FR2778183A1 - Cyclic organoboron (meth)acrylic and allylic derivatives, useful polymerizable monomers - Google Patents

Abstract

Cyclic organoboron (meth)acrylic and allylic derivatives are new. Cyclic organoboron derivatives of formula (I) are new: A = a residue of formula (a) or (b) R2 = H or CH3; R3(same or different) = H or alkyl; n = 2-20; B = boron; R<1> = alkylene, arylene or bivalent heterocyclic residue; either x = 0, y = 1 and z = 0 simultaneously or x = 1, y = 0 and z = 1 simultaneously.

Description

NEW CYCLIC BORON (METH) ACRYLIC COMPOUNDS AND

ALLYLICS, THEIR MANUFACTURING PROCESS AND THEIR APPLICATION

A SYNTHESIS OF NEW (CO) POLYMERS

The present invention relates to novel boron cyclic (meth) acrylic and allylic compounds, a process for making these compounds, and the application of the latter to the synthesis of novel compounds.

polymers and copolymers.

It is widely known that boric acid B (OH) 3 can be esterified into boric esters, and that boric esters can, for their part, be transesterified into other esters (US Pat. No. 2,088,935; Bull. Soc. Chim. Belg., Volume 48, 1939 n 3; J. Appl. Chem., February 4, 1954). It is also known that boric acid or boric esters react with certain difunctional compounds to generate stable cyclic structures: O (CO) x \ R and R 'having various meanings, and x, y and z being as defined hereinafter with reference to the compounds of formula (I) (J. Chem. Soc. 1032, 1962; Indian Chem. Soc.

Flight. 38, No. 1, 1961; J. Chem. Soc. 1959, 1529).

However, no compounds of the general formula above are known at the present time, the group R of which is an allylic or (meth) acrylic group. However, it would be of great interest to be able to easily and economically synthesize such monomers bearing boron ester groups, in order to be able, according to well-known (co) polymerization techniques, to polymerize or copolymerize them with other monomers such as than vinyl and acrylic monomers. This would make it possible to obtain (co) polymers having side chains carrying borated ester functions, which could subsequently

be readily hydrolyzed.

The (co) polymers having pendant chains carrying boron functions are likely, because of the intrinsic properties of boron and boron esters, to present many advantages in fields as varied as nuclear (neutron absorption) or marine paints. (self-leveling of paints), by giving the formulations in which they are incorporated, the

properties specific to boron and boron derivatives.

The applicant company has now developed a process for the synthesis of new borated (meth) acrylic or allylic ester monomers meeting the objectives sought. This new process consists in reacting, in a first step, boric acid or a boron ester with a bifunctional compound of the diol, amino acid, etc. type, the two functional groups of which can be exchanged with two boron ligands, then , in a second step, in exchanging the last ligand with an unsaturated alcohol, allylic or (meth) acrylic, by esterification or transesterification depending on whether the acid has been used

boric or a borated ester.

A subject of the present invention is therefore first of all a compound represented by formula (I): / O (CO) x

A-O-B \ R1 (I)

(O) NH) z in which:

R2

I 3

- A represents a residue CH2 = C-C- (CHR 3) n-

I (R2 representing hydrogen or CH3; the R3, identical or different each representing hydrogen or alkyl; and n = 2-20) or a residue CH2 = CH-CH2-; - B represents boron; - R1 represents an alkylene residue, an arylene residue or the divalent residue of a heterocyclic compound; and - or else simultaneously x = O; y = 1; z = 0O; or

simultaneously x = 1; y = O; z = 1.

By way of example of compounds of formula (I), mention may be made of those for which R1 represents an alkylene residue - (CR4R5) 2 or 3-, the R4 and R5 each independently representing hydrogen or C1-C3 alkyl, or else a

remains orthophenylene.

As examples of divalent residues of a heterocyclic compound falling within the definition of R1, there may be mentioned the residues of heterocyclic compounds whose heteroatoms are chosen from N, O and S. The present invention also relates to a process for the manufacture of a compound of formula (I) as defined above, characterized in that: - in a first step, a compound of formula (II) is reacted:

B (OR6) 3 (II)

in which R6 represents H or C1-C6 alkyl, with a compound of formula (III): HO (CO) xR1 (NH) z (O) yH (III)

in which R1, x, y and z are as defined above

above; and in a second step, the compound of formula (IV) obtained is reacted: R6-cEO (CO) xR (V Ra - O- B / R (IV) with a compound of formula (V):

AOH (V)

in which A is as defined above.

