DE102011081649A1 - Longer chain methacrylates from renewable raw materials - Google Patents

Abstract

The present invention relates to monomer mixtures of isoamyl methacrylates, the isomeric mixture of which corresponds to the isoamyl alcohol component of the isomer composition of an isoamyl alcohol obtained from a renewable raw material source.

Description

The present invention relates to monomer mixtures of isoamyl methacrylates, the isomeric mixture of which corresponds to the isoamyl alcohol component of the isomer composition of an isoamyl alcohol obtained from a renewable raw material source.

State of the art

The preparation of isoamyl methacrylates is known. So claimed CN 1070374 the synthesis of isoamyl methacrylate (isopentyl methacrylate, methylbutyl methacrylate (MBMA)) starting from the corresponding nitrile by means of sulfuric acid using organic acids and metal oxides as catalysts. Transesterifications starting from methyl methacrylate (MMA) by means of magnesium methylate are described in Tuliao Gongye (1985), 87, 13-16 described. Esterifications of methacrylic acid under ion exchange catalysis to the corresponding methacrylate are, for example, in Khimicheskaya Promyshlennost (1967), 43, 258-60 examined. None of these methods of preparation recommends the use of renewable raw material sources.

The production of methacrylates from biomass also belongs to the state of the art. That's how it describes WO 2009156648 the synthesis of MMA via acetone, acetocynohydrin and methanol, wherein at least one of said components or intermediates is obtained from biomass. However, this application is limited to the short-chain methanol. Longer chain alcohols from renewable raw materials for the esterification with acrylates are used in US 20110190464 claimed, but here is limited due to the use of glycerol as starting material on acrylates.

task

The object of the present invention is to provide methacrylate monomer mixtures based on renewable raw materials. In particular, a sustainable availability of even longer-chain methacrylates should be ensured under the aspect of dwindling fossil resources. Further, improvements in the polymers made from the corresponding methacrylates are limited to selected properties, e.g. Improved compatibility with other plastics in the production of blends, greater adhesion to plastic surfaces and increased additives in the production of coating resins to realize, while maintaining good other properties with respect to the petrochemical sources produced analogues.

solution

These are solved as well as other tasks not explicitly mentioned, but which are readily derivable or deducible from the contexts discussed herein by providing monomer mixtures of isoamyl methacrylates whose isomeric mixture corresponds to the isoamyl alcohol component of the isomer composition of an isoamyl alcohol derived from a renewable source of raw material.

(Meth) acrylates are well-known and widely used monomers. Accordingly, various methods are known to obtain these compounds. For the preparation of special (meth) acrylates, transesterification reactions are often carried out in which methyl methacrylate is reacted with a corresponding alcohol. To improve the yield and the selectivity of the reaction, different catalysts have hitherto been used. For example, the document describes DE 28 05 702 the production of esters of unsaturated carboxylic acids. In particular, compounds containing zirconium and / or calcium can be used to catalyze the reactions described. Particularly suitable catalysts include in particular zirconium acetylacetonate. The reactions lead to high yields of about 97%, based on the alcohol used. Furthermore, acids or bases can be used to catalyze the transesterification. Such reactions are for example in CN 1355161 . DE 34 23 443 or EP-A-0 534 666 explained. The basic catalysts include in particular lithium amide, as exemplified in the publications DE 34 23 443, CA 795814 and US 6,194,530 set out

In the present invention, the transesterification of methacrylates with C1-C3 alcohols is particularly preferred, starting from MMA particularly preferred. The transesterifications can be carried out batchwise or continuously with heterogeneous or homogeneous catalysts. Procedures for this are eg in EP 1924547 . EP 2162423 . EP 2294048 and DE 10 2010 000 945 disclosed. The content of these documents is hereby disclosed.

The production of isoamyl alcohol from renewable resources in non-fermentative ways is eg in Nature (2008), 451, 86-89 or BR 20007000631 described. Fermentative processes are for example US 20100216958 . WO 2009076480 or WO 2009008756 refer to. A commercial product from the purification of fusel oils is available from Oxiteno, Brazil.

The isomer ratio of 3-methylbutanol to 2-methylbutanol may vary between 60:40 to 90:10, depending on the natural source of the raw material. Preferred is a composition of 80:20.

