WO2016165979A1

WO2016165979A1 - Dihydro-oligo-cyclopentadienyl (meth)acrylates

Info

Publication number: WO2016165979A1
Application number: PCT/EP2016/057420
Authority: WO
Inventors: Andrea Misske; Friederike Fleischhaker; Christoph Fleckenstein; Martin KALLER; Ulrik Stengel; Mathieu BLANCHOT; Marek Pazicky; Ritesh Nair
Original assignee: Basf Se
Priority date: 2015-04-15
Filing date: 2016-04-05
Publication date: 2016-10-20

Abstract

The invention relates to dihydro-oligocyclopentadienyl (meth)acrylates of general formula (I) wherein R represents H or CH₃; _n represents 1, 2, 3, 4 or 5.

Description

Dihydrooligocyclopentadienyl (meth) acrylates

description

The present invention relates Dihydrooligocyclopentadienyl (meth) acrylates having 3 to 7 derived from cyclopentadiene units, their preparation and copolymers containing them and their use. Dihydrodicyclopentadienyl (meth) acrylate, in the form of its copolymers, is used as UV crosslinker in radiation-curable coatings.

WO 97/25385 discloses radiation-curable lacquers to be processed from melt, solution or dispersion comprising as binders copolymers of a) (meth) acrylic acid or (meth) acrylates and / or (meth) acrylamides, b) dihydrodicyclopentadienyl (meth) acrylate and optionally c) further copolymerizable ethylenically unsaturated monomers.

DE 41 36 660 A1 describes the preparation of esters of dicyclopentadiene and 1 to 5 carbon atoms having organic carboxylic acids, preferably acrylic acid, by reacting the cyclopentadiene with the organic carboxylic acid in the presence of boron trifluoride and separating the ester from the reaction mixture by fractional distillation under reduced Print.

Dihydrodicyclopentadienyl (meth) acrylate is suitable as a monomer for UV crosslinking of copolymers containing this monomer, in particular because it has two differently reactive double bonds. In addition, it has a very high glass transition temperature. However, it has a very intense and unpleasant odor.

The object of the invention is to provide an alternative monomer to Dihydrodicyclopentadienyl (meth) acrylate, which has its advantageous properties, but is not so odorous. In particular, the monomer should be liquid at room temperature and have a low viscosity of preferably <50 mPas at 70 ° C, to be useful also in ink formulations for 3D printing (e.g., by photopolymer jetting). In such radiation-curable compositions, for example, dihydrocyclopentadienyl (meth) acrylate has been used as described in US 2010/0201019, US 2008/0286450, US 2012/0282439 and US 201 1/0104500.

The object is achieved by Dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I)

in which mean:

R H or CHs

n 1, 2, 3, 4 or 5.

In one embodiment of the invention, the dihydrooligocyclopentadienyl (meth) acrylate is dihydrotricyclopentadienyl (meth) acrylate (n = 1). In a further embodiment of the invention, the dihydrooligocyclopentadienyl (meth) acrylate is dihydrotetracyclopentadienyl (meth) acrylate (n = 2).

In a further embodiment of the invention, the dihydrooligocyclopentadienyl (meth) acrylate is dihydropentacyclopentadienyl (meth) acrylate (n = 3).

In one embodiment of the invention, it is the Dihydrooligopentadienylacrylate (R = H). In a further embodiment of the invention, the dihydrooligocyclopentadienyl methacrylates (R =CH 3) are used. The present invention also provides mixtures of dihydrocyclopentadienyl (meth) acrylates of the general formula (I).

The dihydrooligocyclopentadienyl (meth) acrylates can be prepared from the corresponding oligocyclopentadienes and (meth) acrylic acid by adding the acid to a double bond of the oligocyclopentadienes in the presence of boron trifluoride or a strong acid as catalyst and a polymerization inhibitor.

The invention also provides a process for preparing dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I) in which oligocyclopentadienes of the general formula (II)

With

n 1, 2, 3, 4 or 5 with (meth) acrylic acid in the presence of boron trifluoride and a polymerization inhibitor.

