WO2011157534A1

WO2011157534A1 - Novel monomer and method for producing same

Info

Publication number: WO2011157534A1
Application number: PCT/EP2011/058784
Authority: WO
Inventors: Joachim Knebel; Pavel Belik; Bardo Schmitt; Gerold Schmitt
Original assignee: Evonik Röhm Gmbh
Priority date: 2010-06-15
Filing date: 2011-05-30
Publication date: 2011-12-22
Also published as: DE102010030095A1

Abstract

The invention relates to a novel monomer and to a method for producing same (I), where: R₁ can represent hydrogen, methyl, ethyl, propyl, or isopropyl, R₂ can represent H or CH₃, and n can be a whole number from 1 to 20.

Description

New monomer and process for its preparation

Subject of the invention

The invention relates to a new group

polymerizable compounds:

Alkylene glycol monoisobornyl ether (meth) acrylates.

where R i may be hydrogen, methyl, ethyl, propyl or isopropyl, R ₂ = may be H or CH ₃ , n may be an integer from 1 to 20. State of the art

(Meth) acrylic esters containing structural elements of isoborneol are known. The production of

Isobornyl methacrylate is described for example in DE 4316004 or DE 19920796. Camphen will participate

Methacrylic acid in the presence of acidic catalysts for

Reaction brought. One can also Isoborneol or

Isobornyl acetate in the presence of alkaline catalysts with methyl methacrylate react. By-products in this case are methanol or methyl acetate (DE 19930721).

Isobornyl (meth) acrylate is an intense one

terpenic odor characterized in the

Processing can interfere.

task

It was the task, a new low-odor

to develop isobornyl group-containing (meth) acrylate monomer and to provide a simple and inexpensive process for its preparation.

solution

A monomer with the required properties is by transesterification of (meth) acrylic acid with

Dipropylenglycolmonoisobornylether catalysis of

Titanium compounds accessible.

Dipropylene glycol monoisobornyl ether is prepared according to EP 943 599 (Clariant) and is commercially available. The monomer may serve as a component in paints, preferably in high-solids paints. In these formulations

it reduces the solution viscosity of the copolymers. Under a high-solid paint is a paint with a

Solids content of> 60 wt .-%, preferably up to 80 wt .-% understood, the solvent content of the paint is

between 10% by weight and 40% by weight, preferably 20% by weight.

A low viscosity leads to an improved

Processability of the paint. Conventional processing techniques, such as spraying, rolling, spin-coating, etc. are thus possible.

Further, applications as a comonomer are associative

Thickeners, defoamers, Pigmentdispergierhilfsmitteln or Bodenbeschichtungmitteln conceivable.

Implementation of the invention

The monomers

Dipropylene glycol monoisobornyl ether (meth) acrylate is preferably prepared by transesterification, i. It sets Dipropylenglycolmonoisobornylether in the presence of a suitable catalyst and an inhibitor or

Inhibitor mixtures with a generally present in excess alkyl (meth) acrylate to whose basis

lying alcohol is released.

The (meth) acrylates

A particularly preferred group of monomers are (meth) acrylates. The term (meth) acrylates includes methacrylates and acrylates as well as mixtures of both. These monomers are well known. These include, but are not limited to, (meth) acrylates derived from saturated alcohols, such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate,

Isopropyl (meth) acrylate, n-butyl (meth) acrylate,

tert. Butyl (meth) acrylate, butoxymethyl (meth) acrylate,

Pentyl (meth) acrylate, hexyl (meth) acrylate,

Heptyl (meth) acrylate, octyl (meth) acrylate,

Isooctyl (meth) acrylate, isodecyl (meth) acrylate,

Tetrahydrofurfuryl (meth) acrylate, cyclohexyl (meth) acrylate and 2-ethylhexyl (meth) acrylate; (Meth) acrylates derived from unsaturated alcohols, such as

Oleyl (meth) acrylate, 2-propynyl (meth) acrylate,

Allyl (meth) acrylate, vinyl (meth) acrylate; Aryl (meth) acrylates, such as benzyl (meth) acrylate or

Phenyl (meth) acrylate. These monomers may be used singly or as a mixture. Here are mixtures

particularly preferred which contain methacrylic and acrylic esters.

