WO2018037194A1

WO2018037194A1 - Epoxy adduct bearing binding groups, production method thereof and uses of same

Info

Publication number: WO2018037194A1
Application number: PCT/FR2017/052273
Authority: WO
Inventors: Sylvain BEAUDRAIS; Christophe Duquenne
Original assignee: Arkema France
Priority date: 2016-08-25
Filing date: 2017-08-24
Publication date: 2018-03-01
Also published as: FR3055333A1; FR3055333B1

Abstract

The present invention relates to epoxy adducts bearing binding groups, enabling said adducts to bind to one another or to a filler by means of non-covalent bonds. The compounds of the invention can be obtained from a compound comprising at least one epoxy function and from a modifying agent bearing both a nitrogen-heterocycle-containing binding group and a reactive group forming a covalent bond with the epoxy functions. The invention also relates to the use of said adducts as coupling agents that can establish interactions between a polymer and a filler, or for the production of block copolymers that can be used to improve filler dispersion in a polymer comprising unsaturations, or block copolymers having good polar surface adhesion properties.

Description

EPOXY ADDUCT WITH ASSOCIATIVE GROUPS, PROCESS FOR PREPARING SAME AND USES THEREOF

Technical area

The present invention relates to epoxy adducts carrying associative groups, making them capable of associating with each other or with a filler by non-covalent bonds.

The invention also relates to a method for preparing said adducts carrying associative groups, and their use as coupling agents capable of establishing interactions between a polymer and a filler, or for preparing block copolymers that can be used to improve the dispersion of fillers. in a polymer having unsaturations, or block copolymers having good adhesion properties to polar surfaces. Prior art and technical problem

In the industrial field, polymer blends with fillers such as for example carbon black or silica are often used. In order for such mixtures to have good properties, means are constantly sought to improve the dispersion of the fillers within the polymers. For this purpose, it has been proposed in the patent application WO 2012/007684 molecules carrying associative groups ensuring good interaction with the charges by establishing labile bonds between the polymer chains and the load, thus avoiding the disadvantages that too strong polymer-load interaction could cause. These molecules are composed of a group Q comprising a nitrogen dipole, such as a nitrile oxide function, nitrone or nitrile imine capable of binding to a polymer carrying unsaturations, and an associative group A such that the groups imidazolidinyl, triazolyl, triazinyl, bis-ureyl or ureido-pyrimidyl, Q and A being interconnected by a "spacer" group Sp. In the application WO 2012/007685, there are described other molecules carrying associative groups comprising a reactive group Q of azo-dicarbonyl unit and an associative group A connected to each other by a group "spacer" Sp. These molecules make it possible to modify by grafting a polymer comprising at least one double bond, without it being necessary for the polymer in question to comprise reactive functions.

The associative group-bearing molecules of the prior art cited make use of synthetic methods comprising a relatively large number of steps. The multiplication of the steps, which furthermore use solvents and require the isolation / purification of intermediate compounds, has an impact on the overall yield of the synthesis process of the desired compound but also on the investment costs and associated production costs. In addition, in the case of low molecular weight molecules, they represent substances with risks of potential migrability that are harmful for certain applications. This is the reason why other compounds carrying associative groups have been sought which are capable of ensuring a good polymer-filler interaction in the form of non-covalent bonds, and whose synthesis can be carried out in a minimum of steps. .

It has been discovered that epoxy adducts, that is to say polymers of low mass resulting from compounds comprising at least one epoxy function, carrying at least one associative group solved the technical problem. The associative epoxy adducts according to the invention can be easily prepared and can be used as coupling agents to establish interactions between a polymer and a filler. Incorporation of the epoxy adducts according to the invention, as such or as block copolymer sequences, into a polymer / filler mixture is easy and leads to a polymer having improved properties.

US 4,322,459 describes resins of the polyepoxide type modified by an azole group, in particular triazole (examples I and II). However, the synthesis carried out in excess of amine does not make it possible to obtain products terminated by epoxy functions, and requires the use of a solvent. These modified poly epoxies are used to prepare coating compositions and it is not suggested to use them as an agent. coupling between a polymer and a filler, or as a block in the preparation of a block copolymer.

