REACTIVE MONOMERS AS COMONOMERS FOR THE PRODUCTION OF POLYMERS

Abstract

The present invention relates to the use of reactive monomers as plasticizers in copolymers. The invention further relates to copolymers obtainable by using the reactive monomers. The present invention moreover relates to processes for the lowering of the glass transition temperature of copolymers with use of the reactive monomers.

Claims

1. (canceled)

2. The method according to claim 13, where R.sup.1, R.sup.2, and R.sup.3 are H.

3. The method according to claim 13, where R.sup.4 is CH.sub.2CH.sub.2CH.sub.2CH.sub.2.

4. The method according to claim 13, where R.sup.5 is H and R.sup.6 is CH.sub.3.

5. The method according to claim 13, where R.sup.7 is H.

6. The method according to claim 13, where X is O.

7. The method according to claim 13, where the copolymers are produced in a free-radical emulsion polymerization reaction.

8. The method according to claim 13, where the OH number of the compound of formula (I) is from 2 mg KOH/g to 225 mg KOH/g.

9. The method according to claim 13, where a polydispersity of the compound of formula (I) is from 1.0 to 2.0.

10. The method according to claim 13, where the compound is copolymerized with one or more olefinically unsaturated compound.

11. The method according to claim 10, where the one or more olefinically unsaturated compound is selected from the group consisting of vinylaromatic compounds, ethylenically unsaturated carboxylic acids having from 3 to 10 carbon atoms, C.sub.1-C.sub.10-alkyl esters of ethylenically unsaturated carboxylic acids having from 3 to 10 carbon atoms, vinyl acetate, ethene, propene, 1,3-butadiene, isoprene, -olefins having from 10 to 250 carbon atoms, in each case in pure form or as isomer mixture, SO.sub.4-containing monomers, and PO.sub.4-containing monomers.

12. The method according to claim 13, where the glass transition temperature of the copolymer is lowered by from 5 to 70 K.

13. A process for lowering of a glass transition temperature of a copolymer comprising adding, during a polymerization reaction, an effective quantity, based on an entire composition of monomers used, of from 0.1 to 50% by weight, of a compound of general formula (I) ##STR00002## where R.sup.1, R.sup.2, R.sup.3 are mutually independently, being identical or different, H or CH.sub.3, X is O or C.sub.1-C.sub.4-alkoxy, R.sup.4 is a single bond or linear or branched C.sub.1-C.sub.6-alkylene, R.sup.5, R.sup.6 are mutually independently, being identical or different, H, C.sub.1-C.sub.5-alkyl, or aryl, R.sup.7 are mutually independently, being identical or different, H or C.sub.1-C.sub.6-alkyl, and n is an integer from 0 to 200.

14. A process for the production of a copolymer, where an effective quantity, based on an entire composition of monomers used, of from 0.1 to 50% by weight, of a compound of general formula (I) ##STR00003## where R.sup.1, R.sup.2, R.sup.3 are mutually independently, being identical or different, H or CH.sub.3, X is O or C.sub.1-C.sub.4-alkoxy, R.sup.4 is a single bond or linear or branched C.sub.1-C.sub.6-alkylene, R.sup.5, R.sup.6 are mutually independently, being identical or different, H, C.sub.1-C.sub.5-alkyl, or aryl, R.sup.7 are mutually independently, being identical or different, H or C.sub.1-C.sub.6-alkyl, and n an integer from 0 to 200.

15. A copolymer produced according to the process of claim 13.

16. The process according to claim 13 comprising adding from 0.5to 30%, by weight of the compound of general formula (I).

17. The process according to claim 16 comprising adding from 1 to 20%, by weight of the compound of general formula (I).

18. The process according to claim 17 comprising adding from 0.5 to 10%, by weight of the compound of general formula (I).

19. The process according to claim 9 wherein the polydispersity of the compound of formula (I) is 1.0 to 1.5.

20. The process according to claim 19 wherein the polydispersity of the compound of formula (I) is 1.0 to 1.2.

21. The process according to claim 8 wherein the OH number of the compound of formula (I) is from 20 KOH/g to 225 mg KOH/g.

