When using dicyclocarbonates and diamines, linear polyurethanes are then obtained according to equation (9).

+ n · H ₂ N - R'- NH ₂ →

(9)

The use of highly functional substances results in branched or cross-linked polyurethanes. Of particular interest in this connection is the production by the process according to the invention of cyclocarbonates which have at least one polymerizable function. For example:

a) Derivatives of unsaturated monocarboxylic acids, such as (optionally, substituted) acrylic acid, e.g. B.

b) Mono- or polycyclocarbonate derivatives of unsaturated, polybasic carboxylic acids such as maleic acid, fumaric acid, itaconic acid etc., such as. B. o ^;

c) derivatives of the mono- or polyfunctional unsaturated alcohols, such as allyl alcohol, 1,4-butene-2-diol etc., e.g. B.

Z.

d) Cyclocarbonate-functional ethylene derivatives, e.g. B.

Such substances can be converted into polymers with unchanged cyclocarbonate functions by polymerization, which is shown using the example of the cyclocarbonate glyceryl ester of methacrylic acid in equation (10).

Such linear polymers are soluble in organic solvents. By reacting with diamines or polyamines, they can change into a network structure. This process is illustrated by formula scheme (11).

This creates three-dimensional networks that have polyurethane bridges. Such systems, which are usually obtained by reacting hydroxyl-containing polymers with isocyanates, play an extremely important role in the coating sector.

With the use of the polymerizable cyclocarbonates produced by the process according to the invention, polyurethane structures can be produced according to formula (10) and (11) without the use of isocyanates. For this purpose you can use both homopolymers of each

Cyclocarbonate monomers (e.g. CH ₂ =

0

and also use their copolymers with one another or in combination with one or more customary vinyl or acrylic monomers or comparable compounds (for example maleic acid or ester).

After mixing with di- or polyamines, the polymers with cyclocarbonate functions result in mixtures which can be cured to give clear or pigmented, glossy, hard and solvent-resistant films which have all the advantages of a conventional polyurethane coating.

The following examples are intended to explain the process according to the invention in more detail.

Example 1:

A mixture of 53 g of 4-chloro-3-hydroxybutene-1, 100 g of dimethyl sulfoxide and 60 g of sodium hydrogen carbonate is stirred at 80-85 ° C. for 6 hours. After cooling to room temperature, the mixture is filtered, concentrated in vacuo, filtered again and the crude product obtained as a filtrate is distilled in vacuo.

The 4-vinyl-1,3-dioxolan-2-one changes as a colorless liquid at 70 - 72 ° C (1 mbar).

Yield: 36 g (approx. 63% of the theoretical amount)

Example 2:

A mixture of 26 g of 4-chloro-3-hydroxybutin-1, 50 g of dimethyl sulfoxide, 40 g of sodium hydrogen carbonate and 0.3 g of methyltrioctylammonium chloride is reacted and worked up analogously to the information in Example 1.

The 4-ethynyl-1,3-dioxolan-2-one distills as a light yellow liquid at 60 - 62 ° C (0.01 mbar). Example 3:

A mixture of 25 g of 2-chloroaclohexanol, 30 g of sodium bicarbonate, 50 dimethyl sulfoxide and 0.5 g of trioctyl methyl ammonium chloride is made analogously to the information in Example

1 reacted and worked up.

The 1,2-cyclohexylene carbonate boils at 151 - 153 ° C (0.001 mbar) and solidifies very easily to the light brown mass.

Yield: 8.5 g (approx. 32% of theory)

Example 4:

A mixture of 12 g of 3- (2-methoxyphenyl) -2-hydroxypropyl chloride-1, 30 g of dimethyl sulfoxide, 20 g of sodium hydrogen carbonate and 0.3 g of tetraethylammonium chloride is reacted and worked up analogously to the information in Example 1.

The 4- (2-methoxybenzyl) -1,3-dioxolan-2-one boils at 163-165 ° C (0.001 mbar) and solidifies slightly.

