DE102010030095A1 - New monomer and process for its preparation - Google Patents

Abstract

The invention relates to a new monomer and a process for its preparation, where: R1 can represent hydrogen, methyl, ethyl, propyl or isopropyl, R2 = can represent H or CH3, and n can represent an integer from 1 to 20.

Description

Subject of the invention

Formel (I) wobei gilt: R₁ kann Wasserstoff, Methyl, Ethyl, Propyl oder Isopropyl bedeuten,
R₂ = kann H oder CH₃ bedeuten,
n kann eine ganze Zahl von 1 bis 20 darstellen.The invention relates to a new group of polymerizable compounds:
Alkylenglycolmonoisobornylether (meth) acrylates.

Formula (I) where R ₁ may be hydrogen, methyl, ethyl, propyl or isopropyl,
R ₂ = may be H or CH ₃ ,
n can represent an integer from 1 to 20.

State of the art

(Meth) acrylic esters containing structural elements of isoborneol are known. The preparation of isobornyl methacrylate is described, for example, in DE 4316004 or DE 19920796 described. In this case, camphene is reacted with methacrylic acid in the presence of acidic catalysts. It is also possible to react isoborneol or isobornyl acetate in the presence of alkaline catalysts with methyl methacrylate. As by-products are formed in this case, methanol or methyl acetate ( DE 19930721 ). Isobornyl (meth) acrylate is characterized by an intense terpenic odor, which can interfere with processing.

task

The object was to develop a new low odor 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 obtainable by transesterification of (meth) acrylic acid alkyl ester with dipropylene glycol monoisobornyl ether with catalysis of titanium compounds.

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. A high-solids paint is understood as meaning a paint having a solids content of> 60% by weight, preferably up to 80% by weight, the solvent content of the paint being between 10% by weight and 40% by weight, preferably 20 wt .-%.

Low viscosity leads to improved processability of the paint. Conventional processing techniques, such as spraying, rolling, spin-coating, etc. are thus possible.

Furthermore, applications as comonomer in associative thickeners, defoamers, pigment dispersing aids or floor coating agents are conceivable.

Implementation of the invention

The monomers

Dipropylene glycol monoisobornyl ether (meth) acrylate is preferably prepared by transesterification, i. H. It sets Dipropylenglycolmonoisobornylether in the presence of a suitable catalyst and an inhibitor or inhibitor mixture with a generally present in excess alkyl (meth) acrylate whose underlying alcohol is thereby set at liberty.

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. In this case, mixtures are particularly preferred which contain methacrylic and acrylic esters.

The catalysts

As the catalyst, tetraalkyl titanate (the content of tetraalkoxytitanium with respect to the methyl methacrylate used is preferably 0.1% by weight - 0.75% by weight) is 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 abovementioned compounds, furthermore alkali metal hydroxides, alkali metal alkoxides and lithium chloride and lithium hydroxide, it is also possible to use mixtures of the abovementioned compounds with the abovementioned alkaline earth compounds and the Li salts, dialkyltin oxides, alkali metal carbonates, alkali metal carbonates together with quaternary ammonium salts, such as tetrabutylammonium hydroxide or hexadecyltrimethylammonium bromide, further mixed catalysts of diorganyltin oxide and organyltin halide, acidic ion exchangers, phosphomolybdenum-heteropolyacids, titanium alkoh olates, chelate compounds of the metals titanium, zirconium, iron or zinc with 1,3-di-carbonyl compounds, lead compounds such as 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 from 0.1 to 5% by weight, based on the alkyl (meth) acrylate used.

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.

worin
R² einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Halogen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl, Cl, F oder Br; o eine ganze Zahl im Bereich von eins bis vier, vorzugsweise eins oder zwei ist; und
R³ Wasserstoff, einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen oder Aryl bedeutet, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl oder tert.-Butyl.In general, such inhibitors can be represented by the 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, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, 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, more preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec Butyl or tert-butyl.

worin
R² und o die oben angegebene Bedeutung haben.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.

worin
R⁴ einen linearen oder verzweigten Alkylrest mit eins bis acht Kohlenstoffatomen, Aryl oder Aralkyl, Propionsäureester mit 1 bis 4 wertigen Alkoholen, welche auch Heteroatome wie S, O und N enthalten können, vorzugsweise einen Alkylrest mit eins bis vier Kohlenstoffatomen, besonders bevorzugt Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, iso-Butyl, sec-Butyl, tert.-Butyl bedeutet.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 having 1 to 4 valent alcohols, which may also contain heteroatoms such as S, O and N, preferably an alkyl radical having one to four carbon atoms, particularly preferably methyl, Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl.

mit R⁵ = Verbindung der Formel (VI)

worin
R⁶ = C_pH_2p+1
mit p = 1 oder 2 ist.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 H _{2p + 1}
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'-thiodiethyl bis [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 -Hydroxy-2,2,6,6-tetramethylpiperidinooxyl, dissolved oxygen, phenothiazine, 4- (methacryloyloxy) -2,2,6,6-tetramethylpiperidine-1-oxyl, N, N-diethylhydroxylamine, N, N'-diphenyl -p-phenylenediamine or Hydroquinone monomethyl ether used.