Description

EXAMPLES

Examples of the Invention

[0054] 1. Synthesis of the Alkoxylates

[0055] 1.1 HBVE+5 PO

[0056] 1161.6 g (10 mol) of hydroxybutyl vinyl ether (HBVE) and 20.3 g of potassium methanolate (30% in methanol) were charged to a 10 liter autoclave with propeller stirrer. The autoclave was sealed and evacuated by three repetitions of evacuation (<20 mbar) followed by introduction of nitrogen. The mixture was then heated to 75 C., with stirring (100 rpm) and, to remove the methanol, again subjected to four repetitions of evacuation to <20 mbar (in each case for 20 min) and refilling with nitrogen. The system was now heated to a temperature of 110 C., and adjusted to a supply pressure of 0.5 bar with nitrogen, and propylene oxide (PO) metering was begun, while keeping the overall gauge pressure at or below 5 bar. After about 23 hours all of the PO (2904 g, 50 mol) had been metered into the system, and reaction was allowed to continue for a further 24 hours. The reaction mixture was cooled to 80 C., and evacuated for devolatilization purposes, and nitrogen was used to release the vacuum. The system was then cooled to room temperature, and 0.4 g (100 ppm) of BHT (3,5-di-tert-butyl-4-hydroxytoluene) was added for stabilization.

[0057] Total output is 3960 g.

[0058] Characterization:

[0059] pH (EN 1262, solution C)=11.8

[0060] OH number (DIN 53240)=139.7 mg KOH/g

[0061] Polydispersity (GPC)=1.07

[0062] Water content (EN 13267)=0.08%

[0063] 1.2 HBVE+10 PO (Single-Stage Synthesis)

[0064] 2700 g (23.244 mol) of hydroxybutyl vinyl ether (HBVE) and 16.9 g of potassium methanolate (32% in methanol)corresponding to 2000 ppm (based on starting alcohol) were charged to a 20 liter autoclave with propeller stirrer. The autoclave was sealed and evacuated by three repetitions of evacuation (<20 mbar) followed by introduction of nitrogen. The mixture was then heated to 75 C., with stirring (100 rpm) and, to remove the methanol, again subjected to three repetitions of evacuation to <20 mbar (in each case for 10 min) and refilling with nitrogen. The system was now heated to a temperature of from 135 to 140 C., and adjusted to a supply pressure of 0.5 bar with nitrogen, and propylene oxide (PO) metering was begun, while keeping the overall gauge pressure at or below 5 bar. After about 33 hours all of the PO (13 500 g) had been metered into the system, and reaction was allowed to continue for a further 5 hours. The reaction mixture was cooled to 80 C., and evacuated for devolatilization purposes, and nitrogen was used to release the vacuum. 4.6 g of acetic acid (100%) were then used for neutralization, and 0.7 g (100 ppm) of BHT (3,5-di-tert-butyl-4-hydroxytoluene) was added for stabilization.

[0065] Total output is 3960 g.

[0066] Characterization:

[0067] pH (EN 1262, solution C)=6.9

[0068] OH number (DIN 53240)=85.9 mg KOH/g

[0069] OH number (by TAI NMR)=81.5 mg KOH/g

[0070] Polydispersity (GPC)=1.077

[0071] Color number (Hazen, EN 1557)=44

[0072] Water content (EN 13267)=0.2%

[0073] 1.3 HBVE+8 PO (Two-Stage Synthesis)

