DE1568342A1 - Dicarboxylic acid esters containing carbonate groups - Google Patents

Description

Dicarboxylic acid esters containing carbonate groups

It has been found that dicarboxylic acid esters containing carbonate groups can be prepared by carbonate-containing dihydroxy compounds of the general formula

0 -ι

CH ₂ -OCO

CH.

in the η for integers from 1 to 20, preferably from 1 to 15, or mixtures thereof, with dicarboxylic acids, dicarboxylic acid anhydrides or dialkyl dicarboxylates, with the exception of terephthalic acid and its esters, in a manner known per se implements.

Dihydroxy compounds containing carbonate groups of the above general formula can not yet be used for a Process belonging to the state of the art by reacting 1,4-bis (hydroxymethyl) cyclohexane with phosgene in a simple manner Way «, You can also use known methods by transesterification of carbonic acid esters with 1,4 bis (hydroxymethyl) cyclohexane in the presence of conventional transesterification catalysts getting produced. 1,4-bis (hydroxymethyl) cyclohexane can be used here can be used in its trans or cis form or as a mixture of both forms.

Both aromatic and aliphatic acids can be used as dicarboxylic acids Dicarboxylic acids in question; Unsaturated dicarboxylic acids can also be used. Suitable are e.g.

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Phthalic acid and isophthalic acid. Malonic acid are also suitable, Succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid and I-Ia: iahyäror> hthalic acid. As unsaturated dicarboxylic acids can for example maleic acid, fumaric acid, itaconic acid and tetrahydrophthalic acid can be used. Instead of the free dicarboxylic acids, their esters with short-chain alkanols, E.g. the dimethyl, diethyl or dipropyl esters are used will. If the dicarboxylic acids form anhydrides, these can also be used, e.g. maleic anhydride, Succinic anhydride, glutaric anhydride, phthalic anhydride and tetra- and hexahydrophthalic anhydride.

The molar ratio of dihydroxy compound: dicarboxylic acid (or Dicarboxylic acid derivative) can vary between 2: 1 and 1: 2. Preferably, however, the components are used in molar ratios from 2: 1 to 1.1: 1 and from 1: 1.1 to 1: 2 are used. These molar ratios result in condensates with predominantly identical end groups.

To carry out the reaction, the mixture of "dihydroxy compound and diaarboxylic acid (or dicarboxylic acid derivative) at temperatures between 140 and 230 ° C., preferably to 180 to 210 C, heated, and the released water or Alkanol continuously distilled off. ■ It is advantageous to remove the water or alkanol by passing it through to accelerate an inert gas stream. You can dom Add the usual entrainers (e.g. benzene or toluene) to the reaction mixture, thus removing the water of reaction effect by azeotropic distillation. It is possible, but not necessary, to control the course of the reaction by adding conventional To accelerate esterification catalysts. The esterification proceeds almost quantitatively and can be determined by determination the oil and acid numbers are easily tracked will.

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Surprisingly, in the implementation according to the invention the carbonate grouping in the dihydrocycyl compound is not attacked. Less than 0.3% of the carbonate bonds will be split as a result of transesterification with the dicarboxylic acids used.

The products obtained according to the invention are excellent Adhesives or binders. They are colorless, transparent, lightfast and thermally stable up to temperatures of 200 C, V7ie from Ullmann's Encyclopedia of Technical Chemistry, Volume 9, Munich-Berlin 1957, page 578 f, is known Various synthetic, high molecular weight, organic substances have already been used as adhesives or binders and have been used in the adhesive and paint sector. However, since these connections are proportionate If hard and brittle films form, plasticizers such as camphor, phthalic acid ester or phosphoric acid ester are always added; this then results in clear and depending on the plasticizer content more or less plastic films. The aim is to obtain adhesive films that are as smooth as possible, but it can be done only add limited amounts of plasticizer, since the greater the plasticizer content in the films, their cohesive strength as well as the setting speed decrease rapidly, but the physiological danger of these binders increases.

7ms of the French patent specification 1 381 007 it is also known that polycarbonates from cycloaliphatic dihydro: cy compounds represent transparent, elastic plastics that have a good surface gloss and a low tendency to crystallize on v / iron. The high impact strength is retained down to below -40 C. The adhesive strength of these products on glass or body sheet is not sufficient. aside from that

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The polycarbonates dissolve well in aromatics and halogenated ones Carbon hydrogen, but only to a small extent in the esters and ketones commonly used as paint solvents. These disadvantages are associated with the use of the polycarbonates mentioned as opposed to adhesives and binders.

Compared to these known adhesives and binders the products obtained according to the invention have a number of advantages. They are also without the addition of plasticizers highly elastic. Its adhesive strength on bodywork sheet is very good, and on glass it is satisfactory. In addition, the Products obtained according to the invention in the esters and ketones customary as paint solvents, e.g. acetone, methyl ethyl ketone and ethyl acetate, readily soluble. Their adhesiveness is excellent.