The catalysts

As a catalyst tetraalkyl titanate (the

Tetraalkoxytitan content with respect to used

Methyl methacrylate is preferably 0.1 wt .-% - 0.75 wt .-%) used.

As transesterification catalysts, however, it is also possible to use all transesterification catalysts known from the prior art. Examples of suitable catalysts are zirconium acetylacetonate and further 1,3-diketonates of zirconium, furthermore mixtures of alkali metal cyanates or alkali metal thiocyanates and alkali metal halides can be used, furthermore zinc compounds,

Alkaline earth metal oxides or alkaline earth metal hydroxides, such as CaO, Ca (OH) ₂ , MgO, Mg (OH) ₂ or mixtures of the above compounds, further

Alkali metal hydroxides, alkali metal alkoxides and

Lithium chloride and lithium hydroxide, it can also be mixtures of the abovementioned compounds with the

the above-mentioned alkaline earth compounds and the Li salts are used, dialkyltin oxides,

Alkali metal carbonates, alkali metal carbonates together with quaternary ammonium salts, such as

Tetrabutylammonium hydroxide or

Hexadecyltrimethylammoniumbromid, further mixed catalysts of diorganyltin oxide and organyltin halide, acidic

Ion exchangers, phosphomolybdenum-heteropolyacids,

Titanium alcoholates, chelate compounds of the metals titanium, zirconium, iron or zinc with 1,3-di-carbonyl compounds, lead compounds, such as, for example, lead oxides,

Lead hydroxides, lead alkoxides, lead carbonates or lead salts of carboxylic acids.

Further, as the catalyst, an amide of a metal of the first main group can be used, more preferably, as the catalyst, lithium amide can be used.

The catalyst is used in amounts of 0.1- 5 wt.

used on employed alkyl (meth) acrylate

The Inhibitors The inhibitors suitable for this reaction are well known in the art.

Are used mainly 1, 4-dihydroxybenzenes. However, it is also possible to use differently substituted dihydroxybenzenes. In general, such inhibitors can be combined with the

represent general formula (II)

wherein

R ^{2 is} a linear or branched alkyl radical having one to eight carbon atoms, halogen or aryl, preferably an alkyl radical having one to four

Carbon atoms, particularly preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, Cl, F or Br; o is an integer in the range of one to four, preferably one or two; and

R ^{3 is} hydrogen, a linear or branched alkyl radical having one to eight carbon atoms or aryl, preferably an alkyl radical having one to four

Carbon atoms, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl or tert. Butyl.

However, it is also possible to use compounds with 1,4-benzoquinone as the parent compound. These can be described by the formula (III)

wherein

R ² and o have the meaning given above Likewise phenols of the general structure (IV) are used

wherein

R ^{4 is} a linear or branched alkyl radical having one to eight carbon atoms, aryl or aralkyl,

Propionic acid esters with 1 to 4 valent alcohols, which may also contain heteroatoms such as S, 0 and N,

preferably an alkyl radical with one to four

Carbon atoms, particularly preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.

Another advantageous class of substances are hindered phenols based on triazine derivatives of the formula (V)

with R ⁵ = compound of the formula (VI)

wherein R ⁶ = C _p H2p + i with p = 1 or 2.

Particularly successful are the compounds 1,4-dihydroxybenzene, 4-methoxyphenol, 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone, 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert. -butyl-4-methylphenol, 2,4-dimethyl-6-tert. -butylphenol, 2,2-bis [3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl-1-oxopropoxymethyl]] 1,3-propanediyl ester, 2,2'-thiodiethylbis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate,

Octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-bis (1,1-dimethylethyl-2,2-methylenebis (4-methyl-6- tert. butyl) phenol, tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -s-triazine-2, 4, 6- (1H, 3H, 5H) trione, tris (3, 5 Di-tert-butyl-4-hydroxy) -s-triazine-2, 46- (1H, 3H, 5H) trione or tert-butyl-3, 5-dihydroxybenzene used.