[0074] 75 g (0.65 mol) of hydroxybutyl vinyl ether (HBVE) and 0.47 g of potassium methanolate (32% in methanol)corresponding to 0.20% by weight (based on starting alcohol) were charged to a one liter autoclave with crossblade stirrer. The autoclave was sealed and inertized by three repetitions of evacuation (<100 mbar) and introduction of nitrogen. The mixture was then heated to 80 C., with stirring (300 rpm), and methanol was removed by distillation for 1 hour. The system was then aerated with nitrogen and heated to a temperature of from 135 to 140 C., and a nitrogen supply pressure of 0.7 bar was established at this temperature. Metering of propylene oxide (PO) was begun, and was conducted in a way that kept the overall gauge pressure at or below 3.1 bar. After about 10 hours the first quantity of PO (182 ml; 4 molar equivalents, based on HBVE) had been metered into the system, and the reaction was allowed to continue for one further hour. The heating was then switched off, and stirring was continued for 12 hours. The mixture was depressurized to atmospheric pressure, and a further 3.2 g of potassium methanolate (32% in methanol)corresponding to 0.45% by weight (based on mixture) were added. The autoclave was again inertized by three repetitions of evacuation (<100 mbar) and introduction of nitrogen. The mixture was then heated to 80 C., with stirring (300 rpm), and methanol was removed by distillation for 1 hour. After aeration with nitrogen, the system was heated to a temperature of from 135 to 140 C., and a nitrogen supply pressure of 0.7 bar was established at this temperature. Metering of propylene oxide (PO) was restarted, while keeping the overall gauge pressure at or below 3 bar. After about 9 hours the second quantity of PO (275 ml; 3.9 mol) was metered into the system, and the reaction was allowed to continue for a further 4 hours. The system was then cooled to 80 C. and stripped at <100 mbar for 1 hour. The mixture was then aerated with nitrogen and cooled to 60 C., and 1.0 g of acetic acid (90%), and also 0.045 g of BHT were added for stabilization. The reaction mixture was stirred for 30 min and discharged.

[0075] Characterization:

[0076] pH (DIN 19268; 5% in ethanol/distilled water (1:1), 23 C.)=5.0

[0077] OH number (DIN 53240)=94 mg KOH/g

[0078] 1.4 HBVE+10 PO (Two-Stage Synthesis)

[0079] 580 kg (4.99 kmol) of hydroxybutyl vinyl ether (HBVE) and 4.4 kg of potassium methanolate (32% in methanol)corresponding to 0.24% by weight (based on starting alcohol) were charged to a 4.4 m.sup.3 reactor with crossblade stirrer. The latter was evacuated to <100 mbar, while being heated to an internal temperature of 80 C. About 3 kg of methanol was then removed by distillation during 30 min, with stirring. Nitrogen was then used to release the vacuum, and evacuation and introduction of nitrogen were repeated until oxygen content reached <0.3%. The system was then heated to a temperature of 135 to 140 C., and a nitrogen supply pressure of 0.3 bar was established at this temperature. Metering of propylene oxide (PO) was begun, and was conducted so as to keep the overall gauge pressure at or below 1.4 bar. After about 14.5 hours the first quantity of PO (830 kg, 14.39 kmol; 3 molar equivalents, based on HBVE) had been metered into the system, and the reaction was allowed to continue for a further 2 hours. The system was then cooled to 75 C. and simultaneously depressurized. A further 57 kg of potassium methanolate (32% in methanol)corresponding to 1.29% by weight (based on mixture) were then added. The reactor was evacuated to <100 mbar and heated to 140 C. During this procedure, about 39 kg of methanol were removed by distillation in about 1 hour. Nitrogen was used to release the vacuum, and a gauge pressure of 0.05 bar was established. Metering of propylene oxide (PO) was then restarted, while keeping the overall gauge pressure at or below 1.4 bar. After about 13 hours the second quantity of PO (1910 kg, 32.89 kmol; 7 molar equivalents, based on HBVE) had been metered into the system, and the reaction was allowed to continue for a further 2 hours. The system was then cooled to 90 C. and stripped at <100 mbar for 2 hours with a nitrogen flow rate of 15 m.sup.3/h. The mixture was then aerated with nitrogen and cooled to 50 C., and 16.8 kg (0.28 kmol) of acetic acid (100%), and also 3.5 kg of BHT, were added for stabilization. The reaction mixture was stirred for 30 min and discharged.

[0080] Characterization:

[0081] pH (DIN 19268; 5% in ethanol/distilled water (1:1), 23 C.)=6.8

[0082] OH number (DIN 53240)=93.6 mg KOH/g

[0083] OH number (by TAI NMR)=81.2 mg KOH/g

[0084] Color number (Hazen, EN 1557)=3.1

[0085] Polydispersity (GPC)=1.098

[0086] Water content (EN 13267)=0.73%

[0087] Viscosity (23 C., Stabinger, kinematic)=55 mm.sup.2/sec

[0088] 1.5 HBVE+10 BuO

[0089] 348.9 g (3.0 mol) of hydroxybutyl vinyl ether (HBVE) and 7.5 g of potassium tert-butanolate were charged to a 5 liter autoclave with anchor stirrer. The autoclave was sealed and inertized by three repetitions of introduction of nitrogen (up to a pressure of 5 bar) followed by depressurization. The mixture was then heated to 120 C., with stirring (150 rpm), and 2160 g (30.0 mol) of butylene oxide were metered into the system over a total of 1730 min. Once addition had ended, stirring was continued for a further 4 hours at constant pressure. The reaction mixture is cooled to 80 C. and flushed with nitrogen for 30 min for devolatilization. The product was discharged (yield 2478 g), and 3% by weight of Ambosol were admixed for neutralization/desalination, and the product was filtered through a pressure-filter funnel.

[0090] Characterization:

[0091] pH (EN 1262, solution B)=6.1

[0092] OH number (by TAI NMR)=76 mg KOH/g

[0093] Polydispersity (GPC)=1.08

[0094] 1.6 HBVE+10 PeO

[0095] 348.9 g (3.0 mol) of hydroxybutyl vinyl ether (HBVE) and 8.8 g of potassium tert-butanolate were charged to a 5 liter autoclave with anchor stirrer. The autoclave was sealed and inertized by three repetitions of introduction of nitrogen (up to a pressure of 5 bar) followed by depressurization. The mixture was then heated to 120 C., with stirring (150 rpm), and 2580 g (30.0 mol) of pentene oxide were metered into the system over a total of 1210 min. Once addition had ended, stirring was continued for a further 10 hours at constant pressure. The reaction mixture was cooled to 80 C. and flushed with nitrogen for 30 min for devolatilization. The product is discharged, and residual pentene oxide is drawn off on a rotary evaporator. 3% by weight of Ambosol were admixed for neutralization/desalination, and the mixture was filtered through a pressure-filter funnel. Yield was 2985 g.

[0096] Characterization:

[0097] pH (EN 1262, solution B)=6.6

[0098] OH number (by TAI NMR)=69 mg KOH/g

[0099] 1.7 HBVE+11 EO

[0100] 755.95 g (6.5 mol) and 6.1 g of potassium methanolate (30% in methanol) were charged to a 5 liter autoclave with anchor stirrer. The autoclave was sealed and inertized by three repetitions of evacuation (<20 mbar) and introduction of nitrogen. The mixture was then heated to 75 C., with stirring (100 rpm), and, to remove the methanol, again subjected to four repetitions of evacuation to <20 mbar (in each case for 20 min) and refilling with nitrogen. The system was then heated to a temperature of 150 C., a supply pressure of 0.5 bar of nitrogen was established, and metering of ethylene oxide (EO) was begun, while the overall gauge pressure was kept at 5 bar or below. After about 5 hours all of the EO (3146 g, 71.5 mol) had been metered into the system, and reaction was allowed to continue for one further hour. The reaction mixture was cooled to 80 C. and evacuated for devolatilization, and nitrogen was used to release the vacuum. The system was then cooled to room temperature. 3% by weight of Ambosol were then admixed for neutralization/desalination, and the mixture was filtered through a pressure-filter funnel.

[0101] Total output is 3850 g.

[0102] Characterization:

[0103] pH (EN 1262, solution B)=6.1

[0104] OH number (DIN 53240)=97.0 mg KOH/g

[0105] Polydispersity (GPC)=1.07

[0106] General Analytical Method:

[0107] Gel permeation chromatography (GPC): based on DIN 55672-1

[0108] Equipment

[0109] Separating columns: Polymer Laboratories Ltd., Shropshire, GB

[0110] Pump: Merck GmbH, 64239 Darmstadt

[0111] UV detector: L4000 (254 nm), Merck GmbH, 64239 Darmstadt

[0112] RI detector: ERC 7515 B, ERC GmbH, 93087 Alteglofsheim

[0113] Evaluation: Polymer Standard Service (PSS), 55023 Mainz

[0114] Injection: S 5200 autosampler, Duratec, 68799 Reilingen

[0115] Devolatilizer: S 7505 (vacuum devolatilization), Duratec, 68799 Reilingen

[0116] Column sets for various molecular size ranges: [0117] Column set A: quadruple 3007.5 mm; 5m 2500 , 100 , 50 single analytical precolumn; 5 m; mixed-gel [0118] Column set B: quadruple 3007.5 mm; 5 m, 210000 , 21000 single analytical precolumn; 5 m; mixed-gel [0119] Temperature control: both sets are within temperature-controlled ovens at 30 C. [0120] Pump/Flow rate: L-6200 /1 ml/min