Summary of the invention

The subject of the invention is therefore an epoxy adduct bearing at least one associative group corresponding to the following formula (1):

In which :

Cr denotes a hydrocarbon chain which may contain heteroatoms such as, for example, oxygen, resulting from a compound comprising at least one epoxy functional group;

B is an associative group comprising at least one nitrogen atom;

R is an atom or a group of atoms connecting the associative group B to the epoxy adduct; x varies between 1 and 20, preferably between 1 and 10.

By "associative group" is meant groups capable of associating with each other by hydrogen, ionic and / or hydrophobic bonds. It is according to a preferred embodiment of the invention groups capable of associating by hydrogen bonds.

When the associative groups are capable of associating by hydrogen bonds, each associative group comprises at least one donor "site" and one acceptor site with respect to the hydrogen bonding so that two identical associative groups are self-complementary and can associate with each other forming at least two hydrogen bonds.

The associative groups according to the invention are also capable of associating by hydrogen, ionic and / or hydrophobic bonds with functions present on fillers. In the remainder of the discussion, "epoxy adduct carrying at least one associative group" will also be called "associative epoxy adduct".

The invention also relates to a process for synthesizing said associative epoxy adduct comprising at least the following steps:

(a) heating a compound C comprising at least one epoxy function, at a temperature ranging from 20 ° C to 120 ° C;

(b) the reaction of a compound B 'bearing, on the one hand at least one associative group B having a nitrogen atom, and on the other hand a reactive group R' reacting on the product obtained in step ( at) ; steps (a) and (b) can be performed successively or simultaneously.

Another object of the invention is the use of said associative epoxy adduct as a coupling agent between a polymer and a filler.

Another object of the invention is the use of said associative epoxy adduct to prepare a block copolymer comprising at least one associative epoxy adduct sequence.

Another subject of the invention is the use of the block copolymer comprising at least one associative epoxy adduct sequence, for improving the dispersion of charges in a composition comprising at least one polymer comprising unsaturations, or for conferring adhesion to polar surfaces.

DETAILED DESCRIPTION OF THE INVENTION

The invention is now described in more detail and without limitation in the description which follows.

The associative epoxy adduct of formula 1

The associative epoxy adduct according to the invention comprises an epoxy adduct sequence, based on an x repeat of units derived from a compound C comprising at least one epoxy functional group, preferably at least two epoxide functional groups, more preferably having two epoxide functional groups, and has groups associative B comprising at least one nitrogen atom connected to the chain via a group R.

The associative group B comprising at least one nitrogen atom corresponds to one of the following formulas (I) to (IV):

(IV)

or :

X denotes an oxygen atom, sulfur atom or an NH group, preferably an oxygen atom.

Preferably, the formula (I) represents a 5- or 6-membered, preferably diazotized, di or tri-nitrogen heterocycle comprising at least one carbonyl, thiocarbonyl or imine functional group.

Preferentially, the associative group B of formula (I) is the group of formula (Ia):

wherein X is selected from oxygen atom and sulfur atom, preferably oxygen atom.

Preferably, the associative group is an imidazolidone group.

The molar mass of the associative epoxy adduct generally ranges from 200 to 10,000 g / mol.

The epoxy adduct results from a compound C comprising at least one epoxy functional group, preferably having two epoxy functional groups. Compound C is preferably a diglycidyl diepoxide.

Compound C can be a glycidyl type epoxy resin or a non-glycidyl type epoxy resin, preferably a glycidyl resin. The glycidyl epoxy resins are themselves classified as glycidyl ether, glycidyl ester and glycidyl amine. The non-glycidyl epoxy resins are of the aliphatic or cycloaliphatic type. The glycidyl epoxy resins are prepared by a condensation reaction of a diol, diacid or diamine with epichlorohydrin. The non-glycidyl epoxy resins are formed by peroxidation of the olefinic double bonds of a polymer.

Of the epoxy glycidyl ethers, the bisphenol A diglycidyl ether (DGEBA) shown below is the most commonly used.

As a general rule, n varies from 0 to 25.

Novolac epoxy resins (the formula is shown below) are glycidyl ethers of phenolic novolac resins. They are obtained by reacting phenol with formaldehyde in the presence of an acid catalyst to produce a novolac phenolic resin, followed by reaction with epichlorohydrin in the presence of sodium hydroxide as a catalyst.