Yield: 7.3 g (approx. 58.5% of theory)

Example 5:

A mixture of 40 g of 2-chloro-1- (4-chlorophenyl) ethanol, 100 g of dimethyl sulfoxide, 40 g of sodium hydrogen carbonate and 0.5 g of trioctylmethylammonium chloride is reacted and worked up analogously to the instructions in Example 1. The 4- (4-chlorophenyl) -1,3-dioxolan-2-one distills at 156 - 158 ° C (0.001 mbar) as a light yellow, slightly solidifying liquid.

Yield: 22.5 g (approx. 54% of theory)

Example 6:

A mixture of 500 g of 3-chloro-1,2-propanediol, 450 g

Dimethyl sulfoxide, 1 ml trioctylmethylammonium chloride and

567 g of sodium bicarbonate is at 80 for six hours

85 ° C. After cooling to room temperature, the solid constituents are filtered off and the filtrate in vacuo

(approx. 1 mbar) heated to 100 ° C until no more distillate passes over. The non-distillable residue is filtered again. The filtrate, a light yellow, fairly viscous liquid, contains practically only hydroxymethyl-1,3-dioxolan-2-one.

Yield: 502 g (approx. 94% of theory)

Determination of the hydroxyl number of the reaction product: 481 mg KOH / g (theoretical: 475 mg KOH / g)

Example: 7

A mixture of 62 g of 3-methoxy-2-hydroxypropyl chloride-1, 100 g of dimethyl sulfoxide and 50 g of sodium hydrogen carbonate is reacted and worked up analogously to the information in Example 1.

The 4-methoxymethyl-1,3-dioxolan-2-one distills at 92 - 94 ° C (1 mbar) as a low-viscosity ₎ colorless liquid.

Yield: 61.5 g (approx. 93.5% of theory)

Example 8:

A mixture of 105 g of 3-allyloxy-2-hydroxypropyl chloride-1, 70 g of sodium hydrogen carbonate and 150 g of dimethyl sulfoxide is reacted and worked up analogously to the information in Example 1.

The 4-allyloxymethyl-1,3-dioxolan-2-one boils at 105 107 ° C (Imbar) as an easily movable, colorless liquid.

Yield: 92.5 g (approx. 84% of theory)

Example 9:

A mixture of 47 g of 3-phenoxy-2-hydroxypropyl chloride-1, 30 g of sodium hydrogen carbonate and 100 g of dimethyl sulfoxide is reacted and worked up analogously to the information in Example 1.

The 4-phenoxymethyl-1,3-dioxolan-2-one boils at 157-160 ° C (0.001 mbar).

Yield: 30.4 g (approx. 62% of theory)

Example 10:

A mixture of 50 g of 1,10-dichloro-2,9-dihydroxy-4,7-dioxadecane, 70 g of sodium hydrogen carbonate, 100 g of dimethyl sulfoxide and 0.6 g of trioctylmethylammonium chloride is reacted and worked up analogously to the information in Example 1.

The ethylene glycol bis (1,3-dioxolan-2-one-4-ylmethyl) ether boils at 190-195 ° C (0.001 mbar) with partial decomposition.

Yield: 13.5 g (approx. 25.5% of theory

Example 11:

A mixture of 172 g of 3-chloro-2-hydroxypropyl acetate, 344 g

Methyl sulfoxide and 172 sodium hydrogen carbonate are reacted and worked up analogously to the information in Example 1.

The 4-acetyloxymethyl-1,3-dioxolan-2-one boils at 118-120 ° C (0.1 mbar) as a colorless liquid.

Yield: 161 g (approx. 89% of theory) Example 12:

A mixture of 95 g of 3-chloro-2-hydroxypropyl isobutyrate, 65 g of sodium hydrogen carbonate and 150 g of dimethyl sulfoxide is reacted and worked up analogously to the information in Example 1.

The 4-isobutyroxymethyl-1,3-dioxolan-2-one distilled over at 151-152 ° C (0.1 mbar) as a colorless liquid.

Yield: 87 g (approx. 88% of theory)

Example 13:

A mixture of 890 g of 3-chloro-2-hydroxypropyl methacrylate, 1200 g of dimethyl sulfoxide, 672 g of sodium hydrogen carbonate and 10 g of phenothiazine is reacted and worked up analogously to the information in Example 1.

The 4-methacryloyloxy-1,3-dioxolan-2-one distilled at 132-135 ° C (0.001 mbar) as a colorless liquid.