The use of renewable resources in a product can be detected via the isotopic composition of the carbon atoms. In contrast to products made from fossil fuels, the latter contain ¹⁴ C. All carbon samples from natural organisms (plant or animal) contain all three carbon isotopes: ¹² C (about 98.9%), ¹³ C (about 1.1%) and ¹⁴ C (about 1.2 × 10 ^-10 %). The ¹⁴ C / ¹² C ratio in living organisms is virtually identical to that of the atmosphere, as metabolic activity causes a constant exchange with the environment. The isotope ¹² C is stable while the radioactive isotope half-life ¹⁴ C is 5730 years, so that over the life cycle of a monomer, including that of the polymer produced therefrom, the ¹⁴ C / ¹² C ratio remains practically constant. Assuming isoamyl methacrylate that 5 of the 9 C atoms come from a natural source, the ¹⁴ C content should be 0.5 × 10 ^-10 % to 0.7 × 10 ^-10 % based on the total carbon content. The ¹⁴ C content of a sample (as a ratio ¹⁴ C / ¹² C) can be after ASTM D6866 respectively. ASTM D7026 determine.

The monomer mixtures of isomers of isoamyl methacrylate thus obtained can be prepared in a customary manner, such as, for example, in US Pat Stickler, M. and Rhein, T. 2000. Polymethacrylates. Ullmann's Encyclopedia of Industrial Chemistry described, be used for the production of (meth) acrylate copolymers.

The following examples are intended to illustrate the invention in a nonlimiting manner.

Example 1: Preparation of isoamyl methacrylate

A mixture of 793.35 g of biogenic isoamyl alcohol (mixture of 80% 3-methyl-1-butanol and 20% 2-methyl-1-butanol), 2700.0 g of methyl methacrylate, 0.562 g (400 ppm of product) hydroquinone monomethyl ether, 0.281 g ( 200 ppm of product) Phenothiazine and 0.014 g (10 ppm of product) 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl is charged to a 4L four-necked flask with a saber stirrer (stirrer sleeve, stirrer motor), an inlet tube for compressed air , a 50 cm packed column (filled with 6 × 6 × mm glass Raschig rings), an automatic column head, a sump or head thermometer and a heated mushroom submitted. The reaction mixture is heated to boiling while introducing air. When the column head is open, the batch is dehydrated until a head temperature of 100 ° C is reached. After dehydration, the mixture is cooled by about 20 ° C, as a catalyst 3.97 g Tetraisopropyltitanat (0.5% b.a. Alcohol) and the azeotrope equivalent weight of methyl methacrylate (63g) was added and heated to boiling again. At a head temperature of 64.6 ° C, the methyl methacrylate / MeOH azeotrope at a reflux ratio of 5: 1 and a head temperature limit of 70 ° C is separated. During the reaction, the head temperature limiter is gradually increased (5 ° C steps) up to 100 ° C and the apparatus continues to operate with the column head closed. During the alcoholysis, the conversion is determined by measuring the refractive index (nD20).

After completion of the reaction, the excess methyl methacrylate is removed by reducing the pressure to 30 mbar and 80 ° C bottom temperature. The crude ester (1355 g) is fractionally distilled through a 30 cm Vigreux column in vacuo, giving 1157 g of product.

Example 2: Performance Testing of Isoamyl Methacrylate (MBMA) for Use in Varnish Resins