Compound C can be chosen from the following compounds: Novolac epoxy resins with n strictly equal to zero, bisphenol A diglycidyl ether (DGEBA), hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, and tetrabromo bisphenol A diglycidyl ether, or hydroquinone diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether cyclohexanedimethanol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol diglycidyl ether, C8-C10 alkyl diglycidyl ethers, C12-C14 alkyl diglyc idyl ethers, diglycidyl ester of terephthalic acid, diglycidyl acid ester, in particular fatty acid, diglycidyl ester of acid dimer; glycidyl esters of versatic acid such as those sold under the name CARDURA® E8, E10 or E12 by the company Momentive (CARDURA® E10 of CAS 26761-45-5) glycidyl methacrylate, glycidyl (meth) acrylates alkoxylated glycidyl ester of neodecanoic acid, butyl glycidyl ether, cresyl glycidyl ether, phenyl glycidyl ether, p-nonyphenyl glycidyl ether, p-nonylphenyl glycidyl ether, pt-butyl phenyl glycidyl ether, 2-ethylhexyl glycidyl ether ; the epoxidized cycloaliphatic resins sold under the name ARALDITE® CY179, CY184, MY0510 and MY720 by Huntsman, the CY179 and CY184 resins corresponding respectively to the following formulas:

As well as the mixtures of the abovementioned resins.

Preferably, the compound C is a DGEBA resin, bisphenol F diglycidyl ether, 1,6-hexanediol diglycidyl ether, a C8-C10 alkyl diglycidyl ether, a C12-C14 alkyl diglycidyl ether or a diglycidyl ether comprising polyether chains, for example polyoxyethylene, polyoxypropylene, or polyoxybutylene. It is preferably a reaction compound between epichlorohydrin and a polyalkylene glycol. Preferably, the number of oxyalkylene units is between 1 and 100, preferably between 3 and 50.

As Depoxide compounds DER ™ products may be suitable, for example DER ™ resin 736 of the following formula wherein n ~ 4:

The associative groups B are connected to the epoxy adduct via a group R which may be the nitrogen atom or an aminoalkyl or dicarboxyalkyl radical with a linear or branched alkyl chain which may contain heteroatoms and of length ranging from 1 to 100 carbon atoms.

Preferably, the group R is an aminoalkyl radical in which the linear or branched alkyl chain can comprise heteroatoms such as N or O, and comprises from 1 to 100 carbon atoms, preferably from 1 to 18 carbon atoms. Preferably the group R is the group -N (CH ₂ ) ₂ -.

Advantageously, the number of associative groups B in the associative epoxy adduct is between 1 and 10.

Preferably, the associative adduct comprises from 5 to 50% by weight of associative groups B, preferably from 10 to 30% by weight. Method of synthesis of the associative adduct The associative adduct according to the invention may be prepared according to a two-step process. In a first step a), a compound C comprising at least one epoxy function as defined above is heated to a temperature ranging from 20 to 120 ° C.

In a second step b), the product obtained in step a) is modified using a modifying agent B '.

To do this, a modifying agent B 'is added. More specifically, the modification of the epoxy adduct may be carried out by grafting, that is to say by the reaction with a modifying agent B 'bearing, on the one hand, an associative group B based on nitrogen heterocycle according to one of the formulas (I) to (IV) above and, on the other hand, a reactive group R ', chosen for example from amine or acid groups, preferably amine, said reactive group forming a covalent bond with epoxy functions, carried by said adduct, and for connecting the associative group B to the epoxy adduct.

The modifying agent B 'can thus respond to any of the formulas

(B1) to (B4):

(B l)

(B2)

(B3)

(B 4)

Wherein R 'is a unit containing at least one reactive group of amine or diacid type, preferably amine.

Preferred examples of modifying agents B 'are 2-aminoethylimidazolidone (UDETA), N- (6-aminohexyl) -N' - (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea (UPy), 3-amino-1,2,4-triazole (3 -ATA) and 4-amino-1,2,4-triazole (4- AT A).

UDETA is preferred as a modifying agent for use in the present invention.

The modifying agent B 'may be preheated before being added to the product obtained in step a).

The reaction temperature of step b) is generally between 20 and

120 ° C.

The reaction of step b) can be controlled by monitoring the epoxy index (IE).

Advantageously, the modifying agent B 'is reacted in stoichiometric defect with respect to the epoxy functions of the adduct, and the associative epoxy adduct has two identical terminal functions epoxy type.