The reaction of the oligocyclopentadiene can be carried out in a solvent or solvent-free. Suitable solvents are aromatic solvents, e.g. Toluene, xylene, aliphatic solvents, e.g. n-heptane, cydohexane, tert-butylcyclohexane, chlorinated hydrocarbons such as chlorobenzene, dichlorobenzene, dichloromethane or ethers such as e.g. Diethyl ether, tert-butyl methyl ether, tetrahydrofuran or mixtures thereof. It is preferably carried out in bulk, wherein (meth) acrylic acid is preferably used in stoichiometric excess. The molar ratio of acid to oligocyclopentadiene is preferably from 10: 1 to 1: 1, more preferably from 3: 1 to 1.1: 1.

The catalyst boron trifluoride is generally present in amounts of 0.1 to 5 wt .-%, preferably from 0.1 to 1 wt .-% in the reaction mixture. Boron trifluoride is used as adduct. It is possible to use complexes such as e.g. BF3-methanol, BF3-ethanol, BF3-propanol, BF3-n-butanol, BF3-dihydrate, BF3-diethyl etherate, BF3-dimethyl etherate, BF3-tetrahydrofuran, BF3-tert-butylmethyl etherate or mixtures thereof. Boron trifluoride is preferably used as boron trifluoride dimethyl etherate and / or boron trifluoride diethyl etherate. As catalytically active strong acids, acids having a pKA <1 can be used, for example sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid and trifluoromethanesulfonic acid.

Suitable polymerization inhibitors are for example N-oxides (nitroxyl or N-oxyl radicals, ie compounds which have at least one NO group), such as. 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 4-acetoxy-2,2,6,6- tetramethylpiperidine-N-oxyl, 2,2,6,6-tetramethylpiperidine-N-oxyl, bis (1-oxyl-2,6,6-tetramethylpiperidines-4-yl) sebacate, 4,4 ', 4 Tris (2,2,6,6-tetramethylpiperidine-N-oxyl) phosphite or 3-oxo-2,2,5,5-tetramethylpyrrolidine-N-oxyl; mono- or polyhydric phenols which may be have one or more alkyl groups, such as, for example, alkylphenols, for example o-, m- or p-cresol (methylphenol), 2-tert-butylphenol, 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2 - methyl-4-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2,6-tert-butyl-4-methylphenol, 4-tert-butyl-2,6-dimethylphenol or 6-tert Quinones such as hydroquinone, hydroquinone monomethyl ether, 2-methylhydroquinone or 2,5-di-tert-butylhydroquinone; hydroxyphenols such as pyrocatechol (1,2-dihydroxybenzene) or benzoquinone; Alkoxyphenols such as 2-methoxyphenol (G uajacol, catechol monomethyl ether), 2-ethoxyphenol, 2-isopropoxyphenol, 4-methoxyphenol (hydroquinone monomethyl ether), mono- or di-tert-butyl-4-methoxyphenol; Tocipherole, such as α-tocopherol and 2,3-dihydro-2,2-dimethyl-7-hydroxybenzofuran (2,2-dimethyl-7-hydroxycumaran), sulfur-containing compounds such as diphenyl sulfide or phenothiazine. Preference is given to hydroquinone, hydroquinone monomethyl ether, phenothiazine, 4-hydroxy-2, 2,6,6-tetramethylpiperidine-N-oxyl, 4-oxo-2,2,6,6-tetramethylpiperidine-N-oxyl, 2-tert-butylphenol , 4-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4-methylphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di tert-butyl-4-methylphenol and 2-methyl-4-tert-butylphenol.

Particularly preferred is hydroquinone monomethyl ether (MeHQ).

Advantageously, oxygen can additionally be used as the polymerization inhibitor. For further stabilization, an oxygen-containing gas, preferably air or a mixture of air and nitrogen (lean air) may be present.