Yield: 804 g (approx. 87% of theory)

Example 14:

A mixture of 500 g of 3-chloro-2-hydroxypropyl crotonate, 700 g Dimethyl sulfoxide, 323 g of sodium hydrogen carbonate and 3 g of phenothiazine are reacted and worked up analogously to the information in Example 1.

The 4-crotonoyloxymethyl-1,3-dioxolan-2-one boils at 118 - 120 ° C (0.001 mbar) as a colorless liquid.

Yield: 433 g (approx. 83% of theory)

Example 15:

A mixture of 42 g of N- (3-chloro-2-hydroxypropyl) diethylamine, 60 g of dimethyl sulfoxide and 50 g of sodium hydrogen carbonate is reacted and worked up analogously to the information in Example 1.

The 4- (N, N-diethylamino) methyl-1,3-dioxolan-2-one distills as a light yellow liquid at 112 - 115 ° C (0.001 mbar).

Yield: 28.5 g (approx. 65% of theory)

Example 16:

A mixture of 45 g of 1-chloro-2-hydroxy-4-thiaoctane, 60 g of dimethyl sulfoxide and 50 g of sodium hydrogen carbonate is reacted and worked up analogously to the information in Example 1. The (1,3-dioxolan-2-one-4-yl -) - methylbutyl sulfide boils at 118 - 121 ° C (0.001 mbar).

Yield: 32 g (approx. 68% of theory)

Example 17:

A mixture of 51 g of 3-bromo-2-hydroxypropyl acetate, 50 g of sodium hydrogen carbonate, 100 g of dimethyl sulfoxide and 0.6 g of trioctylmethylammonium chloride is reacted and worked up analogously to the information in Example 1.

The 4-acetyloxymethyI-1,3-dioxolan-2-one distills at 114-115 ° C (0.1 mbar) as a colorless liquid.

Yield: 36 g (approx. 87.2% of theory)

Example 18:

A mixture of 35 g of 1-chloro-2-methyl-2-hydroxy-3-methoxypropane, 30 sodium hydrogen carbonate and 50 g of dimethyl sulfoxide is reacted and worked up analogously to the information in Example 1.

The 4-methyl-4-methoxymethyl-1,3-dioxolan-2-one distills at 102-104 ° C (1 mbar) as a colorless liquid.

Yield: 29 g (approx. 78% of theory) Example 19:

A solution of 70 g of 3-chloro-2-hydroxypropyl methacrylate, 70 g of butyl acrylate, 17.5 g of methyl methacrylate, 17.5 g of styrene and 5 g of azo-bis-isobutyronitrile is added dropwise to 155 g of dimethylformamide over the course of two hours, which is heated to 130 ° C. The heating or cooling of the reaction vessel is adjusted so that the polymerization is carried out at 130-135 ° C. The mixture is then left to react for one hour at 135-140 ° C, a solution of 1 g of azo-bis-isobutyronitrile and 15 g of dimethylformamide is added dropwise at this temperature over the course of 15 minutes, and the mixture is left to react for a further hour at 140-145 ° C.

The colorless, clear polymer solution is then cooled to about 80-90 ° C., 130 g of dimethylformamide, 60 g of sodium hydrogen carbonate and 1 g of trioctylmethylammonium chloride are added and the mixture is kept at 85-90 ° C. with stirring for 6 hours. The mixture is then cooled to room temperature, undissolved constituents are filtered off and the clear solution is freed of dimethylformamide in vacuo.

The remaining acrylic resin, still liquid at 80 ° C, is diluted with 75 g of xylene and filtered again after cooling.

The resulting cyclocarbonate-containing solution is weak in monetary terms, has a solids content of approx. 70% and contains practically no chlorine and no hydroxyl groups (OH number: 2-3 mg kOH / g).

After mixing the filtrate with stoichiometric amounts of a di- or polyamide such as hexamethylene diamine, 4,9-dioxadodecane-1,12-diamine, isophorone diamine, polyoxypropylene triamine (e.g. Jeffamine, T-403 from Texaco Chemical Company) etc., paint solutions are formed, that produce hard, shiny, clear, lightfast and solvent-resistant polyurethane coatings both at room temperature and under baking conditions.