Advantageously, combinations of 4-hydroxy-2, 2, 6, 6-tetramethylpiperidinooxyl, dissolved oxygen, phenothiazine, 4- (methacryloyloxy) -2, 2, 6, 6-tetramethylpiperidin-l-oxyl, N, -Diethylhydroxylamin, Ν, Ν'-diphenyl-p-phenylenediamine or hydroquinone monomethyl ether used.

Based on the weight of the total reaction mixture, the proportion of inhibitors is individually or as

Mixture generally 0.01-0.50% (wt / wt), wherein the concentration of the inhibitors is preferably selected so that the color number is not impaired according to DIN 55945. Many of these inhibitors are commercially available. The (meth) acrylate to be reacted is used in molar excess to the alcohol to be incorporated, between 2-fold to 10-fold molar. After addition of a suitable catalyst or catalyst mixture and a suitable inhibitor or inhibitor mixture, the reaction mixture is heated, preferably to the boiling point of the used

(Meth) acrylic ester or the boiling point of

liberated alcohol from the used

(Meth) acrylic acid ester. If necessary, it is possible to work under reduced or elevated pressure.

The starting materials are preferably in anhydrous form

used to avoid side reactions with the catalyst.

The reaction time is controlled depending on the formation of the liberated alcohol.

Depending on the type of catalyst, the catalyst

optionally filtered in the presence of a filter aid, or after addition of an aqueous precipitant, preferably water, precipitated and then filtered off.

By means of distillation, preferably vacuum distillation, the low-boiling by-products and / or educts

distilled off.

The residue contains product to 80-99.5 wt .-%.

The examples given below are given for a better illustration of the present invention, but are not intended to limit the invention to the features disclosed herein. example 1

In a 1 liter round bottom flask with mechanical stirrer,

Air inlet tube and attached column (length: 50 cm, filled with 9 lab packs EX Sulzer) and automatic column head 190 g

Dipropylene glycol monoisobornyl ether at 630 g

Methyl methacrylate (MMA) and 0.12 g

Hydroquinone monomethyl ether and 0.0025 g of 4-hydroxy-2, 2, 6, 6-tetramethylpiperidyl-l-oxyl and heated with stirring and slow introduction of air to boiling. It

Distil 42 g of MMA-water mixture, leaving the

Weighing is dried azeotropically. It is cooled to 60 degrees Celsius and adds the distilled MMA amount by adding fresh MMA in the flask. You give 1.5 g

Lithium amide added and heated to boiling, the

formed MMA-methanol-azeatrop at one

Reflux ratio of 2: 1 distilled off. After 2.5 h, the end of the implementation is reached, recognizable by a

constant column head temperature of 100 ° C. The

Reaction mixture is now at 70 ° C with 1.5 g Tonsil

Standard 312 FF (Bentonite Fa. Südchemie) and 15 min. touched. It is pressure-filtered at room temperature and the filtrate is freed of MMA in vacuo (2 mbar). Of the

Residue (230 g) is the product which after

Gas chromatographic examination to 91.2% from the

Methacrylic acid ester of Dipropylenglycolisobornylethers exists.

Formula (Ia) Example 2

As Example 1, but the MMA is replaced by 630 g of ethyl acrylate. After azeotropic drying, 2 g are added

Isopropyl titanate added as a transesterification catalyst. The formation of the ethyl acrylate-ethanol azeotrope is complete after 4 h. For workup, the mixture is added at 70.degree

Reaction mixture with 8 g of a 1% solution of

Sulfuric acid in water, stirred for 10 min at this temperature and then gives 12 g of a 10% solution of

Add sodium carbonate in water, stirring for 10 min at 70 ° C. Then, as in Example 1 with the addition of 1.5 g Tonsil Standard 312 FF is worked up. Of the

Residue (215 g) consists of gas chromatographic

Investigation to 92.7% from the acrylic ester of

Dipropylene glycol isobornyl ether.