Vernetzung mit HDI (NCO/OH = 1:1), 45 min bei 145 °C, 50 µm Filmdicke Tabelle 5: Quellung von Filmen mit konstanten Gewichtsanteilen an MMA bzw. Tg-angepaßt Monomer X 3-MBMA 2-MBMA MBMA Isomerengemisch Basis Petrochemisch Petrochemisch Biorohstoff von Oxiteno MMA / X 70/30 70/30 70/30 Tg (ber. nach Fox) 79 °C 85 °C 78 °C Quellung nach 5 h 327,1 % 134,9 % 423,4 % MMA / X 68/32 55/45 68/32 Tg (ber. nach Fox) 77 °C 75 °C 76 °C Quellung nach 5 h 277,9 % 184,2 % 467,8 % Table 1: Properties of the starting compounds product 3-MBMA 2-MBMA MBMA isomeric mixture Base petrochemical petrochemical Bio raw material from Oxiteno HQME content 197 ppm 97 ppm 81 ppm color number <5 7 6 purity 97.859% 99.209% 98.203% acidity 0.002% 0.002% 0.002% water content 0.004% 0.010% 0.016% Tg of the polymer 30 ° C 45 ° C 28 ° C Table 2: Determination of the polymerization time including temperature maximum product 3-MBMA 2-MBMA MBMA isomer mixture Base petrochemical petrochemical Bio raw material from Oxiteno HQME content 200 ppm 201 ppm 198 ppm Measurement at 70 ° C 127.7 min 78.4 ° C 123.2 min 81.3 ° C 127.7 min 80.3 ° C Measurement at 75 ° C 78.3 min 88.5 ° C 74.2 min 90.9 ° C 77.2 min 88.2 ° C Table 3: Properties of Lösungscopolymerisaten (65% in Solvesso ^® 100 / n-butyl acetate): Monomer X 3-MBMA 2-MBMA MBMA isomer mixture petrochemical petrochemical Bio raw material from Oxiteno Composition / weight% IBOMA 15.3% 15.3% 15.3% HEMA 29.6% 29.6% 29.6% X 15.3% 15.3% 15.3% BA 11.7% 11.7% 11.7% styrene 28.0% 28.0% 28.0% Composition / mol% IBOMA 9.1% 9.1% 9.1% HEMA 30.2% 30.2% 30.2% X 12.9% 12.9% 12.9% BA 12.2% 12.2% 12.2% styrene 35.6% 35.6% 35.6% color number (Pt-Co) 55 29 34 acid number (mg KOH / g) 1.9 1.5 1.1 OH number (mg KOH / g) 84.6 85.4 87.5 Tg [° C] DSC 20 25 28 Fox 63 66 62 Viscosity at 65% solids content 23 ° C (mPas) 1690 2020 2040 IBOMA = isobornyl methacrylate; HEMA = hydroxyethyl methacrylate; BA = butyl acrylate; Table 4: Film properties of crosslinked films

Crosslinking with HDI (NCO / OH = 1: 1), 45 min at 145 ° C, 50 μm film thickness Table 5: Swelling of films with constant proportions by weight of MMA or Tg-matched Monomer X 3-MBMA 2-MBMA MBMA isomer mixture Base petrochemical petrochemical Bio raw material from Oxiteno MMA / X 70/30 70/30 70/30 Tg (transl. To Fox) 79 ° C 85 ° C 78 ° C Swelling after 5 h 327.1% 134.9% 423.4% MMA / X 68/32 55/45 68/32 Tg (transl. To Fox) 77 ° C 75 ° C 76 ° C Swelling after 5 h 277.9% 184.2% 467.8%

Surprisingly, the swelling experiments showed a significantly increased value for the MBMA isomer mixture from renewable raw material sources. A better swelling capacity can be used in the blend production, since the compatibility with other plastics is improved. Likewise, this leads to better adhesion to plastic surfaces. The Additivierbarkeit in the production of coating resins is significantly increased.

Measuring, testing and polymerization processes

1. purity:

The purity of the monomers was determined by gas chromatography (Agilent) under the following conditions:
Carrier gas: helium
Detector type: FID
Column: Quartz capillary column DB-5, length: 30 m
Temperature program: 50 ° C to 280 ° C with a heating rate of 20 ° C / min
Injection temperature: 250 ° C
Detector temperature: 300 ° C

2nd color number:

The color number of the monomers was determined by the photometric determination of the platinum-cobalt color value ( DIN ISO 6271 ).
DIN ISO 6271 Classification of the color according to the platinum-cobalt scale

3. Acidity:

The acidity of the monomer was determined potentiometrically by titration against sodium hydroxide.
W. Huber: Titrations in non-aqueous solvents, 1964, Akademische Verlagsgesellschaft, Frankfurt am Main ,
L. Safarik and Z. Stransky: Titrimetic Analysis in Organic Solvents, Volume XXII of Wilson and Wilson's Comprehensive
Analytic Chemistry, Elsevier-Verlag, Amsterdam, 1986

4. Water content: Determination of the water content according to Karl Fischer

• 5. Determination of the polymerization time: determined by means of bulk polymerization with 0.20% of 2,2'-azobis (isobutyronitrile) at T = 70 ° C. and T = 75 ° C. in test tubes; with the aid of a temperature sensor, the temperature profile of the reaction was recorded; T _max corresponds to the polymerization time

6. Glass transition temperature (Tg) of the polymers

Preparation of the samples by bulk polymerization with 0.50% ter-butyl per-2-ethylhexanoate in test tubes for 18 h at 80 ° C in a water bath, annealing for 24 h at 130 ° C in a drying oven. Determination of the Tg by means of DSC DIN EN ISO 11357 , The glass transition temperature of the homopolymer of MBMA was determined by extrapolation of the Tg values of the copolymers with MMA.