Preferably, modifying agent B 'is UDETA reacted in stoichiometric defect with respect to the epoxy functions of the adduct, and the associative epoxy adduct is a poly β-aminoalcohol epoxy bearing imidazolidone functional groups corresponding to the following formula:

(the)

With Cr, the resulting residue of compound C comprising at least one epoxy function, preferably two epoxy functions, used in step a). The two steps a) and b) can be performed successively or simultaneously, preferably simultaneously.

Uses of the associative epoxy adduct

Advantageously, the epoxy adduct bearing at least one associative group according to the invention is used as such as a coupling agent in a composition comprising at least one polymer and at least one filler.

Advantageously, the epoxy adduct bearing at least one associative group according to the invention is used to prepare a block copolymer comprising at least one sequence of said adduct carrying at least one associative group.

The block copolymer comprising at least one sequence of said adduct is advantageously used to impart adhesion properties to polar surfaces.

The block copolymer comprising at least one sequence of said adduct is advantageously used to improve the dispersion of charges in a composition comprising at least one polymer comprising unsaturations.

The following examples serve to illustrate the invention without being limiting in nature.

EXAMPLES

Examples 1 to 4 Epoxy adducts having imidazolidone groups of formula la were prepared as follows:

In a reactor equipped with agitation, a reflux column, a dropping funnel, a thermometer and a heating system, the epoxy resin (ml mass) is introduced and heated to 50 ° C. vs.

Then, a mass m2 of UDETA (Reverlink® U), previously heated to 80 ° C., is introduced into the dropping funnel to be introduced in liquid form. UDETA is introduced in 30 minutes while maintaining the temperature between 50 ° C and 55 ° C.

When all the UDETA is introduced, it is heated by respecting a temperature ramp from 50 ° C to 90 ° C in 2 hours followed by a waiting time whose duration is determined by the epoxy index measurement (IE) . When the measured epoxy value has reached a final theoretical value (representing the complete conversion of the epoxy groups) the reaction is stopped. The final epoxy index value does not accurately reflect the number of epoxy groups in the system, given the presence of amino functions. This contribution must be taken into account in the value of the epoxy value.

The final product, cooled to room temperature, is slightly yellow and can be easily handled.

The various tests carried out with the DER ™ 736 resin (Aldrich) and the Grilonit F 704 resin (EMS-Griltech) are collated in Table 1 below.

Table 1

UDETA Epoxy Resin

Time

Final

Ex m2 of atten El adjusted X

El

El EEW ml (g) te (h)

(boy Wut)

1 DE 736 307.6 182.4 150 23.1 1 208.5 150 0.8

2 DE 736 307.6 182.4 150 46 1 133.2 31 6.6

Grilonit 23.1

3 170 330 150 3 89.3 31.3 3.7 F704

4 DER 736 307.6 182.4 141.9 33.45 2 165.9 83.0 2.0

El: epoxy number (mg KOH / g) EEW epoxy equivalent by weight AI amine number (mg KOH / g) Γ UDETA: 870 AHEW: hydrogen equivalent weight of amine of UDETA: 64.5

Example 5 Preparation of a block copolymer from an epoxy adduct of the invention

The block copolymer was prepared according to a two-step process:

1. First step: synthesis of an acid-terminated polybutadiene

437.18 g of Krasol® LBH-P 2000 (polybutadiene containing alcohol-0 chain ends) are introduced into a reactor equipped with stirring, a reflux column, a thermometer and a heating system. 3890 moles of hydroxyls) and then heated to 90 ° C. 25.93 g of succinic anhydride (0.2593 moles of anhydride), and 0.35 g of sodium acetate (4.27 mmol) are then added. The mixture is brought to 115 ° C while respecting a temperature ramp (90 ° C to 115 ° C in lh). The temperature is maintained at 115 ° C for 1 hour and then the mixture is cooled to 80 ° C.

2. Second Step: Synthesis of a Block Copolymer by Reaction of the Product of Step 1 with the Epoxy Adduct Obtained in Example 4

In the reactor used for the synthesis of the acid-terminated polybutadiene of step 1, maintained at 80 ° C., 175.33 g (0.2593 moles of epoxide) of the epoxy adduct of Example 4 are introduced. The mixture of the two products is homogenized by gentle stirring for 15 minutes at 80 ° C., then brought to 130 ° C. and maintained at this temperature for about 9 hours.