The reaction is generally carried out at temperatures of 40 to 1 10 ° C. The reaction time is generally 0.5 to 10, preferably 1 to 5 hours. After completion of the reaction, the reaction may optionally be diluted with an organic solvent. Suitable solvents are aromatic solvents, e.g. Toluene, xylene, aliphatic solvents, e.g. n-heptane, cyclohexane, methylcyclohexane, chlorinated solvents such as chlorobenzene, dichlorobenzene, dichloromethane or ethers such as e.g. Diethyl ether, tert-butyl methyl ether, tetrahydrofuran or mixtures thereof. The reaction mixture, which still contains catalyst and excess (meth) acrylic acid, in a washing apparatus with a 5 to 25 wt .-%, preferably 5 to 20 wt .-%, more preferably 5 to 15 wt .-% aqueous Solution of a base, such as. B. sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, potassium bicarbonate, calcium hydroxide, ammonia water or potassium carbonate, optionally 5 to 15 wt .-% sodium chloride, potassium chloride, ammonium chloride or ammonium sulfate may be added, preferably with sodium bicarbonate solution, sodium hydroxide or sodium hydroxide. Saline solution neutralized.

The addition of the base takes place in such a way that the temperature in the apparatus does not rise above 35 ° C, preferably between 20 and 35 ° C and the pH is 8 to 14. The heat of neutralization is optionally removed by cooling the container by means of internal cooling coils or by double-wall cooling. The quantitative ratio of reaction mixture: neutralizing liquid is generally 1: 0.1 to 1, preferably 1: 0.2 to 0.8, particularly preferably 1: 0.3 to 0.7. The laundry can be carried out, for example, in a stirred tank or in another conventional apparatus, for example in a column or mixer-settler apparatus. In terms of process technology, all the extraction and washing processes and apparatuses known per se can be used for a wash in the process according to the invention, for example those described in Ullmann's Encyclopedia of Industrial Chemistry, 7th ed, 2013 Electronic Release, Chapter Liquid-Liquid Extraction Apparatus , are described. For example, these may be one-stage or multistage, preferably single-stage extractions, as well as those in cocurrent or countercurrent mode. Optionally, a post-wash may be advantageous to remove base or salt traces from the neutralized reaction mixture. For this purpose, the reaction mixture is treated with water or a 5 to 30% strength by weight, preferably 5 to 20% strength by weight, particularly preferably 5 to 15% strength by weight saline solution. The quantitative ratio of reaction mixture: washing liquid is generally 1: 0.1 to 1, preferably 1: 0.2 to 0.8, particularly preferably 1: 0.3 to 0.7.

After separation of the aqueous phase, the solvent can be separated by distillation. For this purpose, the washed reaction mixture can first be admixed with an amount of storage stabilizer, preferably hydroquinone monomethyl ether, such that after removal of the solvent 100 to 500 ppm, preferably 200 to 500 ppm and particularly preferably 200 to 400 ppm thereof are contained in the target ester. The distillative removal of the main amount of solvent is carried out, for example, in a stirred tank with double wall heating and / or heating coils under reduced pressure, for example at 20 to 700 mbar, preferably 30 to 500 mbar and more preferably 50 to 150 mbar and a temperature of 40 to 80 ° C.

Of course, the distillation can also take place in a falling film or thin film evaporator. For this purpose, the reaction mixture, preferably several times in the circulation, under reduced pressure, for example at 20 to 700 mbar, preferably 30 to 500 mbar, more preferably 50 to 150 mbar and a temperature of 40 to 80 ° C passed through the apparatus.

Advantageously, an oxygen-containing gas, preferably air or a mixture of air and nitrogen (lean air), are introduced into the distillation apparatus, for example 0.1 to 1 m ³ / m ³ h, preferably 0.2 to 0.8 m ³ / m ³ h and particularly preferably 0.3 to 0.7 m ³ / m ³ h, based on the volume of the reaction mixture.

The residual solvent content in the residue after distillation is generally below 5% by weight, preferably 0 to 2% by weight. The separated solvent is condensed and preferably used again.