[0121] Reagents [0122] Eluent: Chromatography-grade tetrahydrofuran (provided from 2.5 l brown glass bottle with activated charcoal filter) [0123] Sample volume: 20 l [0124] Sample concentration: 1% in internal standard solution [0125] Internal standard solution: tetrahydrofuran doped with 0.1% of analytical-grade toluene [0126] Calibration: ReadyCal kits (polystyrene, PSS) [0127] 1. Mp from 266 to 67 500 g/mol (column set A) [0128] 2. Mp from 376 to 2 570 000 g/mol (column set B)

[0129] Method

[0130] The anhydrous sample (content <1%) is dissolved in internal standard solution at 1% strength, filtered if necessary, and injected by way of an autosampler onto the separating columns. Intensity and position of the detected peaks are evaluated.

[0131] Calculation

[0132] Data recording/evaluation: WINGPC (PSS)

[0133] The printout includes inter alia the following data: [0134] Distribution curve [0135] Number average Mn [0136] Weight average Mw [0137] Polydispersity D [0138] Molar mass at peak maximum Mp

[0139] Determination of OH Number by TAI NMR:

[0140] 400 MHz .sup.1H NMR in CDCl.sub.3 and TAI (trichloroacetylisocyanate) The method is described inter alia in V. W. Goodlett, Analytical Chemistry, vol. 37, No. 3, pages 431 and 432

[0141] I. Emulsion Polymerization Process

[0142] II.1 Emulsion Polymerization of a Styrene/Acrylate Formulation to Determine the Glass Transition Temperature

[0143] Apparatus: 1.7 liter glass reaction vessel equipped with anchor stirrer and immersed in a water bath for temperature control. Also two storage vessels to provide the feeds (one stirred for the monomer premix and one not stirred for the initiator solution). The feed vessels are suspended on a weighing unit which can determine precisely the quantity metered into the system. Metering is achieved by means of a small gauge pressure in the feed vessel, controlled by way of compressed-air valves. A computer program controls internal reactor temperature, water bath temperature, and feeds.

[0144] Comonomer system: Styrene, n-butyl acrylate (alternatively HBVE+10 PO (as in example 1.2)), methacrylic acid (Screening 1, Karolina)

[0145] Method:

[0146] Production of Comonomer Premix:

[0147] Styrene (A g), n-butyl acrylates (B g) (alternatively HBVE+10 PO (as in example 1.2) C g), methacrylic acid (15 g), deionized water (450 g) and anionic emulsifier (Disponil FES 32 from BASF SEaqueous solution of a C.sub.12C.sub.14 fatty alcohol ether sulfate with 4 EOcorresponding to 20 g of active substance) are mixed and charged to the stirred feed vessel 1.

[0148] For the exact quantities A, B, and C, see table 1.

[0149] Production of Initiator Solution:

[0150] 4 g of sodium metabisulfite (Na.sub.2SO.sub.5) are dissolved in 100 g of deionized water. This solution is charged to the second, unstirred, feed vessel 2.

[0151] Reaction:

[0152] A solution of 4 g of potassium peroxodisulfate (K.sub.2S.sub.2O.sub.5) in 250 g of deionized water was charged to the reaction vessel and 225 g of the pre-emulsion were metered into the system from the feed vessel 1. This mixture was heated to 60 C. and, once the temperature had been reached, 8 g of initiator solution were metered into the system from the feed vessel 2. After stirring for 5 minutes at 60 C., parallel metering of the pre-emulsion from feed vessel 1 and of the initiator from feed vessel 2 began. The pre-emulsion was metered into the system over a period of 150 min, and the initiator was metered into the system over a period of 160 min. The internal temperature was kept at 60 C. during the entire metering period. Once the initiator feed had ended, the internal temperature was increased to 65 C. and was kept at this level for 60 min. For additional stabilization of the dispersion, 26 g of a C.sub.16C.sub.18 fatty alcohol ethoxylate (with 18 EO) were added within this post-reaction phaseafter about 30 minutes.