Based on the weight of the total reaction mixture, the proportion of the inhibitors individually or as a mixture is generally 0.01-0.50% (wt / wt), the concentration of the inhibitors preferably being chosen such that the color number is DIN 55945 is not affected. 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 (meth) acrylic ester used or the boiling point of the liberated alcohol from the (meth) acrylic ester used. If necessary, work can be carried out under reduced or elevated pressure.

The starting materials are preferably used in anhydrous form in order 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 is filtered off, if appropriate in the presence of a filter aid, or after addition of an aqueous precipitant, preferably water, precipitated and then filtered off.

By distillation, preferably vacuum distillation, the low-boiling by-products and / or starting materials are 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

190 g of dipropylene glycol monoisobornyl ether with 630 g of methyl methacrylate (MMA) and 0.12 g of hydroquinone monomethyl ether and 0 are added to a 1 liter round bottom flask with mechanical stirrer, air inlet tube and attached column (length: 50 cm, filled with 9 laboratory packs EX from Sulzer) , 0025 g of 4-hydroxy-2,2,6,6-tetramethylpiperidyl-1-oxyl and heated with stirring and slow introduction of air to boiling. Distil 42 g of MMA-water mixture, so that the sample is dried azeotropically. It is cooled to 60 degrees Celsius and added to the distilled MMA Quantity by adding fresh MMA to the flask. 1.5 g of lithium amide are added and the mixture is heated to boiling, with the resulting MMA-methanol-azeatrop distilling off at a reflux ratio of 2: 1. After 2.5 h, the end of the reaction is reached, recognizable by a constant column head temperature of 100 ° C. The reaction mixture is then added at 70 ° C with 1.5 g of 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). The residue (230 g) is the product which according to gas chromatographic analysis consists of 91.2% of the methacrylic acid ester of dipropylene glycol isobornyl ether.

Formel (Ia)

Formula (Ia)

Example 2

As Example 1, but the MMA is replaced by 630 g of ethyl acrylate. After azeotropic drying, 2 g of isopropyl titanate are added as transesterification catalyst. The formation of the ethyl acrylate-ethanol azeotrope is complete after 4 h. For workup, the reaction mixture is mixed at 70 ° C. with 8 g of a 1% strength solution of sulfuric acid in water, stirred for 10 minutes at this temperature and then 12 g of a 10% solution of sodium carbonate in water are added, again Stirred at 70 ° C for 10 min. Then, as in Example 1 with the addition of 1.5 g Tonsil Standard 312 FF is worked up. The residue (215 g) consists according to gas chromatographic analysis to 92.7% of the acrylic acid ester of Dipropylenglycolisobornylethers.

Example 3

Production of a high-solids paint resin

In a 0.5 liter four-necked round bottom flask with reflux condenser, mechanical stirrer, thermometer, metering pump and oil bath heating 41.7 g of Solvesso 100 (aromatic hydrocarbon mixture from ExxonMobil) presented and heated to 140 ° C. A mixture of 12.8 g Ditert.butylperoxid, 49.7 g Dipropylenglycolisobornylethermethacrylat 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 with a Metering pump added 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. 0.18 g of di-tert-butyl peroxide are dissolved in 10 g of Solvesso 100 added to the post-reaction. It is stirred for 2 h at 80 ° C. 10.83 g Solvesso 100 is added and then stirred without heating for about 30 min. 38.46 g of n-butyl acetate are added to adjust the polymer content to 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

It can be seen that using dipropylene glycol isobornyl ether methacrylate gives a similar or lower viscosity than when using the known isobornyl methacrylate.

Comparative example

Preparation of a high-solids paint resin using isobornyl methacrylate

In a 0.5 liter four-necked round bottom flask with reflux condenser, mechanical stirrer, thermometer, metering pump and oil bath heating 100 g Solvesso 100 is initially charged and heated to 140 ° C. A mixture of 30.7 g Ditert.butylperoxid, 82.3 g of isobornyl methacrylate, 123.5 g of hydroxyethyl methacrylate, 82.3 g of 2-ethylhexyl methacrylate, 123.5 g of styrene and 7.4 g of 2-mercaptoethanol with a metering pump within 4 hours under nitrogen added. 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-butyl peroxide are dissolved in 50 g of Solvesso 100 added to the post-reaction. 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

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 4316004 [0002]
• DE 19920796 [0002]
• DE 19930721 [0002]
• EP 943599 [0005]

Cited non-patent literature

• DIN 55945 [0023]

Claims (11)

Alkylenglycolmonoisobornylether (meth) acrylate

where R ₁ may be hydrogen, methyl, ethyl, propyl or isopropyl, R ₂ = may be H or CH ₃ , and n may be an integer from 1 to 20. A process for the preparation of the compound according to claim 1, characterized in that one converts Dipropylenglycolmonoisobornylether catalysis with methyl methacrylate, methyl acrylate, ethyl (meth) acrylate or butyl (meth) acrylate. A method according to claim 2, characterized in that the catalyst used is a lithium amide. A 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). Use of the monomer according to claim 1 as a component in a paint resin. Use of the monomer according to claim 1 as a component in a copolymer as an associative thickener. Use of the monomer according to claim 1 as a component in a defoamer. Use of the monomer of claim 1 as a component in a pigment dispersing aid. Use of the monomer of claim 1 as a component in a floor coating composition.