Oligocyclopentadiene mixtures are obtained in a known manner by polycycloaddition of cyclopentadiene under pressure at temperatures of 170 to 300 ° C. These mixtures can be worked up by distillation. Processes for the preparation of oligocyclopentadienes are also described in US 3,701,812 and US 5,446,222.

Copolymers which comprise the dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I) according to the invention in copolymerized form can be used as UV-crosslinking binders in curable compositions, for example radiation-curable coatings or in inks for 3D printing (for example photopolymer jetting). In contrast to the dihydrocyclopentadienyl (meth) acrylates, which smell intensely and unpleasantly, dihydrooligocyclopentadiene enyl (meth) acrylates have the advantage that they are odorless or smell much less intense and unpleasant. Subject of the invention are also

Copolymers of a) one or more Dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I) as monomer A and b) at least one further, copolymerizable with monomer A, ethylenically unsaturated monomer B.

As further ethylenically unsaturated monomers B, the copolymers according to the invention monomers b1) of the general formula (III) CH ₂ = C (R ¹ ) -CO-OR ² with

R ¹ = H or CH ₃ or C ₂ H ₅ and

R ² = H, CnF n + i where n = 1 to 30, an alicyclic, araliphatic or heterocyclic radical, a hydroxyalkyl, alkoxyalkyl, glycidyl or aminoalkyl radical, or the general formula (IV)

CH ₂ = C (R ¹ ) -CO-NR ³ R ⁴ with

R ¹ = H or CH 3, where R ³ and R ⁴ may be identical or different and for H, CH ₂ OH, C _n H ₂ n ₊ i with n = 1 to 30 or CH 2 OR ⁵ with R ⁵ = C _m H ₂ m ₊ i with m = 1 to 12 are included.

Suitable further monomers b1) of the general formula (III) are, for example, the esters of acrylic acid and methacrylic acid with aliphatic, cycloaliphatic, araliphatic and aromatic alcohols having 1 to 30, preferably 1 to 20, carbon atoms, for example methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl

(meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth ) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl ( meth) acrylate, furfuryl (meth) acrylate and the esters of 3-phenylacrylic acid and its various isomer forms, for example methyl cinnamate, ethyl cinnamate, butyl cinnamate, benzyl cinnamate, cyclohexyl cinnamate mat, isoamyl cinnamate, tetrahydrofurfuryl cinnamate, furfuryl cinnamate, acrylamide, methacrylamide, methylol acrylamide and methylol methacrylamide. Suitable compounds of the general formula (IV) are, for example, (meth) acrylamides, such as acrylic acid, methacrylic acid, 3-phenylacrylic acid, hydroxyalkyl (meth) acrylates, such as ethyl glycol mono (meth) acrylate, butylglycol mono (meth) acrylate, hexanediol mono (meth) acrylate , Ether (meth) acrylates such as methoxyethyl glycol monomethacrylate, ethyloxyethyl glycol mono (meth) acrylate, butyloxyethylglycol mono (meth) acrylate, phenyloxyethyl glycol mono (meth) acrylate, glycidyl acrylate, glycidyl methacrylate, and amino (meth) acrylates such as 2-aminoethyl (meth) acrylate. In one embodiment of the invention, the copolymers contain as monomers b1) acrylic or methacrylic acid (cyclo) alkyl esters having 1 to 10 carbon atoms in the alkyl radical or mixtures thereof with glycidyl (meth) acrylate and / or methacrylic acid.

In a further embodiment, the copolymers according to the invention contain, as further monomers b1), a compound selected from the group consisting of isobornyl acrylate, isobornyl methacrylate, isobornyl methacrylate, isobornyl cinnamate, adamanthaneacrylate, adamanthan methacrylate, adamanthanethacrylate and adamanthanemoninnamate.

In addition to the other monomers b1), other copolymerizable monomers B may also be styrene, 4-tert-butylstyrene and / or 1-methylstyrene as further monomers b2). In addition, other monomers B besides b1) and optionally b2) may also be copolymerized copolymerizable, ethylenically unsaturated compounds b3) which are capable of hydrogen abstraction in the triplet-excited state. Such compounds b3) are preferably derived from an aromatic or partially aromatic ketone, preferably from benzophenone and its derivatives, or have thioxanthone structures. Such monomers b3) are disclosed, for example, in WO 97/25385, structures (III) to (XLIII).