[0153] The dispersion was now cooled to room temperature and adjusted to pH from 7 to 8 with 25% aqueous ammonia solution.

[0154] Work-Up and Analysis:

[0155] The dispersion was drawn off into packs by way of a 150 micrometer filter.

TABLE-US-00001 TABLE 1 Input weight [g] Glass transition Styrene n-Butyl HBVE + 10PO Methacrylic temperature (A) acrylate (B) (C) acid (Tg) [ C.] 800 0 0 15 92 600 200 0 15 56 400 400 0 15 20 200 600 0 15 15 0 800 0 15 46 600 0 200 15 51 400 0 400 15 16 200 0 600 15 67

[0156] II.2 Emulsion Polymerization of a Styrene/Acrylate Formulation to Determine Emulsion Properties

[0157] Apparatus: 1.7 liter glass reaction vessel equipped with anchor stirrer and immersed in a water bath for temperature control. Also two storage vessels to provide the feeds (one stirred for the monomer premix and one not stirred for the initiator solution). The feed vessels are suspended on a weighing unit which can determine precisely the quantity metered into the system. Metering is achieved by means of a small gauge pressure in the feed vessel, controlled by way of compressed-air valves. A computer program controls internal reactor temperature, water bath temperature, and feeds.

[0158] Comonomer system: Styrene, n-butyl acrylate (alternatively HBVE+10 PO (as in example 1.2)), methacrylic acid (Screening 1, Linda)

[0159] Method:

[0160] Production of Comonomer Premix:

[0161] Styrene (A g), n-butyl acrylates (B g) (alternatively HBVE+10 PO (as in example 1.2) C g), methacrylic acid (15 g), deionized water (450 g) and anionic emulsifier (Disponil FES 77 from BASF SEaqueous solution of a C.sub.12C.sub.14 fatty alcohol ether sulfate with 30 EOcorresponding to 20 g of active substance) are mixed and charged to the stirred feed vessel 1.

[0162] For the exact quantities A, B, and C, see table 2.

[0163] Production of Initiator Solution:

[0164] 4 g of sodium metabisulfite (Na.sub.2SO.sub.5) are dissolved in 100 g of deionized water. This solution is charged to the second, unstirred, feed vessel 2.

[0165] Reaction:

[0166] A solution of 4 g of potassium peroxodisulfate (K.sub.2S.sub.2O.sub.5) in 250 g of deionized water was charged to the reaction vessel and 225 g of the pre-emulsion were metered into the system from the feed vessel 1. This mixture was heated to 60 C. and, once the temperature had been reached, 8 g of initiator solution were metered into the system from the feed vessel 2.

[0167] After stirring for 5 minutes at 60 C., parallel metering of the pre-emulsion from feed vessel 1 and of the initiator from feed vessel 2 began. The pre-emulsion was metered into the system over a period of 150 min, and the initiator was metered into the system over a period of 160 min. The internal temperature was kept at 60 C. during the entire metering period. Once the initiator feed had ended, the internal temperature was increased to 65 C. and was kept at this level for 60 min.

[0168] The dispersion was now cooled to room temperature and adjusted to pH from 7 to 8 with 25% aqueous ammonia solution.

[0169] Work-Up and Analysis:

[0170] The dispersion was drawn off into packs by way of a 150 micrometer filter.

[0171] Determination of coagulate: The coagulate collected in the filter was washed with deionized water and dried at 50 C. for 24 hours. It was weighed together with the coagulate scraped from stirrer and thermometer and dabbed dry in a cloth. The quantity of coagulate was stated as % of total theoretical dry content.

[0172] Conversion: The dry content of the dispersion was determined by drying of about 5 g at 150 C. for 20 min in an HR 83 Mettler Toledo halogen moisture analyzer. The quotient calculated from the dry content determined and the theoretical dry content was stated as conversion (in %).

[0173] Particle size: Particle size was determined by means of laser diffraction in a LS 13320 Beckman Coulter diffraction particle size analyzer. The d.sub.50 value determined on the equipment was stated as particle size (in nm).