7. Carrying out the solution polymerization

• 8. Bestimmung der dynamischen Viskosität mit dem Brookfield-Viskosimeter Die Lackharze wurden im Wasserbadthermostat auf 23 °C temperiert und die dynamische Viskosität mit dem Brookfield-Rotationsviskosimeter LVT DV II mit Schutzbügel mit Spindel III bzw. IV gemessen.

Apparatus: 0.5L four-necked round bottomed flask, reflux condenser, saber stirrer (200 rpm), stirrer motor, dosing pump, Pt100 digital thermometer in the sump, controlled oil bath with stirring motor for mixing, nitrogen bottle with supply line and flow meter. Procedure: Solvesso ^® 100 was placed in a flask and heated. The oil bath temperature was maintained at 149 ° C. The bottom temperature was about 140 ° C. The polymerization was carried out under N ₂ atmosphere (flow: 7.50 L / min). The respective monomer mixture was prepared and dosed with a metering pump within 4 h (1.0 mL / min). The bottom temperature dropped during the addition to about 137 ° C, the mixture boiled. After completion of the addition, stirring was continued for 30 minutes. The bath temperature was still 149 ° C. It was cooled to 80 ° C. 0.07% DTBP were dissolved in 10 g Solvesso ^® 100 added for post-reaction. It was stirred for 2 h at 80 ° C. 15 g Solvesso ^® 100 was added and then stirred without heating for about 30 minutes was added 46.16 g of n-butyl acetate to adjust a polymer content of 65%. The batch was bottled.

• 8. Determination of the dynamic viscosity with the Brookfield viscometer The coating resins were tempered in a water bath thermostat to 23 ° C and the dynamic viscosity measured with the Brookfield rotational viscometer LVT DV II with guard with spindle III or IV.

9. Preparation of the crosslinked polymer films

For the preparation of films from the polymers a 65% solution of HDI Desmodur ^® N3300 in Solvesso ^® was prepared 100th To determine the weight, the required amount of isocyanate was calculated based on the measured OH numbers of the resins. It was set a molar ratio NCO / OH = 1/1. The catalyst used was 0.01% dibutyltin dilaurate (DBTL), based on the solids content of the polymer. The dibutyltin dilaurate was mixed in a beaker with the isocyanate solution. This mixture was added to the resin in a beaker and the mixture was homogenized on the magnetic stirrer. After a short waiting time in order to remove air bubbles have occurred, films using a film-drawing doctor blade (gap width 150 .mu.m) to chromated aluminum panels (Alodine ^® 1200 Fa. Henkel) applied. The nominal layer thickness after drying is 50 +/- 5 μm. For the measurement of gloss and abrasion in the Reibradversuch black painted aluminum plates were used as substrates. The coated films were crosslinked in a drying oven at 145 ° C for 25 min. Before all measurements, the films were conditioned in a climate chamber at 23 ° C.

10. Determination of the layer thickness

The layer thicknesses of the dried polymer films were determined by the Byko test 4500 Fe / NFe from Byk Gardner in the eddy current method with the probe for non-magnetic substrates. For this purpose measurements were taken at intervals of about 0.5 cm along the films, the measured values recorded, and the area of the film having the target layer thickness of 50 +/- 5 microns and 30 +/- 5 microns, marked. The subsequent measurements were made within this range.

11. Determination of pendulum hardness

• 12. Bestimmung der Haftungseigenschaften durch Gitterschnittprüfung Mit einem Gitterschnittgerät mit 6 parallelen Klingen wurden zwei Schnitte im rechten Winkel zueinander durch die Filme geführt. Das Aussehen der Schnittränder und die Menge der abgeplatzten Teilstücke wurden anhand der Beschreibung nach DIN EN ISO 2409 visuell beurteilt.

The pendulum hardness was carried out according to König with the pendulum hardening device of BYK Mallinckrodt. In each case, a duplicate determination was carried out at different points of the coated films. The result was given after conversion of the required oscillations by multiplication by a factor of 1.4 in seconds ( DIN EN ISO 1522 ).

• 12. Determination of the adhesion properties by cross-hatching test With a cross-hatch cutter with 6 parallel blades, two cuts were made at right angles to each other through the films. The appearance of the cut edges and the amount of chipped cuts became apparent from the description DIN EN ISO 2409 assessed visually.

13. Resistance testing against various test media

Reagents to be tested were brake fluid, diesel, 2-propanol and methyl ethyl ketone (MEK). The films produced were examined for their resistance by pressing 0.70 g of pulp soaked with 1.0 g of the respective test liquid and covered with a glass plate (about 500 g) for 15 minutes on the film. The films were dried at room temperature for 24 h, then the pendulum hardness was again determined at the treated sites and compared with the values of the untreated films.