Example 20:

An acrylic polymer is prepared from 70 g of 3-chloro-2-hydroxypropyl methacrylate, 70 g of butyl acrylate, 40 g of styrene and 5 g of tert-butyl perbenzoate analogously to the information in Example 19 and then converted into a chlorine- and hydroxyl-free, cyclocarbonate-containing polymer.

The properties of the acrylic resin obtained and its behavior when crosslinking with diamines or polyamines are analogous to those described in Example 19.

Examples 21-29:

A mixture of 65 g of 1,3-dichloro-2-propanol, 100 g of a solvent, 70 g of sodium hydrogen carbonate and optionally 0.5 g of a catalyst is heated to 50-120 ° C. with stirring for two to six hours. The reaction mixture is then filtered, in Vacuum removed the solvent and the crude reaction product was distilled in a short column in vacuo.

The 4-chloromethyl-1,3-dioxolan-2-one is colorless and clear at 102-105 ° C (1 mbar).

Table 1 contains detailed information on Examples 21 to 29.

1) Yield of distilled 4-chloromethyl-1,3-dioxolan-2- o ⁿ

2) Trioctylmethylammonium chloride

3) Crown ether Dibenzo-18-crown-6 Example 30:

A mixture of 65 g of 1,3-dichloro-2-propanol, 100 g of dimethyl sulfoxide and 80 potassium hydrogen carbonate is reacted and worked up analogously to the information in Example 1.

The 4-chloromethyl-1,3-dioxolan-2-one distilled at 101 103 ° C (1 mbar).

Example 31:

A mixture of 90 g of 3-chloro-2-hydroxypropyl isobutyrate, 200 g of dimethyl sulfoxide, 35 g of cyclohexane, 67 g of sodium hydrogen carbonate and 1 g of trioctylmethylammonium chloride is heated to boiling under reflux and the water formed is removed continuously via a water separator.

After about 9 g of water have been formed, the mixture is cooled and worked up analogously to the information in Example 1.

The 4-isobutylroxymethyl-1,3-dioxolan-2-one is isolated as a colorless liquid distilling at 138-140 ° C (0.01 mbar).

Yield: 893 g (approx. 89% of theory) Examples 32-43:

A mixture of 39.0 g of pivalic acid 3-chloro-2-hydroxy-1-propyl ester, 80 g of a solvent and 25 g of sodium hydrogen carbonate is added for three to ten hours

Stirring heated to 90-110 ° C. The mixture is then filtered and the majority of the solvent is distilled off in vacuo (approx. 10 ^-3 mbar).

The distillation residue is taken up in 200 g of toluene. The mixture is then filtered and the filtrate washed twice with 20 ml of water. The organic phase is concentrated in a water jet pump vacuum and the remaining crude product is distilled in vacuo over a short column.

The 4-pivaloyloxymethyl-1,3-dioxolan-2-one is colorless and clear at 108-110 ° C / 0.001 mbar.

Detailed information on the examples - see table 2.

Example 44:

A mixture of 33 g of 3-phenoxy-2-hydroxypropyl fluoride-1 (prepared according to D. LANDINI et al., Synthesis 1974, 428 from the corresponding chlorine compound), 30 g of sodium hydrogen carbonate and 80 g of dimethyl sulfoxide is 4 hours at 100 - 105 ° C stirred.

The mixture is then filtered hot, the solvent is distilled off in vacuo at bath temperature by 110-120 ° C and the remaining, slightly solidifying crude product is recrystallized from boiling xylene.

The 4-phenoxymethyl-1,3-dioxolan-2-one is obtained in the form of colorless crystals; Mp: 98.5-100 ° C.

Yield. 22.9 g (approx. 59 times theory)

Example 45:

A mixture of 56 g of 3-phenoxy-2-hydroxypropyl iodide-1 (prepared according to HOUBEN-WEYL, Volume V / 4, p. 597 (1969) from the corresponding chlorine compound), 30 g of sodium hydrogen carbonate and 100 g of dimethyl sulfoxide is used for 4 hours stirred at 95-100 ° C.