The inventive method offers the possibility of Variation of the molar ratio of dihydroxy compound: dicarboxylic acid products that are optimally suited for certain purposes to manufacture. If, for example, a molar ratio of 2: 1 to 1.1: 1 is chosen, the product contains predominantly hydroxyl end groups, which leads to particularly good solubilities. The variation in the number of links in the chain offers further options for tuning η in the dihydroxy compound; this allows the viscosity and softening interval, and thus the softness and adjust the elasticity of the resins at certain temperatures in the desired manner.

Due to their properties, those obtained according to the invention can Products as plasticizer-free coatings and adhesives be used. The transparency of the invention made resins also allows gluing transparent

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tiger materials. Products with a low number of chain links η are soft resins and can be processed as hot-melt adhesives (pressure-sensitive adhesives) will. By adding pigments, dyes and fillers, such as lithopone, chalk, carbon black or talc, leave it behind the products adapt to special uses, whereby their cohesive strength increases. The products are suitable for gluing and coating leather, artificial leather, Plastics, felt, wood, textile fabrics, cardboard and paper.

The condensates produced according to the invention can also as polymer plasticizers, especially for polyvinyl halides such as polyvinyl chloride, polyvinylidene chloride and copolymers made of vinyl chloride and vinyl acetate.

"The parts given in the following examples are parts by weight."

example 1

959 parts (3 mol) of a dihydroxy compound of the above general formula (n * » 1) are heated with 150 parts (1.5 mol) of maleic anhydride to 180 ^° C. for ^{6 hours while passing nitrogen through. 1 The} remaining amounts of water of reaction are then removed through Apply a vacuum of about 20 torr. 1,070 parts of a colorless and clear, viscous condensate with a molecular weight of 724 (calculated: 708) and an acid number <3 result.

From a solution of the product in acetone or ethyl acetate films with good adhesive properties can be produced.

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Example 2

208.5 parts (0.92 moles) of a dihydroxy compound of the above general formula (n = 1) with 53.3 parts (0.46 mol) Fumaric acid heated to ISO G for 6 hours while passing nitrogen through, 13.5 g of water being distilled off. Afterward one removes residual amounts of water from the reaction mixture by applying a vacuum of about 1 torr. It the result is 315 parts of a viscous, clear and colorless condensate with a molecular weight of 650 (calculated: 708) and an acid number <3. The resin is readily soluble in methyl ethyl ketone and ethyl acetate.

Example 3

400 parts (0.59 moles) of a dihydroxy compound of the above general formula (n »3) with 34.3 parts (0.29 mol) Fumaric acid heated to 180 ° C. for 6 hours while passing nitrogen through. Remaining amounts of water of reaction are stripped in vacuo (about 1 torr). 420 parts of a colorless and clear condensate with a molecular weight are obtained of 1,390 (calculated: 1,354) and an acid number of about From a solution in methyl ethyl ketone or ethyl acetate films with very good adhesion to body panels and glass are obtained.

Example 4

400 parts (0.49 mol) of a dihydroxy compound of the above general formula (n = 4) are mixed with 27.3 parts (0.24 mol) Fumaric acid mixed and heated to 180 ° C for 6 hours while passing a stream of nitrogen through. After removing of the remaining water by applying a vacuum of about 1 Torr becomes 413 parts of a clear condensate with an acid number of <3 and a molecular weight of 1790 (calculated

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net: 1736). The condensate shows a significantly better Solubility in methyl ethyl ketone and ethyl acetate on as the dihydroxy compound used, although the molecular weight was more than doubled.

Example 5

410 parts (0.46 moles) of a dihydroxy compound of the above general formula (n = 5) with 22.7 parts (0.23 mol) Succinic anhydride mixed and heated to 180 C for 6 hours heated while passing through a stream of nitrogen. The rest Water is removed by applying a vacuum of approximately 1 torr. 424 parts of a clear and colorless condensate with an acid number of about 3 and a molecular weight are obtained from 1,920 (calculated: 1,882). The condensate forms clear, transparent, elastic from the melt or solution Films with good adhesion to body panels and glass and excellent adhesive properties.

Example 6

305 parts (0.35 mol) of a dihydroxy compound of the above general formula (n = 5) are mixed with 20 parts (0.17 mol) Fumaric acid mixed and heated to 180 ° C. for 6 hours while passing a stream of nitrogen through. Then will the remaining water of reaction is removed by applying a vacuum of about 1 Torr. 316 parts of a colorless one are obtained and clear condensate with an acid number of 3 and a molecular weight of 1,990 (calculated: 2,070). The product forms transparent, colorless films with high elasticity and good adhesive strength from the melt and solution Sheet metal and glass.