14. Determination of Acid / Base Resistance, BART Test (BASF Acid Resistance Test)

The films produced on aluminum plates were divided into three strips each about 1 cm wide. In these areas, a drop of 36% sulfuric acid, 20% hydrochloric acid or 5% sodium hydroxide solution was applied. The pretreated films were stored for 30 min at 50 ° C in a drying oven. After rinsing the reagents under running demineralized water, the surface of the films was visually evaluated as follows: 0 no defect 1 slight mark 2 Marking / matting / no softening 3 Marking / Matting / Color change / Softening 4 Cracks / incipient etching 5 through etch

 Thereafter, a re-application of the test solutions next to the previously used bodies and storage for 30 min at 80 ° C. Subsequently, the films were rinsed again and evaluated.

15. Determination of the Erichsen depression

The Erichsen cupping was determined with the thermoforming device of Byk Chemie. The value given is the penetration depth of the sphere in mm, at which the first flaking / tearing of the film is observed ( DIN EN 50101 ).

16. Gloss measurement

The gloss of the films was measured with Picogloss Model 503 from Erichsen under the irradiation angles of 20 °, 60 ° and 85 ° on black-painted sheets. 5-fold determinations were carried out, the highest and lowest value were deleted and the mean value of the remaining measured values was determined ( DIN 67530 ).

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

• CN 1070374 [0002]
• WO 2009156648 [0003]
• US 20110190464 [0003]
• DE 2805702 [0006]
• CN 1355161 [0006]
• DE 3423443 [0006]
• EP 0534666 A [0006]
• CA 795814 [0006]
• US 6194530 [0006]
• EP 1924547 [0007]
• EP 2162423 [0007]
• EP 2294048 [0007]
• DE 102010000945 [0007]
• BR 20007000631 [0008]
• US 20100216958 [0008]
• WO 2009076480 [0008]
• WO 2009008756 [0008]

Cited non-patent literature

• Tuliao Gongye (1985), 87, 13-16 [0002]
• Khimicheskaya Promyshlennost (1967), 43, 258-60 [0002]
• Nature (2008), 451, 86-89 [0008]
• ASTM D6866 [0010]
• ASTM D7026 [0010]
• Stickler, M. and Rhein, T. 2000. Polymethacrylates. Ullmann's Encyclopedia of Industrial Chemistry [0011]
• DIN ISO 6271 [0018]
• W. Huber: Titrations in Nonaqueous Solvents, 1964, Akademische Verlagsgesellschaft, Frankfurt am Main [0019]
• L. Safarik and Z. Stransky: Titrimetic Analysis in Organic Solvents, Volume XXII of Wilson and Wilson's Comprehensive [0019]
• Analytic Chemistry, Elsevier-Verlag, Amsterdam, 1986 [0019]
• DIN EN ISO 11357 [0020]
• DIN EN ISO 1522 [0024]
• DIN EN ISO 2409 [0024]
• DIN EN 50101 [0028]
• DIN 67530 [0029]

Claims (9)

Monomeric mixture of isoamylmethacrylates whose isomeric mixture of the isoamyl alcohol component of the isomeric composition corresponds to an isoamyl alcohol obtained from a renewable source of raw material. Monomer mixture according to claim 1, characterized in that the isomer ratio of the isoamyl alcohol 3-methylbutanol to 2-methylbutanol is 60:40 to 90:10. Monomer mixture according to claim 1, characterized in that the C content at 0.5 × 10 ^-10 % to 0.7 × 10 ^-10 % based on the total carbon content. A process for preparing a monomer mixture according to claim 1, characterized in that a lower methacrylate is transesterified with the corresponding isoamyl alcohol isomer mixture. A process for the preparation of a mixture according to claim 1, characterized in that the transesterification is carried out by means of homogeneous catalysis. A process for preparing a mixture according to claim 1, characterized in that the transesterification is carried out by means of heterogeneous catalysis. A process for the preparation of a mixture according to claim 1, characterized in that the transesterification is carried out continuously. Use of a monomer mixture according to claim 1 for the preparation of copolymers by copolymerization with vinylic comonomers, which are suitable for copolymerization with this monomer mixture. Copolymers containing, as comonomer component, isomers of isoamyl methacrylate whose isomer ratio of 3-methylbutyl methacrylate to 2-methylbutyl methacrylate is 60:40 to 90:10.