Esters

-CH₂CHCH₂A

Where each A is independently H, Cl, Br or OX; each X is independently H or the residue of a saturated or unsaturated carboxylic acid, with the proviso that at least one R 'is 3-hydroxy-1,2-propyl and at least one is a group of the formula

-CH₂CHCH₂OX

in which X is the acid radical of a saturated or an aJJ-unsaturated carboxylic acid 1st; and m and π are such integers that the total number of R'O groups is at least 2 1st and η is 1 to 8. 2. A process for the preparation of ölartlger or semi-solid linear or not -Hnearer compounds of the formula

R (R'O)_fflX

by reaction of a carboxylic acid or its anhydride or halides with a polymer or copolymer of tertiary butylglycidyl ether in the presence of a strongly acidic catalyst, wherein in the formula R the radical of an initiator compound remaining after removal of η active hydrogen atoms is R "" for the polymerization of alkylene oxides free from groups other than OH 1st which react with an alkylene oxide; ..

each R 'is independently an alkylene radical selected from the group consisting of ethylene, trimethylene, tetramethylene, 1,2-butylene, 2,2-Bls (halomethyl) -1,3-propylene and the groups of the formula

-CH₂CHCH₂A

1st, in which each A is independently H, Cl, Br or OX; each X is independently H or the acid radical of a saturated or unsaturated carboxylic acid with the proviso that at least one R 'is 3-hydroxy-1,2-propyl and at least one is a group of formula

-CH₂CHCH₂OX

In the X, the acid residue is a saturated or an unsaturated carboxylic acid 1st; and m and η are such integers that the total number of R'O groups is at least 2 and η is 1 to 8, characterized in that the acid, anhydride or acid halide is added in such amounts that some of the Hydroxyl groups of the polymer can not be esterified. 3. Use of the compounds according to claim 1 as coating compositions.

In the US-PS 35 19 559 polymers of tertiary-butylglycldyläther (TBGÄ) and copolymers thereof with alkylene oxides are disclosed. It is further stated there that the terminal hydroxyl groups can be reacted with polycarboxylic acids to form polymeric esters suitable for breaking water-in-oil emulsions.

From GB-PS 12 67 259 is the condensation of TBGA with a variety of compounds containing at least one active hydrogen atom known. In a second step, the tertiary butyl groups are removed to form linear polyglycidols.

US Pat. No. 2,680,109 discloses the polymerization of glycidyl methacrylate via the epoxy group to form a linear polymer which can then be further polymerized and crosslinked via the methacrylate groups.

From US-PS 35 09074 the copolymerization of teobutylene oxide and Glycldyimethacrylat In the weight ratio 95: 5 is known.

In FR-PS 14 38 201 (CA, 66, 2877, 29874 m) is the copolymerization of a mixture of ethylene oxide. Propylene oxide and glycidyl methacrylate described.

US Pat. No. 3,446,757 discloses homopolymerization and copolymerization of silicone esters of glycidol followed by hydrolysis to remove the esterified group to form homopolymers and copolymers of glycidol. These can be crosslinked by reaction with a polyfunctional compound such as an acid, anhydride, isocyanate or epoxide.

The US-PS 35 78 719, 35 95 924 and 36 66 671 show the "hydroxylation" of homopolymers or copolymers of Eplchlorhydrins by reaction with Kallacetat and glycol with the polymers. It also small random amounts of acetylated materials are formed and hydrolyzed in the subsequent stage.

The invention relates to oily or semi-solid linear or non-linear compounds of the formula

in which R is the residue of an initiator compound remaining after removal of η active hydrogens, for the polymerization of alkylene oxides free of groups other than OH, which react with an alkylene oxide; is; each R 'is independently an alkylene radical selected from the group consisting of ethylene, trimethylene, tetramethylene, 1,2-butylene, 2,2-bis (halomethyl) -1,3-propylene and the groups of formula

-CH₂CHCH₂A

is. wherein each A is independently H, Cl, Br or OX; each X is independently H or the acid radical of a saturated or ar, / 3-unsaturated carboxylic acid, with the proviso that at least one R 'is 3-hydroxy-1,2-propyl and at least one is a group of the formula

-CH₂CHCH₂OX

Is. Where X is the acid radical of a saturated or unsaturated carboxylic acid; and m and η are such integers that the total number of R'O groups is at least 2 1st and η is 1 to 8.

The term "linear" refers to any of the polyoxyalkylene chains of the backbone attached to the interna torrest R. If η in the above form! greater than 2 1st, the molecule can be considered as branched.

The invention also includes a process for preparing oleaginous or semi-solid linear or non-linear compounds of the formula

(R¹O)₁₁₁X

by reacting a carboxylic acid or its anhydride or halide with a polymer or copolymer of tertiary butylglycidyl ether in the presence of a strongly acidic catalyst. In the above formula, the general symbols have the meaning already given. In this process, it is essential that the acid, anhydride or acid halide be added in such amounts that some of the hydroxyl groups of the polymer are not esterified.

In the process, the tertiary butyl groups of a polymer or copolymer of tertiary-butylglycidyl ether (TBGÄ) are removed and a desired proportion thereof is replaced by ester groups. This is done. By heating the polymer or copolymer in the presence of the strong acid catalyst, preferably a sulfonic acid, and the acid or acid anhydride or acid halide salt required for the esterification.

Those tertiary alkyl groups which are not converted to ester groups are predominantly converted to primary hydroxyl groups. This reaction can be explained by the following scheme:

ίΛ ι »CH₂OH

In this formula, R 1 is a tertiary alkyl radical, R'COOH is a carboxylic acid, and the wavy lines represent; v is the polyoxyalkylene backbone of the polymer. The proportion of tertiary alkyl ether groups that are In ester or

.if hydroxyl groups are converted by the consumed portion of the esterified acid and / or the

sj 'S amount of water formed in the reaction determined.