The mixture is then filtered hot, the solvent is distilled off in vacuo at a bath temperature of 110-120 ° C. and the remaining, slightly solidifying crude product is recrystallized from boiling xylene. The 4-phenoxymethyl-1,3-dioxolan-2-one is obtained in the form of yellowish crystals; Mp: 97-99 ° C.

Yield: 31 g (approx. 79% of theory).

Example 46:

In a stirred solution of 372 g Epiclon 840 (diglycidyl ether of bisphenol A, commercial product from Danippon Ink & Chemicals, Inc., Japan) and 11.2 g of toluene, 208.4 g of 35% hydrochloric acid are added dropwise within 1 hour so that the internal temperature is kept between 40 and 80 ° C. The mixture is then stirred at 80 ° C for 3 hours, the organic phase is separated off and washed with 200 g of water. The re-separated organic phase is concentrated at 120 ° C in a water pump vacuum.

174.5 g of dimethyl sulfoxide and 223.05 g of sodium hydrogen carbonate are added to 393.8 g of the toluene-free chlorohydrin obtained and the mixture is stirred at 100 ° C. for 4 hours. The reaction mixture is then filtered and the filtrate is freed from dimethyl sulfoxide at about 2 mbar and 100 ° C. The distillation residue is taken up with methyl isobutyl ketone and filtered again.

765 g of a clear solution are obtained.

Contains the properties of the synthesized product Table 3.

Example 47:

Analogously to the information in Example 46, Epiclon 830 (diglycidyl ether of bisphenol F, commercial product from Dainippon Ink & Chemicals, Inc. Japan) is converted into the corresponding chlorohydrin using hydrochloric acid, the product obtained is dissolved in dimethylformamide and reacted with sodium hydrogen carbonate to form the reaction product containing cyclocarbonate groups.

The properties of the synthesized product are shown in Table 3.

Example 48:

Analogously to the information in Example 46, DENACOL EX-211 (neopentyl glycol diglycidyl ether, commercial product from Nagase Kasei Co., Japan) is converted into a cyclocarbonate derivative via the corresponding chlorohydrin.

The properties of the synthesized product are shown in Table 3.

Example 49:

Analogous to the information in Example 46, Epiclon 730 (Epoxidized Novolac resin, commercial product from Dainippon Ink & Chemicals Inc., Japan) converted into a cyclocarbonate derivative via the corresponding chlorohydrin.

The properties of the synthesized product are shown in Table 3.

Ä

Example 50:

111 g of epichlorohydrin are added dropwise to a solution of 116 g of diethanolamine and 100 g of ethanol at 50-55 ° C. in the course of 30 minutes, and the mixture obtained is stirred at 60 ° C. for 7 hours. The solution is then concentrated at 60 ° C and 10 mbar. The residue is mixed with 120 g of sodium hydrogen carbonate and 120 g of dimethylformamide and stirred at 60 ° C for 7 hours. After cooling, the mixture is filtered and

Extracted 3 times with 100 ml of toluene. The crude reaction product is then freed from the volatile constituents at 60 ° C. and 1 mbar,

The N- (2-oxo-1,3-dioxolan-4-ylmethyl) diethanolamine remains as a yellowish, highly viscous liquid.

Yield: 206 g (approx. 91%)

Viscosity of the 70% solution in DMF / toluene (2: 1): M-N (Gardner-Holdt)

IR: 3400 cm-1 (-OH), 1785 cm-1 (C = 00 cyclocarbonate) 1080-1040 cm-1 (C-0)

MS (after derivatization with N, O- (bistrimethylsilyl acetamide): 349, 290, 262, 246, 202.

Example 51:

67.5 g of 2,2-bis-hydroxymethylpropionic acid and 100 g Methyl glycol acetate are homogenized at 125-130 ° C and 0.5 g of tetramethylammonium chloride is added. 46.5 g of epichlorohydrin are added dropwise to the resulting solution over the course of 1 hour in such a way that the reaction temperature is in the range from 130 to 140 ° C. The mixture is then stirred at 130 ° C. for 3 h and the volatile constituents are distilled off in vacuo. The colorless, clear distillation residue is diluted with 200 g of dimethyl sulfoxide and mixed with 66 g of sodium bicarbonate. The mixture is stirred at 95-100 ° C for 3 hours. After cooling, the

Solids filtered off and the filtrate distilled at about 1 mbar dimethyl sulfoxide. The residue is taken up in 200 g of methyl ethyl ketone, the mixture is heated to boiling and filtered hot. The filtrate is concentrated at about 1 mbar. A light brown, viscous mass remains, which solidifies when standing. The compound is insoluble in hydrocarbons, but readily soluble in alcohols, ketones, DMF and DMSO.