The above two reactions are generally carried out under stoichiometric or substantially

stoichiometric. The temperature of the reaction medium during each step is generally between 50 and 5 120 C, preferably between 75 and 95 C.

Furthermore, at each stage, the procedure is generally carried out by distilling off the compound R6OH -

water or light alcohol - as it is formed, each of the reactions can advantageously be carried out in an aliphatic or aromatic solvent which forms an azeotrope with said compound R6OH. Among the solvents which can be used, there may be mentioned, in a nonlimiting manner, cyclohexane, toluene, heptane and hexane. The second step is generally carried out under air bubbling in the presence of at least one polymerization inhibitor, at a rate of 100 to 5,000 ppm relative to the

final product (I). The polymerization inhibitor can be selected, for example, from hydroquinone monomethyl ether, hydroquinone, phenothiazine and ditertiobutylparacresol.

The present invention finally relates to the application of the new compounds of formula (I), which have been described above, to the constitution of new polymers and copolymers. More specifically, the present invention relates to polymers and copolymers comprising at least one unit derived from at least one compound of formula (I). Such

copolymers may further comprise at least one unit derived from at least one comonomer copolymerizable with said compound of formula (I), such as a vinyl or acrylic comonomer.

The following Examples illustrate the present invention without, however, limiting its scope. Percentages are by weight unless otherwise indicated. The following abbreviations were used: HEMA: 2-hydroxyethyl methacrylate HEA: 2-hydroxyethyl acrylate EMHQ: hydroquinone monomethyl ether

EXAMPLE 1

First step HereC I% cI,

B (OCM) HO - C-CI <H-OH CCH2 2 C% OH

CC \ In a reactor stirred using an anchor and surmounted by a Multiknit packed distillation column (12 theoretical plates), are introduced: - 208 g (2 moles) of trimethylborate; - 236 g (2 moles) of 2-methyl-2,4-pentanediol; and

- 250 ml of toluene.

The mixture is heated under an operating pressure of 2.66 x 104 Pa (200 mm Hg) and the methanol is distilled off in the form of an azeotrope with toluene. The temperature of

column head is 30 C; the temperature of the reactor changes from 40 to 900C.

The amount of methanol distilled off in the first step is 128 g (4 moles). At the end of the first stage, 457 g of toluene / methyl 1,1,3-trimethyltrimethylene borate mixture containing 69.1% of methyl 1,1,3-trimethyltrimethylene borate are obtained. Second stage CH3x / CH3

O-C CH3

CH30-B CH2 + CH2 = --- C-O-CH2-CH2-OH

O-C CH3

CH3 \ CH3

CH3 0-C

- 'CH2 = C-C-O - CH2-CH2 -_- B CH2 + CH30H

The following are then charged into the reactor: - 144 g of toluene; - 0.26 g (500 ppm) of EMEHQ;

- 260 g of HEMA.

Air bubbling is maintained in the reactor and the transesterification reaction is carried out by distilling off the toluene / methanol azeotrope. The second step is carried out under 2.66 x 104 Pa

(200 mmHg) between 85-95 C.

The excess toluene is then removed by distillation by gradually lowering the pressure of

2.66 x 104 Pa to 2.66 x 103 Pa (200 mmHg to 20 mmHg).

At the end, 508.8 g (yield> 99%) are recovered, the structure of which was verified by 13C NMR and by

IRTF, corresponds to that of the expected methacrylic ester.

EXAMPLE 2 Synthesis of the compound of formula:

CH3 / CH3

-Cx

CH2 = CH-CH2-O - B CH2

CH3 Example 1 is repeated, replacing the HEMA by

allylic alcohol.

302.9 g of a solution of methyl 1,1,3-trimethyltrimethylene borate at 48.7% in toluene are mixed with

41 g of allyl alcohol. 0.08 g of QMEA is added, and air bubbling is maintained throughout the reaction.

The reaction is carried out under a pressure of 2.66 x 104 Pa (200 mmHg) by removing the methanol generated in the form of an azeotrope with toluene. Temperature

reaction range is between 80 and 90 C.

The excess toluene is then removed by distillation by gradually lowering the pressure of

2.66 x 104 Pa to 2.66 x 103 Pa (200 mmHg to 20 mmHg).