Ί · 1 Many of the unique properties and uses of such compounds made from unsaturated acids

^:i% are due to the presence of both hydroxymethyl and polymerizable acyloxymethyl

;_:; groups that occur as substituents on the backbone of the chain-like compounds. These substituents

are more or less randomly arranged and can, as the formula indicates. In a wide range of

- "Relationships occur.

Already, a very small amount of polymerizable acyloxymethyl groups, or even just a single such group, is sufficient to produce the novel compounds with other vinyl type monomers, the

by free radicals are polymerizable to make polymerizable. As a result, coatings of such compounds are polymerizable by the action of free radicals. But they are also due to heat^:"and / or radiation or in combination with organic peroxides or other free radical initiators polymerizable.

On the other hand, the presence of one or more hydroxymethyl groups opens up numerous possibilities for the modification of the compounds. One or all of these hydroxyl groups can be with one or^: several acids, isocyanates or other reaction components are reacted. By using

Hydrophobic acids, such as long-chain fatty acids, can be modified within a wide range of hydrophobic-hydrophlic equilibria of the compounds, for example, hydrophobic coating materials can be prepared by esterifying a portion of the hydroxymethyl groups with stearic acid Materials can then be crosslinked by polymerization of the residues of unsaturated acids and made resistant to solvents. In similar catfish, the aldehydes, especially glyoxal. JS: JS can be used to link two hydroxyl groups by hemiacetal bonds. Such bonds

can be split again by treatment with an aqueous base. Under severe conditions irreversible acetal crosslinks can be formed.

The saturated acid compounds of the invention are oleaginous liquids or semi-solids which can be used as coating compositions, lubricants, plasticizers, antistatic agents for textiles, and surfactants. This broad scope is based on the fact that the compounds can be "tailor made" within a wide range depending on the desired structure and property. By changing the number of free hydroxyl groups and the number and length of the carbon chain of the acyl groups, the hydrophobic-hydrophlic equilibrium can be adjusted to any value, whereby a wide range of surface active agents can be obtained which serve as emulsifiers and wetting agents can. Such compounds containing a variety of fatty acid residues up to 10 carbon atoms are preferably used as softeners and lubricants for leather, textiles and paper, and as plasticizers for cellulose ether resins. Such compounds containing fatty acid residues of 8 to 20 or even more carbon atoms are useful as plasticizers and antistatic agents for polyvinyl chloride and polyesters and films and fibers of polyesters S "and polyamides. Such compounds containing a plurality of free hydroxyl groups are useful as intermediates for the preparation of polymerizable vinyl monomers by esterification with an acid having a polymerizable vinyl group such as acrylic, methacrylic, chloroacrylic, cyanoacrylic, maleic and itaconic acid, suitable. The esters obtained are polymerizable by free-radical initiators, resulting in resins which are suitable as coating compositions and as molding compositions or as casting resins for the production of solid ss objects.

The compounds preferred in the invention are those in which R is the residue of an initiator compound RH_n 1st, which is a hydroxy compound free of other substituents capable of reacting with alkylene oxide than the alcoholic hydroxyl groups. Suitable compounds of this type are alkenols, such as methanol, butanol, octanol, dodecanol and octadecanol; Alkenols such as allyl alcohol, 10-undecene-1-ol, oleylal^Halkyl alcohol, such as ethylene, propylene, butylene, 1,4-tetramethylene and 1,3-hexylene glycol; higher polyhydric polyols, such as glycerine, pentaerythritol, sorbitol, sucrose, hexane triol; phenols, such as phenol, cresols. Xylenols, hydroquinone, resorcinol, naphthols and aralkanols, such as benzyl alcohol and phenethyl alcohol, Preferably, the initiator contains not more than 8 active hydrogen atoms, and more preferably not more than 3. Particularly suitable initiators are water and the glycols. Water reacts with Alkylenoxlden or tertiary ^{(L <} Butylglycidyl ether (TBGÄ) under opening of the Oxlranrlngs, creating a glycol that can be considered as a "in situ" produced Glycollnltlator. With oxetanes and tetrahydrofurans similar reactions occur. The essentially linear polymers or copolymers of glycidol can be used for this purpose

to produce the compounds of the invention in various catfish. So you can z. B. a polymer of TBGÄ or a copolymer thereof with one or more Alkylenoxlden according to the method of the aforementioned US Patent 35 19 559. The tertiary butyl groups can then be removed by heating the material in the presence of an arylsulfonic acid according to the previously mentioned GB-PS 12 67 259. As a result, the tertiary butoxy groups are replaced by hydroxy groups. Any proportion of these groups can be esterified with a carboxylic acid. The terminal hydroxyl groups can also be esterified.

In a preferred method, TBGÄ, optionally in association with one or more alkylene oxides, is condensed with an initiator compound, which may be the moisture present in the source materials and / or the unit. Then the tertiary butoxy groups are removed and the desired proportion of ester groups is introduced simultaneously. By heating the polymer in the presence of catalytic amounts of an arylsulfonic acid or similar catalyst and sufficient amounts of a carboxylic acid intended for esterification. Examples of suitable catalysts are benzenesulfonic acid, toluenesulfonic acid and naphthalenesulfonic acid.