Example 3

Production of a high-solids paint resin

In a 0, 51-four-neck round bottom flask with reflux condenser, mechanical stirrer, thermometer, metering pump and

Oil bath heating is 41.7 g Solvesso 100 (aromatic

Hydrocarbon mixture from ExxonMobil) submitted and heated to 140 ° C. A mixture of 12.8 g of di- tert. butyl peroxide, 49.7 g

Dipropylene glycol isobornyl ether methacrylate from Example 1, 51.4 g of hydroxyethyl methacrylate, 17.2 g of 2-ethylhexyl methacrylate, 53.2 g of styrene and 3.1 g of 2-mercaptoethanol is added with a metering pump within 4 h under nitrogen. It sinks

Sump temperature at 137 ° C. After completion of the addition, stirring is continued for 30 minutes. It is then cooled to 80 ° C. 0.18 g of di-tert. butylperoxide is dissolved in 10 g Solvesso 100 metered to the post-reaction. It will be 2h at 80 ° C touched. 10.83 g Solvesso 100 is added and

then stirred without heating for about 30 min. There is added 38.46 g of n-butyl acetate to a

Adjust polymer content of 65%. Analysis of the resin:

Pt Co color number: 114

Hydroxyl number: 86.6 mg KOH / g

Acid value: 1.9 mg KOH / g

Viscosity (23 ° C): 1920 mPa * s Glass transition temperature (DSC): 33 ° C

Molar mass (gel permeation chromatography):

Mn = 1850 g / mol

Mw = 4430 g / mol

You can see that you are using

Dipropylene glycol isobornyl ether methacrylate obtains a similar or lower viscosity than when using the known Isobornylmethacrylats.

Comparative Example Preparation of a high-solids coating resin using isobornyl methacrylate

Oil bath heating is submitted to 100 g of Solvesso 100 and heated to 140 ° C. A mixture of 30.7 g of di- tert. butyl peroxide, 82.3 g isobornyl methacrylate, 123.5 g hydroxyethyl methacrylate, 82.3 g 2-ethylhexyl methacrylate, 123.5 g of styrene and 7.4 g of 2-mercaptoethanol is added with a metering pump within 4 h under nitrogen. The sump temperature drops to 137 ° C. After completion of the addition, stirring is continued for 30 minutes. It is then cooled to 80 ° C. 0.42 g of di-tert. butylperoxide is dissolved in 50g Solvesso 100 for postreaction

added. It is stirred for 2 h at 80 ° C. 40 g Solvesso 100 is added and then stirred without heating for about 30 min. 92.3 g of n-butyl acetate are added to adjust the polymer content to 65%.

Analysis of the resin:

Pt Co color number: 32

Hydroxyl number: 86.4 mg KOH / g

Acid value: 1.8 mg KOH / g Viscosity (23 ° C): 1950 mPa * s

Glass transition temperature (DSC): 22 ° C

Molar mass (gel permeation chromatography):

Mn = 1990 g / mol

Mw = 4630 g / mol

Claims

claims

1. Alkylene glycol monoisobornyl ether (meth) acrylate

Ri may be hydrogen, methyl, ethyl, propyl or isopropyl,

R ₂ = may denote H or CH ₃ , and n may represent an integer of 1 to 20.

Process for the preparation of the compound according to Claim 1, characterized in that

Dipropylenglycolmonoisobornylether catalysis with methyl methacrylate, methyl acrylate, ethyl (meth) acrylate or butyl (meth) acrylate.

3. The method according to claim 2, characterized in that the catalyst used is a lithium amide.

4. The method according to claim 2, characterized in that the catalyst used is a Titanalkoholat

Use of the monomer of claim 1 as a component in a copolymer.

Copolymer obtainable by polymerization of a mixture containing the monomer of formula (I).

7. Use of the monomer according to claim 1 as a component in a paint resin.

8. Use of the monomer according to claim 1 as a component in a copolymer as associative thickener.

9. Use of the monomer according to claim 1 as a component in a defoamer.

10. Use of the monomer according to claim 1 as a component in a Pigmentdispergierhilfsmittel.

11. Use of the monomer according to claim 1 as a component in a soil coating agent.