150 g (yield: 94.6%) are recovered at the end of a liquid product whose structure, established by 13C NMR,

corresponds to that of the expected compound.

EXAMPLE 3 Synthesis of the compound of formula:

CH3 \ / CH3

0-C

CH2 = CH-C-0-CH2-CH2-0-B C2

II \ 1 CH3 Example 1 is repeated, replacing the HEMA by

1'HEA.

Starting with 310.1 g of a solution of methyl 1,1,3-trimethyltrimethylene borate 48.4% in

toluene and 110.2 g of HEA, 225 g10 (yield: 98%) of boron acrylic ester having the expected structure are obtained at the end.

EXAMPLE 4 Synthesis variant of the compound prepared for

Example 1

Example 1 is repeated, replacing the borate

methyl with butyl borate B (OBu) 3. The entire synthesis is carried out without solvent.

Starting with 1 mole of butyl borate, one mole of 2-methyl-2,4pentanediol and one mole of HEMA, we

At the end, 254 g (yield> 99%) of the expected boron methacrylic ester are obtained.

EXAMPLE 5 Synthesis variant of the compound prepared from

Example 1

Example 1 is repeated, replacing the methyl borate with boric acid B (OH) 3.

Boric acid (62 g; 1 mole) is reacted with 2-methyl2,4-pentanediol (118 g; 1 mole) in toluene medium (210.6 g), at a temperature of about 80 C, under a pressure of 2.66 x 104 Pa (200 mm Hg). The water of reaction is removed as an azeotrope with toluene. The amount of distilled water is 36 g, which corresponds to 100% conversion into:

CH3 / CH3

HO-B CH2

O-CH UI3 CH3

structure identified by 13C NMR.

130 g of HEMA (1 mole) and 13 g of HEMA are then introduced into the medium. The esterification is carried out under air bubbling. Water of reaction (17.5 g)

is removed by distillation as a toluene / water azeotrope. At the end, after distillation of the excess toluene, 254 g of the expected boron methacrylic ester are obtained (yield> 98%).

EXAMPLE 6 Synthesis of the compound of formula: CH3

CH2 = C-C - CH-C2-O-I <I

III

Example 4 is repeated, replacing 2-methyl-

2,4-pentanediol by catechol.

The butyl borate (345 g; 1.5 mol) is charged to the reactor with the catechol (165 g; 1.5 mol), in the presence of 220 g of toluene. The mixture is heated under a pressure of 1.33 x 104 Pa to 6.66 x 103 Pa (100 to

mmHg) at a temperature of 80 to 120 C, removing the butanol in the form of a toluene / butanol azeotrope.

The following intermediate product is thus obtained: BuC) -B ::

'NOT. <

structure which was confirmed by NMR.

Then introduced 130 g (1.5 mol) of HEMA, 0.19 g of MHQ, and the temperature of the mixture is brought to -1350C under a pressure which is changed from

6.66 x 103 Pa to 1.33 x 103 Pa (50 to 10 mmHg).

After removing the excess toluene, 370 g (yield: 99.5%) of the ester are obtained at the end.

borated methacrylic expected.

EXAMPLE 7 Synthesis of the compound of formula: CH3

CH3 1O-C-CH3

CH2 = C-C - O-CH2-CH2 - O-E <

IH O-C-CH3

OI CH3

Example 5 is repeated, replacing 2-methyl-

2,4-pentanediol by pinacol. At the end, the expected boron methacrylic ester is obtained with a yield of 98%.

EXAMPLE 8 Synthesis of the compound of formula:

CH3 -C CH3

CH2 = C-C-O CH2-CH2 - B Cc I l /

O 0 - CH2

Example 5 is repeated, replacing 2-methyl-

2,4-pentanediol by neopentylglycol. At the end, the expected borated methacrylic ester is obtained with a yield of

99.5%.

EXAMPLE 9

First step Example 4 is repeated, replacing 2-methyl-

2,4-pentamethiol with anthranilic acid.

NH MIN

B (OBU) 3> B-OBu + 2BOH C - OH v Il

O O

230 g (1 mole) of butyl borate B (OBu) 3 are mixed with 137 g (1 mole) of anthranilic acid in the medium

toluene (400 g).

The mixture is heated to a temperature between 80 and 120 ° C. while changing the pressure from 1.33 x 104 Pa to 2.66 x 103 Pa (100 to 20 mmHg). Butanol is removed as an azeotrope

toluene / butanol, then the excess toluene.