If a fatty acid is used in significant amounts for the esterification, then it is preferably used in the form of its anhydride, with one mole of anhydride used being an esterifiable hydroxyl equivalent so that the acid esters are formed. If you try to completely esterify such an acid, your polyvalence leads to a branching and finally a cross-linking. In addition, because of the likelihood of transesterification and the occurrence of cross-linking, it is advantageous to have the anhydride of the polycarboxylic acid separated and react with the monocarboxylic acid which may be used only after the reaction, unless the latter is also used in the form of its anhydride. In such a case, the anhydrides can be mixed and reacted simultaneously. The by-produced acid can be removed under conditions which indicate further esterification of the tell esters of the acids.

For the preparation of the esters in the invention any carboxylic acids into consideration. The monocarbon:? acids give esters with the same polymer backbone as when tertiary alkyl ether is used as the starting material, the difference being that most or all of the tertiary alkyl groups have been removed and replaced to the extent desired by acyl groups of the starting acid. Those that have not been removed have been converted to hydroxyl groups. The carboxylic acids extend the chain of the backbone of the polymer and can also cause some branching, ultimately leading to crosslinking of the polymer. Polycarboxylic acids of higher valence than two also result in rapid crosslinking and gelation of the polymer in small amounts. For this reason, they are usually used only in very small quantities or not at all.

The preferred monocarboxylic acids are the saturated fatty acids such as acetic, butyric, lauric and stearic; olefinically unsaturated fatty acids such as acrylic, methacrylic, undecylenic, oleic and linolenic acids; the aromatic acids such as benzoic, alkylbenzoic and naphthoic acids and the chloro and bromo derivatives of these acids. Instead of the acids one can use their anhydrides. These are of particular interest when partial esters of the polycarboxylic acids are desired as the final product, with one mole of the anhydride being used on each carboxyl group desired in the product and the esterification carried out under mild conditions so that the formation of diesters of the acid is minimized is reduced. Suitable polycarboxylic acids and their anhydrides are alkanedicarboxylic acid, such as succinic, adipic and sebacic acid; Alkenylcarboxylic acid, such as maleic, itaconic, citraconic and glutaconic acid, and aromatic dicarboxylic acids, such as phthalic, isophthalic and terephthalic acid.

To carry out the invention, a polyoxyalkylene compound is prepared which comprises a tertiary alkylglycidyl ether radical, ie a group of the formula - »5

-CH₂CHO! OR

contains, in which R is a tertiary alkyl radical. The preparation is carried out by known methods. In an appropriate way, you can achieve that. By subjecting a tertiary Alkylglycidyläther the polymerization or copolymerization. For the copolymerization, one or more other cyclic ethers are considered, such as ethylene oxide, propylene oxide, Butylenoxld, trimethylene oxide, tetrahydrofuran, Eplchlorhydrin and 2.2-Bls- (haIomethy!) - oxetane. Such polymerizations can be carried out with the aid of different catalysts *. be performed, such. As by alkali hydroxide, Friedel-Crafts catalysts, Alumlniumalkylverbindungen. Zinkalkylverblndungen or other catalysts for the polymerization of alkylene oxides. In the presence of initiator compounds having one or more active hydrogen atoms, polymer chains are initiated in the known manner at the site of these active atoms. These polymers have terminal hydroxyl groups which may optionally be esterified before or simultaneously with the sites of the tertiary alkyl ether groups The essential step of the process of the invention, ie the simultaneous dealkylation and esterification reaction is carried out by heating the polymer having tertiary alkyl ether groups with the acid required for esterification or its anhydride in the presence of a strongly acidic catalyst, simultaneously the alkene corresponding to the tertiary alkyl group and that in the reaction optionally formed water is removed. The reaction can be effected by simply mixing the starting materials and the catalyst and heating to the reaction temperature. The removal of the by-product alkene can be facilitated by operating under reduced pressure and / or passing a stream of an inert gas through the reaction mixture. These work wonders

also facilitate the removal of any water formed in the reaction. The removal of water is further facilitated by the use of a water-immiscible organic solvent, which is conveniently a hydrocarbon or a halogenated hydrocarbon having a suitable boiling point so that it is distilled off with water as a low-boiling azeotropic mixture can. After the completion of the reaction, the by-products such as catalyst residues, solvent and still-reacted acid are separated.

Since the polyether starting material is more or less of a polymeric nature. The esterification reaction with the carboxylic acid tends to be very slow and incomplete toward the end unless it is driven very vigorously. When complete esterification is important, it is often useful to add the anhydride to the acid towards the end of the reaction because it is much more reactive than the acid itself. The use of a stoichiometric excess of the acid or its anhydride also favors complete esterification.

The unsaturated acid compounds of the invention are polymers which are oil-species to solids, depending on their molecular weight, the nature of the ingredient inventory, and the identity, proportion, and location of various other molecular entities. Those compounds which are initially liquid can be converted into the solid form by polymerization or copolymerization via the polymerizable double bonds of the α, ί-unsaturated acid. These materials are useful as curable resins that can be made into coatings or moldings that can then be cured by the action of heat, radiation, or free radical-forming compounds, making them harder and more resistant to heat and solvents.

In the following examples, the invention will be explained in more detail.

A. Preparation of TBGÄ polymer and mixed polymers

Monomeric tertiary butylglycidyl ether (TBGÄ) is subjected to polymerization or copolymerization in various proportions with other cyclic ethers in known welders, the products and their preparation being listed in Table I. The stated initiators are the active hydrogen compounds used to initiate the polymer chain. In all experiments, the reaction was continued until all of the TBGÄ and other alkylene oxides, if used, had been consumed, to ensure that the final product had the same composition as the starting materials introduced into the reactor. The molecular weights of the products were estimated by the acetic anhydride method, which relies on the expected number of hydroxyl groups per molecule.