[0174] Viscosity: Dynamic viscosity was determined with a Brookfield DV-II+ viscometer with RV spindle set (spindle 1) and stated in [mPas].

TABLE-US-00002 TABLE 2 Input weight [g] Con- Par- Sty- n-Butyl HBVE + Meth- ver- Coag- ticle Viscos- rene acrylate 10PO acrylic sion ulate size ity (A) (B) (C) acid [%] [%] [nm] [mPas] 400 400 0 15 97.8 0.7 175 200 400 0 400 15 94.7 2.2 105 75 400 200 200 15 98.1 0.4 135 75 600 0 200 15 97.5 0.8 135 100

TABLE-US-00003 TABLE 3 Input weight [g] Con- Par- Sty- n-Butyl HBVE + Meth- ver- Coag- ticle Viscos- rene acrylate 10PO acrylic sion ulate size ity (A) (B) (C) acid [%] [%] [nm] [mPas] 400 400 0 15 97.8 0.7 175 200 400 0 400 15 94.7 2.2 105 75 400 200 200 15 98.1 0.4 135 75 600 0 200 15 97.5 0.8 135 100

[0175] II.3 Emulsion Polymerization of a Vinyl Acetate Copolymer Formulation

[0176] Apparatus: 1.7 liter glass reaction vessel equipped with anchor stirrer and immersed in a water bath for temperature control. Also two storage vessels to provide the feeds (one stirred for the monomer premix and one not stirred for the initiator solution). The feed vessels are suspended on a weighing unit which can determine precisely the quantity metered into the system. Metering is achieved by means of a small gauge pressure in the feed vessel, controlled by way of compressed-air valves. A computer program controls internal reactor temperature, water bath temperature, and feeds.

[0177] Comonomer system: Vinyl acetate, VeoVA 10 from Momentive Specialty Chemicals Inc. (alternatively HBVE+10 PO (as in example 1.2)), acrylic acid (Screening 4, Karolina)

[0178] Method:

[0179] Production of Comonomer Premix:

[0180] Vinyl acetate (A g), VeoVA 10 (B g) (alternatively HBVE+10 PO (as in example 1.2) C g), acrylic acid (9 g), deionized water (355 g), disodium tetraborate (4 g), anionic emulsifier (Disponil FES 32 from BASF SEaqueous solution of a C.sub.12C.sub.14 fatty alcohol ether sulfate with 4 EOcorresponding to 2 g of active substance), and nonionic emulsifier (Disponil A 3065 from BASF SEaqueous solution of a modified C.sub.12C.sub.14 fatty alcohol ethoxylate with 30 EOcorresponding to 20 g of active substance) were mixed and charged to the stirred feed vessel 1.

[0181] For the exact quantities A, B, and C, see table 2.

[0182] Production of Initiator Solution:

[0183] 3.2 g were dissolved in 70 g of deionized water. This solution is charged to the second, unstirred, feed vessel 2.

[0184] Reaction:

[0185] A solution of 0.8 g of potassium peroxodisulfate (K.sub.2S.sub.2O.sub.5), 0.4 g of disodium tetraborate (Na.sub.2B.sub.4O.sub.7), and anionic emulsifier (Disponil FES 32 from BASF SEaqueous solution of a C.sub.12C.sub.14 fatty alcohol ether sulfate with 4 EOcorresponding to 2.6 g of active substance) in a total of 395 g of deionized water were to the reaction vessel. This mixture was heated to 80 C., and once the temperature had been reached parallel metering of the pre-emulsion from feed vessel 1 and of the initiator from feed vessel 2 was begun. The pre-emulsion was metered into the system over a period of 180 min and the initiator was metered into the system over a period of 190 min. Internal temperature was kept at 80 C. during the entire metering time. Once the initiator feed had ended internal temperature was kept at 80 C., with stirring, for a further 60 min. Within this post-reaction phaseafter about 30 minutes27 g of a C.sub.16C.sub.18 fatty alcohol ethoxylate (with 18 EO) were added for additional stabilization of the dispersion.

[0186] The dispersion was now cooled to room temperature and adjusted to pH from 7 to 8 with 25% aqueous ammonia solution.

[0187] Work-Up and Analysis:

[0188] The dispersion was drawn off into packs by way of a 150 micrometer filter.