The intermediate compound which appears is isolated

in the form of a solid with a yield of 95%.

Second step NEl CH3 <B-OBu + CH2 = C-C-O - CH2- CH2-OH Co O

NH-I CH3

BO-CH2-CH2-O - CC - = CH2 + BuOH o il O 197.1 g (0.9 mol) of the compound thus obtained are then reacted with 117 g (0.9 mol) of HEMA in presence of 0.13 g of EMEH and under air bubbling at a temperature between 100 and 130 C, by changing the pressure from 6.66 x 103 Pa to 1.33 x 103 Pa (50 to 10 mmHg) . The butanol generated is removed as it is formed by distillation. The conversion rate,

calculated from the butanol formed, is greater than 99%.

At the end, 245 g of a very viscous liquid are obtained, the structure of which, confirmed by 13C NMR, is the

expected structure.

EXAMPLE 10 Synthesis of the compound of formula:

CH3 O0-CH2

I / \

CHI2-C-C-O-CH2-CH2 - O- B CH-CH3

O O - CH2

Example 5 is repeated, replacing 2-methyl-

2,4-pentanediol by 2-methyl-1,3-propanediol. At the end, the boron methacrylic ester is obtained with a

96.5% yield.

EXAMPLE 11 Synthesis of the compound of formula: / CH3 CH3 / p- CH ^ CHj = C-1-0-CHI-CH2 - Bu CH2

0 O-CH2

Example 5 is repeated, replacing 2-methyl-

2,4-pentadiol by butanediol-1,3. At the end, the expected borated methacrylic ester is obtained with a yield of

98.2%.

EXAMPLE 12 Synthesis of the compound of formula:

CH3 0-CH2

I \., CH2-CH3

CHC2 - C-0-CH2-CH2-0-B CH

it \ / NC H2-CH3 o O-CH2C

Example 5 is repeated, replacing 2-methyl-

2,4-pentanediol by 2,2-diethyl-propanediol-1,3. At the end, with a yield of 95%, the ester

borated methacrylic expected.

Claims (5)

1 - Compound represented by the formula (I): / O (CO) x \ A-OO-B \> / in which: R2 I - A represents a residue CH2 = CC- (CHR3) n II o (R2 representing hydrogen or CH3; the R3, identical or different each representing hydrogen or aikyle; and n = 2-20) or a residue CH2 = CH-CH2 -; - B represents boron; - R 1 represents an alkylene residue, an arylene residue or the divalent residue of a heterocyclic compound; and - or else simultaneously x = 0; y = 1; z = 0; or simultaneously x = 1; y = O; z = 1. 2 - Compound represented by formula (I), characterized in that R represents an alkylene residue - (CR4R5) 2ou3- the R4 and R5 each independently representing hydrogen or C1-C3 alkyl, or an orthophenylene residue. 3 - Process for manufacturing a compound such as defined in one of claims 1 and 2, characterized by the fact that: - in a first step, a compound of formula (II) is reacted: B (OR6) 3 (II) in which R6 represents H or C-C6 alkyl, with a compound of formula (III): HO (CO) xR1l (NH) z (O) yH (III) in which Ri, x, y and z are as defined to claim 1; and - in a second step, the compound of formula (IV) obtained is reacted: O (Co) x \ (094HÉ (IV) with a compound of formula (V) AOH (V) wherein A is as defined in claim 1. 4 - Process according to claim 3, characterized in that the two reactions are carried out under stoichiometric or substantially stoichiometric conditions. - Method according to one of claims 3 and 4, characterized in that the temperature of the reaction medium during each step is between 50 and 120 C, preferably between 75 and 95 C. 6 - Method according to one of claims 3 to 6, characterized in that at each stage, the compound R60H - water or light alcohol - is removed by distillation as it is formed, each of the reactions being able to be carried out in an aliphatic or aromatic solvent which forms an azeotrope with said compound R60H. 7 - Method according to one of claims 3 to 6, characterized in that the second step is carried out under air bubbling in the presence of at least one polymerization inhibitor, at a rate of 100 to 5,000 ppm relative to the final product (I). 8 - Process according to claim 7, characterized in that the polymerization inhibitor is chosen from hydroquinone monomethyl ether, hydroquinone, phenothiazine and ditertiobutylparacresol. 9 - Co (polymer) comprising at least one unit of at least one compound of formula (I) as defined in one of claims 1 and 2.