Table I

<p><tgroup cols="8"><tbody><row><entry> Experiment No. </entry><entry> Initiator" </entry><entry> catalyst </entry><entry> Monomers, Mol% TBGÄ Others » </entry><entry>PO, 50</entry><entry> Molecular weight of the product </entry><entry> Monomer units per mole of TBGÄ others </entry><entry>1.9</entry></row><row><entry>1</entry><entry>DAY</entry><entry>N / A</entry><entry>50</entry><entry>-</entry><entry>500</entry><entry>1.9</entry><entry>1,0</entry></row><row><entry>2</entry><entry> AG </entry><entry>BF₃</entry><entry>100</entry><entry>PO, 25</entry><entry>790</entry><entry>5,6</entry><entry>3,8</entry></row><row><entry>3</entry><entry>DAY</entry><entry>N / A</entry><entry>75</entry><entry>-</entry><entry>500</entry><entry>2,3</entry><entry>1.0</entry></row><row><entry>4</entry><entry>EC</entry><entry>N / A</entry><entry>100</entry><entry>-</entry><entry>2 350</entry><entry>17,6</entry><entry>3.0</entry></row><row><entry>5</entry><entry>DAY</entry><entry>N / A</entry><entry>100</entry><entry>-</entry><entry>4 950</entry><entry>37,0</entry><entry>0</entry></row><row><entry>6</entry><entry>H₂O</entry><entry>NaOH</entry><entry>100</entry><entry>EO, 50</entry><entry>709</entry><entry>5,3</entry><entry> 11,4 </entry></row><row><entry>7</entry><entry>H₂O</entry><entry>NaOH</entry><entry>50</entry><entry>-</entry><entry>2 000</entry><entry>11,4</entry><entry>0</entry></row><row><entry>8</entry><entry>H₂O</entry><entry>BF₃</entry><entry>100</entry><entry>-</entry><entry>1000</entry><entry>7,6</entry><entry>3,0</entry></row><row><entry>9</entry><entry>DAY</entry><entry>N / A</entry><entry>100</entry><entry> PO, 86</entry><entry>17 000</entry><entry>- 130,0</entry><entry>25,0</entry></row><row><entry>10</entry><entry>PG</entry><entry>KOH</entry><entry>14</entry><entry>EO, 50</entry><entry>1900</entry><entry>4,0</entry><entry>6.8</entry></row><row><entry>11</entry><entry>H₂O</entry><entry>KOH</entry><entry>50</entry><entry>EO, 25</entry><entry>1200</entry><entry>6,8</entry><entry>15,8</entry></row><row><entry>12</entry><entry>AG</entry><entry> KOH </entry><entry>75</entry><entry> PO, 29</entry><entry>6 500</entry><entry>44,5</entry><entry> U </entry></row><row><entry>13</entry><entry>CH₃OH</entry><entry>N / A</entry><entry>71</entry><entry>-</entry><entry>700</entry><entry>4,4</entry><entry>0</entry></row><row><entry>14</entry><entry>CH₃OH</entry><entry>BF₃</entry><entry>100</entry><entry>EO, 50</entry><entry>700</entry><entry>5,1</entry><entry>5,6</entry></row><row><entry>15</entry><entry> BPA </entry><entry> KOH </entry><entry>50</entry><entry>EO, 25</entry><entry>1200</entry><entry>5,6</entry><entry>3,2</entry></row><row><entry>16</entry><entry>AG</entry><entry>KOH</entry><entry>75</entry><entry>1000</entry><entry>6,5</entry></row></tbody></tgroup></p>