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Example 7

410 parts (0.46 moles) of a dihydroxy compound of the above general Formula (n = 5) v / earth mixed with 37.7 parts (0.23 mol) of isophthalic acid and while passing through a stream of nitrogen Heated to 210 ° C. for 7 hours. Remaining amounts of water are removed by applying a vacuum of about 1 Torr. 435 parts of a clear condensate with an acid number of 5 and a molecular weight of 1,960 are obtained (calculated: 1 930). The product is dissolved in methyl ethyl ketone and ethyl acetate better solubilities than the dihydroxy compound used, although the molecular weight due to the esterification was more than doubled. The resin forms films with high elasticity and good properties from the melt and solution Adhesion to sheet metal and glass.

Example 8

370 parts (0.2 mol) of an oligomeric dihydroxy compound of the above general formula (n = 10) are mixed with 60 parts (0.4 mol) of phthalic anhydride and ^{esterified at 210 °} C. for 6 hours with stirring. 430 parts of a transparent, colorless resin with a molecular weight of 2,050 (calculated: 2,142) are obtained. The condensate softens at about 70 ° C. and has good solubilities in methyl ethyl ketone and ethyl acetate. The resin forms transparent * films with high lightfastness from the melt and solution.

Example 9

470 parts (0.20 mol) of a dihydroxy compound of the above general formula (n = 13) are mixed with 11.6 parts (0.10 mol) Mixed fumaric acid and heated to 180 ° C. for 6 hours while passing a stream of nitrogen through. Then will the rest of the heating water by applying a vacuum of about 1 Torr away. 475 parts of a colorless and are obtained transparent condensate with an acid number of 2 and one

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Molecular weight of 4,700 (calculated; 4,800). The product Forms transparent, colorless films with high elasticity and good adhesive strength from the melt and solution.

Example 10

725 parts (1.5 moles) of a dihydroxy compound of the above general formula (η = 2) are mixed with 100 parts (1 mol) of succinic anhydride and heated for 11 hours at 180.degree heated while passing through a stream of nitrogen. The rest Water is removed by applying a vacuum of approximately 1 torr. 790 parts of a clear and colorless condensate are obtained with an acid number of about 4 and a molecular weight of 1,650 (calculated 1,616) good solubility in common paint solvents.

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Claims (7)

Claims 1. Process for the preparation of dicarboxylic acid esters containing carbonate groups ^ characterized in that one carbonate group-containing dihydroxy compounds of the general formula 0 CH ₂ -OCO CH ₂ OH, in the η for integers from 1 to 20, preferably 1 to 15, stands, or mixtures thereof, with dicarboxylic acids, dicarboxylic anhydrides or dicarboxylic acid dialkyl esters, with the exception of terephthalic acid and its esters, in a manner known per se. 2. The method according to claim 1, characterized in that the dihydroxy compounds with the dicarboxylic acids, 'dicarboxylic anhydrides or dicarboxylic acid dialkyl esters in a molar ratio of 2: 1 to 1: 2. 3. Carbonate groups with predominantly terminal hydroxyl groups containing linear polyesters of the general formula O OO 0 -0-C-O} Q-O-C-R-C-O -? (Q-O-C-O η - m Q-OH in the η for integers from 1 to 20, preferably 1 to 15, m for integers from 1 to 10, Q for the 1,4-dimethylene cyclohexane radical and R stands for a saturated or unsaturated, aliphatic or cycloaliphatic alkylene radical or a Arylene radical (with the exception of 1,4-pheny learns) stshen. 09821/1969 BATH ORIGINAL - 11 - 0.2. 2137 July 16, 1969 4. Carbonate groups with predominantly terminal carboxyl groups containing linear polyesters of the general formula - OO 0 0 HO-CRCO QOCO -fjj— QOCRCO ^ 7 ^ - H, in the η for integers from 1 to 20, preferably 1 to 15, m for integers from 1 to 10, Q for the 1,4-dimethylene cyclohexane radical and R stands for a saturated or unsaturated, aliphatic or eyeloaliphatic alkylene radical or a Arylene radical (with the exception of the 1,4-phenylene radical). 5. Polyester according to claim 3 or 4, wherein R is a straight chain ,, saturated, aliphatic Alkylene radical with 1 to 12 carbon atoms. 6. Polyester according to claim 3 or 4, wherein R is an unsaturated, aliphatic alkylene radical with 2 or 3 carbon atoms. 7. Polyester according to claim 3 or 4, wherein R is a 1,2- or 1,3-phenylene radical. 8, polyester according to claim 3 or 4, wherein R is a 1,2-cyclohexylene or 1,2-cyclohexenylene radical stands. BATH ORIGINAL 00 9821/195