The reaction between the two products was verified by measuring the molecular mass by steric exclusion chromatography (SEC) according to the analysis conditions below:

Columns: 2 linear columns 100 to 106 Å + 1 column 500Â Mobile phase flow (THF): 1 ml / min, T °: 35 ° C, detection RI.

Calibration: PS standards (Mw: 6.035.000, 2.698.000, 660.500, 325.600, 128.600, 69.650, 30.230, 9.960, 2.980, 980, 580, 374g / mol).

An increase in the molar mass with respect to the initial mass of the hydroxylated polybutadiene was observed: Krasol ^® LBH-P 2000: Mw (in g / mol) = 4044

Block copolymer: Mw (in g / mol) = 10433

The epoxy value, <5 mg KOH / g, confirms the reaction between the two products.

The block copolymer thus obtained is advantageously used to improve the dispersion of charges in a composition comprising at least one polymer comprising unsaturations, in particular in an elastomer composition.

Claims

An epoxy adduct bearing at least one associative group corresponding to the following formula (1):

In which :

Cr denotes a hydrocarbon chain which may contain heteroatoms, resulting from a compound comprising at least one epoxy function;

B is an associative group comprising at least one nitrogen atom;

R is an atom or a group of atoms connecting the associative group B to the epoxy adduct;

x varies between 1 and 20, preferably between 1 and 10.

Adduct according to Claim 1, characterized in that the associative group B corresponds to one of the following formulas (I) to (IV):

(IV)

where X denotes an oxygen atom, sulfur atom or an NH group, preferentially an oxygen atom.

Adduct according to claim 1 or 2, characterized in that the associative group B corresponds to the formula (la):

wherein X is selected from oxygen atom and sulfur atom, preferably oxygen atom.

Adduct according to any one of the preceding claims, characterized in that the number of associative groups is between 1 and 10.

Adduct according to any one of the preceding claims, characterized in that in formula (1) the Cr group results from a compound C chosen from epoxy resins of the glycidyl type, or non-glycidyl type epoxy resins.

6. Adduct according to claim 5 characterized in that the compound C is a DGEBA resin, bisphenol F diglycidyl ether, 1,6-hexanediol diglycidyl ether, a C8-C10 alkyl diglycidyl ether, a C12-C14 alkyl diglycidyl ether or a diglycidyl ether comprising polyether chains, for example polyoxyethylene, polyoxypropylene, or polyoxybutylene. Process for synthesizing an epoxy adduct bearing at least one associative group as defined according to any one of Claims 1 to 6, comprising at least the following steps:

(b) the reaction of a compound B 'bearing, on the one hand at least one associative group B having a nitrogen atom, and on the other hand a reactive group R' reacting on the product obtained in step ( at) ;

steps (a) and (b) can be performed successively or simultaneously.

8. Process according to claim 7, characterized in that the associative epoxy adduct has a molar mass ranging from 200 to 10,000 g / mol. 9. Process according to claim 7 or 8, characterized in that compound B 'corresponds to any one of formulas (B1) to (B4):

(Bl)

R'N Ί

(B2)

(B4) in which R 'is a unit containing at least one type of reactive group or diacid, preferably amine.

10. Process according to any one of claims 7 to 9 characterized in that the compound B 'is 2-aminoethylimidazolidone (UDETA), N- (6-aminohexyl) -

N '- (6-methyl-4-oxo-1,4-dihydropyrimidin-2-yl) urea (UPy), 3-amino-1,2,4-triazole (3-AT) and 4-amino 1,2,4-triazole (4-ATA), preferably UDETA.

11. Use of the adduct according to any one of claims 1 to 6 or obtained according to the process of any one of claims 7 to 10, as coupling agent between a polymer and a filler.

12. Use of the adduct according to any one of claims 1 to 6 or obtained according to the method of any one of claims 7 to 10, for preparing a block copolymer comprising at least one sequence of said adduct.

Use of a block copolymer comprising at least one epoxy adduct sequence bearing at least one associative group according to any one of claims 1 to 6 or obtained according to the method of any one of claims 7 to 10 to improve the dispersion of fillers in a composition comprising at least one unsaturated polymer, or to impart adhesion properties to polar surfaces.