<p><tgroup cols="8"><tbody><row><entry></entry><entry>Initiator ■</entry><entry>catalyst</entry><entry> 25 06 803 </entry><entry> - </entry><entry>Molecular weight of the product</entry><entry>Monomer units per mole of TBGÄ others</entry><entry>0</entry></row><row><entry></entry><entry>2-ethyl-hexanol</entry><entry>N / A</entry><entry></entry><entry> - </entry><entry>700</entry><entry>4,4</entry><entry>0</entry></row><row><entry>continuation</entry><entry>isooctanol</entry><entry>N / A</entry><entry>Monomers, mol% TBGÄ others^b</entry><entry>EO, 75</entry><entry>600</entry><entry>3,6</entry><entry>11,5</entry></row><row><entry>Experiment No.</entry><entry>glycerin</entry><entry>KOH</entry><entry>100</entry><entry>PO, 91</entry><entry>1 100</entry><entry>3,9</entry><entry>47,5</entry></row><row><entry>17 ·</entry><entry>p-400</entry><entry>N / A</entry><entry>100</entry><entry>THF, 54</entry><entry>3 300</entry><entry>4,0</entry><entry>8.6</entry></row><row><entry>18</entry><entry>H₂O</entry><entry>BF₃</entry><entry>25</entry><entry>EO, 79 ^c</entry><entry>1600</entry><entry>7,4</entry><entry>30,0</entry></row><row><entry>19</entry><entry>H₂O</entry><entry>KOH</entry><entry>9</entry><entry>PO, 29</entry><entry>2 300</entry><entry>8,0</entry><entry>2.0</entry></row><row><entry>20</entry><entry>CH₃OH</entry><entry>BF₃</entry><entry>46</entry><entry>BO, 50</entry><entry>800</entry><entry>5,0</entry><entry>&gt;5 000</entry></row><row><entry>21</entry><entry>none</entry><entry>Al (At)₃</entry><entry>21</entry><entry>-</entry><entry>&gt; 1 x 10 &lt;·</entry><entry>&gt;5 000</entry><entry>3,0</entry></row><row><entry>22</entry><entry>DAY</entry><entry>N / A</entry><entry>71</entry><entry>-</entry><entry>6 150</entry><entry>46,0</entry><entry>1,0</entry></row><row><entry>23</entry><entry>EW</entry><entry>BF₃</entry><entry>50</entry><entry>PO, 67</entry><entry>1000</entry><entry>7,2</entry><entry>7.9</entry></row><row><entry>24</entry><entry>H₂O</entry><entry>KOH</entry><entry>100</entry><entry>EO, 75</entry><entry>996</entry><entry>4,0</entry><entry>57,3</entry></row><row><entry>25</entry><entry>H₂O</entry><entry>KOH</entry><entry>100</entry><entry>EO, 50</entry><entry>5 000</entry><entry>19,0</entry><entry>29,3</entry></row><row><entry>26</entry><entry>H₂O</entry><entry>KOH</entry><entry>33</entry><entry>PO, 48; BO, 39</entry><entry>5 100</entry><entry>29,3</entry><entry>9.8 BO 12.1 PO</entry></row><row><entry>27</entry><entry>EW</entry><entry>KOH</entry><entry>25</entry><entry>EO, 75</entry><entry>1820</entry><entry>3,1</entry><entry>229,0</entry></row><row><entry>28</entry><entry>EW</entry><entry>KOH</entry><entry>50</entry><entry>EO, 90</entry><entry>20 000</entry><entry>76,3</entry><entry>85,6</entry></row><row><entry>29</entry><entry>H₂O</entry><entry>KOH</entry><entry>13</entry><entry>EO, 95</entry><entry>5 000</entry><entry>9,5</entry><entry>11.8</entry></row><row><entry>30</entry><entry>H, 0</entry><entry>KOH</entry><entry>25</entry><entry></entry><entry>6 000</entry><entry>6,2</entry></row><row><entry>31</entry><entry></entry><entry></entry><entry>10</entry><entry></entry><entry></entry></row><row><entry>32</entry><entry></entry><entry></entry><entry>5</entry><entry></entry></row><row><entry>33</entry><entry></entry></row><row><entry></entry></row></tbody></tgroup></p>

'TAG = tri-ethylene glycol. ÄG = Ählhylenglycol. PG = propylene glycol. BPA = bisphenol A and P-400 = polypropylene glycol of molecular weight 400.

¹¹ PO is propylene oxide. ÄO isi ethylene oxide, THF is tetrahydrofuran and BO is 1,2-butylcnoxide.

^c Block copolymer. by reacting one equivalent of water with first 6 equivalents of EA. then 4 equivalents TBGÄ. then 12 equivalents of AO, then 4 equivalents of TBGA and finally 12 equivalents of AO was obtained.

^d triethylaluminum

B. Dealkylation and esterification of the polymers of Table I.

The polymers of Table 1 have η terminal hydroxyl groups, where η indicates the functionality or valence of the initiator RH ". These hydroxyl groups can be esterified by reaction with an acid anhydride or in the presence of a base with an acid halide without disturbing the tertiary butoxy groups. Attempts to esterify with a carboxylic acid in the presence of a siark acidic catalyst lead to a dealkylation (loss of isobutylene), at the same time occurs esterification of the forming primary hydroxyl groups. Therefore, a particular feature of this invention is the discovery that the polymers and copolymers of the tertiary butylglycidyl ether can be terminally esterified independently of the tertiary butoxy groups and that the latter groups dealkyllert simultaneously and in a single step and to any desired extent by reaction with a carboxylic acid can be esterified. The latter reactions are catalyzed by strongly acidic catalysts, in particular by arylsulfonic acids.

The esterification of the terminal hydroxyl groups of the polymers and copolymers of tertiary butyl ether and the use of acid halides or the partial esterification with acid anhydrides can be achieved under mild conditions, such as at 30 to 90 ° C, whereas the dealkylation and / or esterification with carboxylic acids acidic catalysts and Temperatures of about 90 ° C or higher required for a satisfactory reaction rate. Temperatures of about 120 to 150 ° C are generally preferred. When very easily polymerizable acids such as acrylic acid or methacrylic acid are used, it is necessary to use a polymerization inhibitor such as Cu₂O or hydroquinone. However, lower temperatures, such as 90 to 110 ° C may be used to absorb this higher reactivity. The progress of the reactions can be tracked by measuring the amount of isobutylene and / or water formed. The removal of the water can be by adding a solvent, such as toluene, with

Water forms a low-boiling azeotropic mixture, be relieved. As the desired end products have a certain content of non-esterified hydroxyl groups, this is usually accomplished by adding to the reaction mixture only the amount of acid or acid anhydride required to esterify the hydroxyl groups in the desired proportion. But you can also use an excess of acid and monitor the esterification by measuring the amount of water formed and stops the reaction at the desired point. The removal of isobutylene and / or water can be facilitated by passing a slow stream of an inert gas through the reaction mixture.

Since the presence of some primary hydroxyl groups in the products is desired, these examples show only a partial esterification of the polymers. However, complete esterification can be readily achieved by using at least the stoichlometric amount of the acyllate and continuing the reaction until essentially complete. To this was repeated the reaction of Run 49 except that 46 moles of stearic acid were used. The product obtained was completely esterified and contained essentially no primary hydroxyl groups.

Table II shows the results of a series of experiments in which the polymers listed in Table I are dealkyiated and partially esterified as described above. The starting material is identified by specifying the experimental number of Table I. The amount of acid used for the esterification reaction is based on the starting material in moles / mol. It should be noted that in most cases an excess of acid was used. When esterification was carried out stepwise with two different acids, the acid used in the first step was completely reacted and then the second acid was added and reacted either partially or completely (e.g., Runs 45, 49, 55 and 61) , In all experiments using both acrylic acid and maleic anhydride, these two starting materials were mixed and reacted simultaneously.