Yield of 2,2-bishydroxymethylpropionic acid (2-oxo-1,3-dioxolan-4-yl) methyl ester: 107 g (approx. 91% of theory).

Cyclocarbonate group content: 35.1% (theoretical: 37.2%)

Hydroxyl number: 471 mg KOH / g (theoretical: 479.5 mg KOH / g). Acid number: 8 mg KOH / g. IR: 3392 cm-1 (-OH) 1730 cm-1 (C = 0, ester)

1795 cm-1 (C = 00 cyclocarbonate). Example 52:

55 g of 1-chloropropanediol-2,3 are added to a polyurethane, prepared by heating a mixture of 57.9 g of hexamethylene diisocyanate and 38.1 g of triethylene glycol, and the resulting mixture is stirred at 90 ° C. for 3 hours. The reaction mixture becomes increasingly tough. The bath temperature is then raised to 130-135 ° C and the excess chloropropanediol is distilled off at 1 mbar. The remaining, slightly more rigid reaction mixture is taken up with 300 g of dimethyl sulfoxide, 60 g of sodium hydrogen carbonate are added and the mixture is stirred at 95-100 ° C. in the course of 3 hours. After cooling, the mixture is filtered and the solvent is distilled off from the filtrate at 1 mbar and 120 ° C. bath temperature. The viscous residue is mixed with 1200 g of methyl ethyl ketone and heated to boiling until the polymer goes into solution. It is filtered hot from the undissolved portions and left to cool. When cooling, the cyclocarbonate-containing polyurethane precipitates as a white, granular substance. The precipitate formed is filtered off and dried in a vacuum drying cabinet at 80 ° C. for 12 hours.

Yield: 103 g (approx. 88%)

The polymer melts in the range 96-102 ° C.

It contains no isocyanates and practically no hydroxyl groups (hydroxyl number: 6 mg / KOH / g).

Cyclocarbonate group content: 11.8% (theoretical: 13.4%) IR: 1800 cm-1 (C = 0, cyclocarbonate)

3318 cm-1, 1700 cm-1, 1538 cm-1 (-NHCOO-).

Example 53:

65 g of Cymel 303 (melamine resin, trade name of the company "Dyno-Cyanamid"), 200 g of 1-chloropropanedio-2,3 and 0.6 g of maleic anhydride are stirred at 100-105 ° C for 6 hours and the methanol formed is distilled off in a weak vacuum at 40-45 ° C . 1.2 g of sodium bicarbonate are added to the mixture and the excess chloropropanediol is distilled off at 1 mbar and 130 ° C. bath temperature. The colorless, viscous residue is diluted with 300 g of dimethyl sulfoxide and the solution is mixed with 154 g of sodium hydrogen carbonate. The mixture is stirred at 95-105 ° C for 3 hours and filtered as usual. The filtrate is slowly dripped into 3 liters of water. The water, which contains the water-soluble constituents of the reaction mixture, is decanted, and the sticky polymer is dissolved with 600 ml of methyl glycol acetate with gentle heating. The solution obtained is slowly dropped again in 3 l of water. The aqueous phase is poured off again, the remaining sticky polymer is dried in a vacuum drying cabinet at approx. 100 ° C. The polymer melts in the process and solidifies on cooling to a yellowish, glass-like, brittle mass which is soluble in glycol ethers or ether esters, but is insoluble in water.

Yield: 119 (approx. 79%) Cyclocarbonate group content: 48% (theoretically at complete reaction: 57%).