The dihydrooligocyclopentadienyl (meth) acrylates are generally contained in the copolymers according to the invention in amounts of from 2 to 90% by weight, preferably from 10 to 60% by weight, based on the total amount of the monomers.

The present invention also relates to the use of the copolymers of dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I) and other ethylenically unsaturated monomers which can be copolymerized with these as binders in curable compositions, such as, for example, radiation-curable varnishes or in inks for 3D printing (for example, photopolymer jetting).

The invention is further illustrated by the following examples.

Examples example 1

In a 100 mL three-necked flask fitted with reflux condenser, thermometer and stirrer 10 g of oligocyclopentadiene (oligomer mixture with a determined via H-NMR quotient of CH-unsaturated: CH saturated of 0.18: calculated according to a mixture of tetra and Pentacyclopentadiene), 7.2 g of acrylic acid and 17 mg MeHQ presented at a bath temperature of 50 ° C. 284 mg of boron trifluoride diethyl etherate are added. The reaction mixture is heated to 90 ° C. After 2 h is cooled and 100 mL of methylene chloride and 50 mL of 8% NaHCOs solution are added. After separating off the aqueous phase, 50 ml of 8% strength NaHCOs solution are again added and the phases are separated. The organic phase is concentrated in vacuo. The product dihydrooligocyclopentadienyl acrylate is obtained quantitatively in a purity of> 90% (H-NMR).

Example 2

In a 500 mL four-necked flask with attached reflux condenser, thermometer and stirrer 50 g tricyclopentadiene (purity 99.7 GC-FI .-%), 36 g of acrylic acid and 86 mg MeHQ at a bath temperature of 50 ° C presented. Add 1, 42 g of boron trifluoride diethyl etherate. The reaction mixture is heated to 90 ° C. After 2 h, it is cooled and 300 mL of methylene chloride and 250 mL of 8% NaHCO 3 solution are added. After separating off the aqueous phase, 250 ml of 8% NaHCOs solution are added again and the phases are separated. The organic phase is concentrated in vacuo. The product dihydrotriccyclopentadienyl acrylate is obtained quantitatively in a purity of> 90% (H-NMR). It contains 130 ppm MeHQ (HPLC). The dynamic viscosity is 402 mPa ^* s at 25 ° C and 24 mPa ^* s at 70 ° C.

Example 3

100 g of tricyclopentadiene (purity 99.7 GC-FI .-%), 86 g of methacrylic acid and 180 mg of MeHQ at a bath temperature of 50 ° C. are placed in a 0.75 L flat-section reactor with column, condenser, liquid divider, anchor stirrer and air inlet , 2.82 g of boron trifluoride diethyl etherate are added. The reaction mixture is heated to 90 ° C. After 2 h, it is cooled and transferred to a separatory funnel. Add 600 mL of methylene chloride and 500 mL of 8% NaHCOs solution. After separating off the aqueous phase, 500 ml of 8% strength NaHCO 3 solution are again added and the phases are separated. The organic phase is concentrated in vacuo. The product dihydrotricyclopentadienyl methacrylate is obtained quantitatively in a purity of> 90% (H-NMR) and contains 200 ppm MeHQ.

Claims

claims

1 . Dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I)

in which mean

R H or CHs

n 1, 2, 3, 4 or 5.

Dihydrooligocyclopentadienyl (meth) acrylates of the general formula (I), characterized in that n is 1, 2 or 3.

Process for the preparation of dihydrooligocyclopentadienyl (meth) acrylates of general formula (I) in which oligocyclopentadienes of general formula (II)

With

n 1,

2,

3,

4 or 5,

with (meth) acrylic acid in the presence of boron trifluoride and a polymerization inhibitor.

5. Use of the copolymers according to claim 4 as a binder in radiation-curable coatings or inks for 3D printing.