In Table II, the products are characterized by the number of α, β-unsaturated acyl groups, the number of any other acyl groups that may be present, and the number of primary hydroxyl groups (glycidol units) per molecule of the final product. The ester groups were determined by NMR spectroscopy and the hydroxyl groups were calculated from the difference. All calculations are based on the molecular weight shown in Table I.

<p><tgroup cols="9"><tbody><row><entry></entry><entry>Table II</entry><entry> Starting material </entry><entry> Acylating agent · </entry><entry>2,3</entry><entry> final product, </entry><entry> Units / mol </entry><entry> other ^b</entry><entry>1,5</entry></row><row><entry>ί</entry><entry></entry><entry> Table I experiment no. </entry><entry> Mol / mol </entry><entry>8,8</entry><entry> unsaturated ester</entry><entry> primary hydroxyl </entry><entry></entry><entry>2,0</entry></row><row><entry></entry><entry> Trial 35 ^No· </entry><entry>1</entry><entry>AS,</entry><entry>2,9</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry>2</entry><entry>AS,</entry><entry>26,0</entry><entry></entry><entry></entry><entry></entry><entry>2,0</entry></row><row><entry></entry><entry>34</entry><entry>3</entry><entry>AS,</entry><entry>56,5</entry><entry></entry><entry></entry><entry></entry><entry>0,5</entry></row><row><entry></entry><entry>35</entry><entry>4</entry><entry>AS,</entry><entry>4,0</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry> ι </entry><entry>36</entry><entry>5</entry><entry>AS,</entry><entry>4,7</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry> ί </entry><entry>37</entry><entry>1</entry><entry>AS,</entry><entry>8_:2</entry><entry></entry><entry></entry><entry></entry><entry>1.5</entry></row><row><entry></entry><entry>38</entry><entry>3</entry><entry>AS,</entry><entry>3,0</entry><entry>1,7</entry><entry>0,2</entry><entry></entry></row><row><entry></entry><entry>39</entry><entry>5</entry><entry>AS.</entry><entry>7,5</entry><entry>1,9</entry><entry>0,4</entry><entry></entry></row><row><entry></entry><entry>40</entry><entry>7</entry><entry>AS,</entry><entry>129,0</entry><entry>4,7</entry><entry>0,6</entry><entry></entry></row><row><entry></entry><entry>⁵⁽¹ 41</entry><entry>6</entry><entry>MAS,</entry><entry>3,5</entry><entry>3,0</entry><entry>8,5</entry><entry></entry></row><row><entry></entry><entry>42</entry><entry>9</entry><entry>MAS,</entry><entry>4,0</entry><entry>5,3</entry><entry>0,2</entry><entry></entry></row><row><entry> &gt; Ι </entry><entry>43</entry><entry>10</entry><entry>AS,</entry><entry>8,9</entry><entry>96,0</entry><entry>34,0</entry><entry>octanoate,</entry></row><row><entry></entry><entry> 55 44 </entry><entry>10</entry><entry>AS,</entry><entry>11,5</entry><entry>2,4</entry><entry>0,2</entry><entry>maleate,</entry></row><row><entry> S </entry><entry>45</entry><entry>11</entry><entry>AS,</entry><entry>26,4</entry><entry>3,9</entry><entry>0,1</entry><entry></entry></row><row><entry></entry><entry>46</entry><entry>11</entry><entry>AS,</entry><entry>7,0</entry><entry>4,7</entry><entry>. 2,2</entry><entry>maleate,</entry></row><row><entry> i </entry><entry> wi 47 </entry><entry>12</entry><entry>AS,</entry><entry>8,3</entry><entry>5,3</entry><entry>1,6</entry><entry>phthalate,</entry></row><row><entry> 1 </entry><entry>48</entry><entry>13</entry><entry>AS,</entry><entry>5,8</entry><entry>20,8</entry><entry>3,8</entry><entry></entry></row><row><entry> I </entry><entry>49</entry><entry>15</entry><entry>AS,</entry><entry></entry><entry>3,5</entry><entry>0,9</entry><entry></entry></row><row><entry></entry><entry> 65 50 </entry><entry>16</entry><entry>AS,</entry><entry>3,9</entry><entry>1,7</entry><entry>TB Ä,</entry></row><row><entry> 1 </entry><entry>51</entry><entry></entry><entry>2,3</entry><entry>3,4</entry><entry></entry></row><row><entry></entry><entry>52</entry><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row></tbody></tgroup></p>

continuation

No.

starting material

Table I experiment no.

Final product. Units / mol

Acylating agent ■

Mol / mol

unsaturated ester

primary hydroxyl

other'