Hydroxyl number: 12 mg KOH / g

IR: 1795 cm-1 (C = 0, cyclocarbonate)

1553 cm-1 (ring vibration, triazine)

Example 54:

A polyester is prepared from 45.1 g of 1,4-butanediol, 109.6 g of adipic acid and 0.5 g of p-toluenesulfonic acid in 175 g of toluene by removing the water of reaction by azeotropic distillation. After water no longer forms, the solution is mixed with 110.5 g of 1-chloropropanediol-2,3 and further heated to boiling on a water separator. 8.8 ml of water are separated off within 4 h. Then the toluene is distilled off at about 15 mbar, then the excess chloropropanediol at about 1 mbar and a bath temperature around 130 ° C. The

Distillation residue is dissolved in 200 g of dimethyl sulfoxide and mixed with 67.3 g of sodium hydrogen carbonate, the mixture is stirred at 95-102 ° C within 4 hours.

After cooling, the undissolved portions are filtered off and the at 1 mbar and a bath temperature of around 120 ° C

Dimethyl sulfoxide distilled off. The cyclocarbonate-containing polyester remains as a yellow to light brown, viscous liquid.

Yield: 179 g (approx. 96%) Cyclocarbonate group content: 22.1%) (theoretical: 23.3%).

Hydroxyl number: 11 mg KOH / g

Acid number: 4 mg KOH / g

Viscosity Gardner-Holdt: Z 2 - Z 3

IR: 1806 cm-1 (C = 0, cyclocarbonate) 1731 cm-1 (C = 0, ester)

Example 55:

From 207.7 isophthalic acid, 210.1 g trimellitic acid, 36.5 g

Adipic acid and 208.3 g of neopentyl glycol are added within

10 hours at 210 ° C a polyester with the molecular weight of

1666, acid number of 230 mg KOH / g and hydroxyl number of 16 mg KOH / g. 139 g of this polyester are mixed with 64 g of dimethylformamide and 0.3 triphenylphosphine and heated to 100 ° C. While stirring, 65 g of epichlorohydrin are added dropwise to the solution thus obtained over a period of 1 hour and the mixture is stirred at 100 ° C. for a further 3 hours. The reaction mixture is then mixed with 50 g of dimethylformamide and 69 g of sodium hydrogen carbonate and stirred at 100 C for 2 h. After cooling, the solid constituents are filtered off and the filtrate is concentrated at 10 mbar and 120 ° C. The cyclocarbonate-containing polyester remains as a light brown, tough mass.

Yield: 189 g Cyclocarbonate group content: 27%.

Example 56:

From 0.843 mol isophthalic acid, 1.62 mol trimellitic acid,

1.63 mol of Cardure E 10 (commercial product from "SHELL") and 0.289 mol of neopentyl glycol are added within 10 hours

210 C is a polyester with a molecular weight of 2100, acid number of 176 mg KOH / g and hydroxyl number of 13 mg

KOH / g produced. 224 g of this polyester are stirred with 133 g of dimethylformamide, 0.3 g of triphenylphosphine and 77 g of epichlorohydrin within 4 hours at 100 ° C.

The volatile constituents are then distilled off at 10 mbar and 120.degree. The resulting chlorohydrin product is mixed with 100 g of dimethylformamide and with 90 g

Sodium bicarbonate was added and the mixture was stirred at 100 ° C. in the course of 2 hours, after cooling the mixture was filtered and the filtrate was concentrated at 10 mbar and 120 ° C.

The cyclocarbonate-containing polyester is a light brown, tough material.

Yield: 281 g

Cyclocarbonate group content: 18.4%

Claims

1. Process for the preparation of cyclocarbonate compounds of the general formula

from vicinal halohydrins in which R ¹ , R ² , R ³ and R ⁴ each represent a hydrogen atom or an optionally substituted aliphatic, cycloaliphatic, aromatic or arylaliphatic hydrocarbon radical having 1 to 12 carbon atoms or the radicals R ¹ and R ³ or R ⁴ or R ² and R ³ or R ^{4 are} constituents of a 5- or 6-membered carbocyclic ring, where R ¹ , R ² , R ³ and R ⁴ can be identical or different from one another and at least one of the R ¹ , R ² , R ³ and R ^{4 are} at least one functional group with at least one heteroatom from the IV to VII group of the Periodic Table of the Elements and / or at least one unsaturated C = C or / and C≡C function carries