<p><tgroup cols="7"><tbody><row><entry>53</entry><entry>17</entry><entry>AS,</entry><entry>8,4</entry><entry>2,8</entry><entry>1,8</entry><entry>HDC, 0.5</entry></row><row><entry>54</entry><entry>18</entry><entry>AS,</entry><entry>8,6</entry><entry>2,6</entry><entry>2,2</entry><entry></entry></row><row><entry>55</entry><entry>19</entry><entry>AS,</entry><entry>7,5</entry><entry>3,0</entry><entry>0,9</entry><entry></entry></row><row><entry>56</entry><entry>16</entry><entry>AS,</entry><entry>7,0</entry><entry>4,8</entry><entry>2,4</entry><entry></entry></row><row><entry>57</entry><entry>20</entry><entry>AS.</entry><entry>4,7</entry><entry>2,1</entry><entry>1,9</entry><entry></entry></row><row><entry>58</entry><entry>21</entry><entry>AS,</entry><entry>9,7</entry><entry>4,0</entry><entry>3,5</entry><entry></entry></row><row><entry>59</entry><entry>3</entry><entry>AS,</entry><entry>2,9</entry><entry>1,1</entry><entry>1,2</entry><entry>Stearate 2.5</entry></row><row><entry>60</entry><entry>22</entry><entry>AS,</entry><entry>9,8</entry><entry>5,3</entry><entry>2,5</entry><entry></entry></row><row><entry>61</entry><entry>23</entry><entry>AS,</entry><entry>6,6</entry><entry>4,0</entry><entry>1,0</entry></row><row><entry>62</entry><entry>8</entry><entry>MA,</entry><entry>4,7</entry><entry>4,7</entry><entry>0,3</entry></row><row><entry>63</entry><entry>24</entry><entry>AS,</entry><entry>100%'</entry><entry>50%^c</entry><entry>50%^c</entry></row><row><entry></entry></row><row><entry></entry></row><row><entry></entry></row></tbody></tgroup></p>

'AS = acrylic acid. MA = maleic anhydride. MAS = methacrylic acid

The maleates are maleic acid halides obtained by reaction with maleic anhydride The phthalate was the diester obtained by reaction with the anhydride TBA = tertiary butyl ether ie incomplete dealkylated material HDC ester = hcpandicarboxylal.

Since the molecular weight of the starting material (Run 24) was too high to be reliably determined, the results are expressed as a percentage rather than in moles, ie the starting material was reacted with a large excess, more than 100% by weight of acrylic acid. whereby 50% of the hydroxyl groups present were esterified.

Table HI summarizes the results of another series of experiments in which the products are characterized by the number of acyl groups and the number of primary hydroxyl groups (glycidol unit p.n) per molecule of the final product. The ester groups were determined by NMR spectroscopy and the hydroxyl groups by reaction with TrifluoresslgsSure. All calculations are based on the molecular weights given in Table I.

<p><tgroup cols="6"><tbody><row><entry>Table III</entry><entry> Starting Color Table I Experiment No. </entry><entry> Acylating agent mol / mol </entry><entry>4,8</entry><entry> Final product. </entry><entry> Units / mol </entry></row><row><entry></entry><entry>8</entry><entry>Stearic.</entry><entry>7,3</entry><entry> ester </entry><entry> Primary hydroxyl </entry></row><row><entry> Experiment No. </entry><entry>8</entry><entry>Stearic.</entry><entry>9,2</entry><entry>4,8</entry><entry>2,9</entry></row><row><entry>64</entry><entry>25</entry><entry>Stearic.</entry><entry>27,6</entry><entry>7,3</entry><entry>0,4</entry></row><row><entry>65</entry><entry>25</entry><entry>Stearic.</entry><entry>4,1</entry><entry>9,2</entry><entry>36.8</entry></row><row><entry>66</entry><entry>26</entry><entry>Stearic.</entry><entry>2,5</entry><entry>27,6</entry><entry>18,4</entry></row><row><entry>67</entry><entry>27</entry><entry>PA</entry><entry>4,0</entry><entry>4,1</entry><entry>3,1</entry></row><row><entry>68</entry><entry>28</entry><entry>Stearic.</entry><entry>1,5</entry><entry>2,5</entry><entry>2,3</entry></row><row><entry>69</entry><entry>28</entry><entry>Stearic.</entry><entry>1,6</entry><entry>4,0</entry><entry>15.0</entry></row><row><entry>70</entry><entry>29</entry><entry>Stearic.</entry><entry>4,0</entry><entry>1,5</entry><entry>17.5</entry></row><row><entry>71</entry><entry>29</entry><entry>Stearic.</entry><entry>15,5</entry><entry>1,6</entry><entry>27.7</entry></row><row><entry>72</entry><entry>29</entry><entry>Stearic.</entry><entry>23,0</entry><entry>4,0</entry><entry>25,3</entry></row><row><entry>73</entry><entry>29</entry><entry>Stearic.</entry><entry></entry><entry>15,5</entry><entry>13,8</entry></row><row><entry>74</entry><entry></entry><entry>23,0</entry><entry>6.3</entry></row><row><entry>75</entry><entry></entry><entry></entry></row><row><entry></entry><entry></entry></row><row><entry></entry><entry></entry></row></tbody></tgroup></p>

continuation

"Try No.

starting material

Table I experiment no.

<p><tgroup cols="2"><tbody><row><entry>acylating</entry><entry>1,6</entry></row><row><entry>Mol / mol</entry><entry>7,7</entry></row><row><entry>Laurin.</entry><entry>15,5</entry></row><row><entry>Laurin.</entry><entry>23,0</entry></row><row><entry>Laurin.</entry><entry>1,5</entry></row><row><entry>Laurin.</entry><entry>1,5</entry></row><row><entry>Stearic.</entry><entry>1,5</entry></row><row><entry>Laurin.</entry><entry>5,8</entry></row><row><entry>Octane.</entry><entry>1,0</entry></row><row><entry>Stearic.</entry><entry>1,0</entry></row><row><entry>FA-2 »</entry><entry>1,5</entry></row><row><entry>TFS-2 ^a</entry><entry></entry></row><row><entry>acetic acid</entry><entry>3,4</entry></row><row><entry>anhydride</entry><entry>0,5</entry></row><row><entry>AS</entry><entry>4,8</entry></row><row><entry>ADCS</entry></row><row><entry>AS</entry></row><row><entry></entry></row></tbody></tgroup></p>

<p><tgroup cols="2"><tbody><row><entry>final product,</entry><entry>Units / mol</entry></row><row><entry>ester</entry><entry>Primary hydroxyl</entry></row><row><entry>1,6</entry><entry>27,7</entry></row><row><entry>7,7</entry><entry>21,6</entry></row><row><entry>15,5</entry><entry>13.8</entry></row><row><entry>23,0</entry><entry>6,3</entry></row><row><entry>1,5</entry><entry>2.5</entry></row><row><entry>1,5</entry><entry>2,5</entry></row><row><entry>1,5</entry><entry>2.5</entry></row><row><entry>5,8</entry><entry>70,5</entry></row><row><entry>1,0</entry><entry>8,5</entry></row><row><entry>1,0</entry><entry>5,2</entry></row><row><entry>4,9</entry><entry>0,2</entry></row></tbody></tgroup></p>

76 77 78 79

¹⁵ 80 81 82

2" 83 84 85

25 86

87

29 29 29 29 10 10 10 31 32 33 14

16

5,3

2,4

PA = phthalic anhydride. HDCS = heptanedicarboxylic acid and FA-2 is a mixture of tall oil celts.

The products shown in Tables II and HI are not pure compounds but mixtures whose average composition is given. When the number of primary hydroxyl groups is less than one. this means that some molecules do not contain such a group. It has been found that the advantageous properties and uses of the products according to the invention are frequently also present in such mixtures, if on average only a small part, such as 10%, of the molecules contains the ester groups and the primary hydroxyl groups.

The esters shown in Table II, depending on their molecular weight and functionality, are oil-like liquids to resinous solids. They are all readily soluble in most organic solvents, but in water some are insoluble or only slightly soluble depending on the number and size of hydrophobic groups present.

To demonstrate the usefulness of the esters of Table II, they were applied alone or in admixture with another polymerizable monomer to a sheet of cold rolled steel as a film about 0.025 mm thick. The coatings were then exposed to a radiation dose of 1 to 3 megarads in the form of a 2-milli-volt volt electron beam. The resulting films were harder and more waterfast after irradiation than before.

These compounds were also coated on paper and on an aluminum substrate and cured by exposure to UV light from a 100 watt mercury arc at a distance of 5 mm for one second. Also in this case, the films were harder and more water resistant after irradiation. It follows that a polymerization and / or crosslinking has occurred by the action of the UV light.

In other experiments, the polymers of Table II were acidified with phosphoric acid and mixed with 15% by weight of a 40% aqueous solution of glyoxal. The solutions were coated as films on an aluminum surface and dried at room temperature or at 60 ° C. In both cases, a tack-free, water-insoluble coating was obtained which was readily soluble in aqueous alkali. When the films were irradiated with ultraviolet light or an electron beam, they also became insoluble in alkali.

In these coating experiments, the compounds of Table II were used alone or in admixture with up to 98% of one or more other polymerizable vinyl compounds. Such vinyl monomers were, for example, butyl acrylate, 2-hydroxypropyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile and styrene. In each case, a crosslinked polymer was obtained.

The esters of Table III were ö'iartlge liquids or solids depending on their molecular weight and their functionality. In most cases, they were well soluble in most organic solvents and some were soluble to slightly soluble in water.

In the following series of experiments, the use of the compounds of Table II as surface-active agents is explained.

10

A commercial clay powder was coated with 0.1% by weight of the compound to be tested, and the wetting time of the clay was then determined. In this experiment, the wetting tent was the time required for a clay sample to sink to the bottom of a one liter graduated cylinder containing one liter of water. The tent was measured by placing the clay on the surface of the water.

The results are summarized in the following table. The compounds are identified by the experimental number of Table III.

Table IV

Experiment No.

88 89 90 91 92 93

Compound of Table III

73 74 77 78 81 none

Wetting time, sec.

5 4 4 3 3 &gt;25

Due to their free hydroxyl groups, the compounds of the invention are reactive with and crosslinkable by polyfunctional compounds which react with reactive hydroxyl groups, such as formaldehyde, glyoxal and organic polyisocyanates. By using such curing rolls, curable coatings can be applied to various substrates and then cured into tough, UV resistant coatings. Such Arbeltswelsen are explained in the following experiments.

The compounds are identified by their experimental number in Table III. In each experiment, the compound was mixed with the indicated percentage of hexakis (methoxymethyl) melamine. The composition was then applied to aluminum plates and cured in an oven for S minutes at 180 ° C.

The cured coatings were smooth and strongly adherent. When immersed in water for 1 hour, no deterioration of adhesion or other visible effects occurred. The resistance to organic solvents was determined by wetting the surface with methyl ethyl ketone (MAK) and rubbing with a finger until visibly releasing, rupturing or otherwise damaging the film. The results are given in the following table.

<p><tgroup cols="4"><tbody><row><entry> Table V </entry><entry> Connection Experiment No. of Table III </entry><entry> % HMM *) </entry><entry> Number of MÄK friction </entry></row><row><entry> Experiment No. </entry><entry> 80 </entry><entry> 21 </entry><entry> 24 </entry></row><row><entry> 94 </entry><entry> 81 </entry><entry> 22 </entry><entry> &gt;100 </entry></row><row><entry> 95 </entry><entry> 82 </entry><entry> 22 </entry><entry> &gt;100 </entry></row><row><entry> 96 </entry><entry></entry><entry></entry></row><row><entry></entry></row></tbody></tgroup></p>

*) Hexakis (methoxymethyl) melamine