characterized in that

vicinal halohydrins of the general formula

wherein R ¹ , R ² , R ³ and R ^{4 have} the meaning given above and X is a halogen, are reacted with an alkali metal bicarbonate in the presence of a polar aprotic organic solvent at temperatures between 50 ° C. to 160 ° C. 2. Process for the preparation of polymeric cyclocarbonate compounds which contain at least one cyclocarbonate group per macromolecule,

characterized in that

a polymer which has at least one vicinal halohydrin of the general formula

where R ² , R ³ and R ⁴ each represent a hydrogen atom or an optionally substituted aliphatic, cycloaliphatic, aromatic or arylaliphatic hydrocarbon radical having 1 to 12 carbon atoms or the radicals R ² and R ³ or R ⁴

Components of a 5- or 6-membered carbocyclic ring are, where R ² , R ³ and R ⁴ can be identical or different from one another and optionally one of the radicals R ² , R ³ and R ⁴ , optionally a heteroatom from IV to VII group of the Periodic Table of the Elements and / or at least one unsaturated C = C or / and C = C function and X is a halogen, with an alkali metal bicarbonate in the presence of an aprotic organic solvent at temperatures between 50 ° - 160 ° C is implemented.

3. Process for the preparation of polymeric cyclocarbonate compounds which contain at least one cyclocarbonate group per macromolecule,

characterized in that

a polymer which has at least one vicinal halohydrin of the general formula

where R ² , R ³ and R ⁴ each represent a hydrogen atom or an optionally substituted aliphatic, cycloaliphatic, aromatic or arylaliphatic hydrocarbon radical having 1 to 12 carbon atoms or the radicals R ² and or R ⁴

Components of a 5- or 6-membered carbocyclic ring are where R ² , R ³ , R ⁴ can be identical or different from one another and, if appropriate, one of the radicals R ² , R ³ and R ^{4 has} at least one functional group with, if appropriate, a hetero atom from the IV to VII group of the Periodic Table of the Elements and / or at least one unsaturated C = C or / and C = C function and X is a halogen, with an alkali metal bicarbonate in the presence of an aprotic organic solvent at temperatures between 50 ° to 160 ° C is implemented.

4. The method according to claims 1, 2 or 3,

characterized in that

one uses a chlorine, bromine or iodine hydrine as the halohydrin.

5. The method according to claim 1, 2, 3 or 4,

characterized in that

one uses sodium or potassium bicarbonate as alkali metal bicarbonate.

6. The method according to at least one of claims 1 to 5,

characterized in that

one as a polar aprotic organic solvent dimethylformamide, acetonitrile, dimethyl sulfoxide, hexamethylphosphoric acid triamide, dimethyl sulfone, N-methylformamide, N-methyl-2-pyrrolidinone, trimethylphosphate, N, N-diethylformamide, tetramethylurea or 1,3-dimethylimidazolidin-2-one starts.

7. The method according to claim 1,

characterized in that

the radicals R ¹ , R ² , R ³ and / or R ^{4 of} the halohydrin used have a polymerizable, optionally substituted vinyl, allyl or acrylic group.

8. The method according to at least one of claims 1

characterized in that

in the functional groups of the radicals R ¹ , R ² , R ³ and / or R ^{4 used} as the starting compound

Halogenhydrins oxygen and / or sulfur and / or nitrogen atoms are included.

Method according to at least one of claims 1-3, characterized in that

the functional groups present in the radicals R ¹ , R ² , R ³ and / or R ^{4 of} the halohydrin used likewise have halohydrin structural elements.

10. Use of the cyclocarbonate compounds prepared according to claim 1 for the preparation of urethanes of the general formula

wherein R ¹ , R ² , R ³ and R ^{4 have} the meaning given above and R ⁵ and R ^{6 represent} a hydrogen atom or a substituted aliphatic, cycloaliphatic or aromatic radical having 1 to 12 carbon atoms.

11. Use of the polymeric cyclocarbonate compounds prepared according to claims 2 or 3 for the production of urethanes according to claim 10.

12. N- (2-oxo-1,3-dioxolan-4-yl-methyl) -diethanolamine

13. 2,2-bis (hydroxymethyl) propionic acid (2-oxo-1,3-dioxolan- 4-yl-methyl) ester