[0189] Glass transition temperature was determined by means of dynamic scanning calorimetry (DSC). For this, the dispersion was cast and filmed overnight and then dried at 120 C. in vacuo for one hour. About 9 mg of the material was used for measurement, and this was cooled rapidly from 150 C. before the actual measurement. The heating rate used for the subsequent measurement was 20 K/min.

TABLE-US-00004 TABLE 4 Input weight [g] Vinyl acetate Glass transition (A) VeoVA 10 (B) HBVE + 10PO (C) temperature (Tg) [g] [g] [g] [ C.] 670 170 0 23 500 340 0 14 333 507 0 4 0 840 0 5 840 0 0 31 670 0 170 10 500 0 340 22 333 0 507 56

TABLE-US-00005 TABLE 5 Input weight [g] Vinyl acetate VeoVA HBVE + 10PO Glass transition (A) 10 (B) (C) Acrylic temperature [g] [g] [g] acid (Tg) [ C.] 670 170 0 9 23 500 340 0 9 14 333 507 0 9 4 0 840 0 9 5 840 0 0 9 31 670 0 170 9 10 500 0 340 9 22 333 0 507 9 56

[0190] II.3 Emulsion Polymerization in an Acrylate-Only Formulation

[0191] Apparatus: 1.7 liter glass reaction vessel equipped with anchor stirrer. Temperature control was achieved by way of the jacket of the vessel, by means of a thermostat. Also two storage vessels to provide the feeds (one stirred for the monomer premix and one not stirred for the initiator solution). The feed vessels are suspended on a weighing unit which can determine precisely the quantity metered into the system. Metering is achieved by means of a small gauge pressure in the feed vessel, controlled by way of compressed-air valves. A computer program controls internal reactor temperature, water bath temperature, and feeds.

[0192] Comonomer system: Methyl methacrylate, 2-ethylhexyl acrylate (alternatively HBVE+10 PO (as in example 1.2)), methacrylic acid

[0193] Method:

[0194] Production of Comonomer Premix:

[0195] Methyl methacrylate (A g), 2-ethylhexyl acrylate (B g), HBVE+10 PO (as in example 1.2) C g, methacrylic acid (15 g), deionized water (268.44 g) and anionic emulsifier (Disponil FES 32 from BASF SEaqueous solution of a C.sub.12C.sub.14 fatty alcohol ether sulfate with 4 EOcorresponding to 5 g of active substance) are mixed and charged to the stirred feed vessel 1

[0196] For the exact quantities A, B, and C, see table 1.

[0197] Production of Initiator Solution:

[0198] 3 g of potassium peroxodisulfate (K.sub.2S.sub.2O.sub.5) were dissolved in 60 g of deionized water. This solution was charged to the second, unstirred, feed vessel 2.

[0199] Reaction:

[0200] A solution of 0.4 g of potassium peroxodisulfate (K.sub.2S.sub.2O.sub.5), 0.8 g of sodium hydrogencarbonate (NaHCO.sub.3), and 36.42 g of anionic emulsifier (Disponil FES 32 from BASF SEaqueous solution of a C.sub.12C.sub.14 fatty alcohol ether sulfate with 4 EOcorresponding to 11 g of active substance) in 405 g of deionized water was charged to the reaction vessel. Parallel metering of the pre-emulsion from feed vessel 1 and of the initiator from feed vessel 2 now began. The pre-emulsion was metered into the system over a period of 80 min and the initiator was metered into the system over a period of 90 min. Internal temperature was kept at 85 C. during the entire metering time. Once the initiator feed had ended internal temperature was kept at 85 C. and stirring was continued for 60 min.

[0201] The dispersion was now cooled to room temperature, and a solution of 8.8 g of sodium hydrogencarbonate in 30 g of deionized water was added.

[0202] Work-Up and Analysis:

[0203] The dispersion was drawn off into packs by way of a 150 micrometer filter.

[0204] Determination of coagulate: The coagulate collected in the filter was washed with deionized water and dried at 50 C. for 24 hours. It was weighed together with the coagulate scraped from stirrer and thermometer and dabbed dry in a cloth. The quantity of coagulate was stated as % of total theoretical dry content.

[0205] Conversion: The dry content of the dispersion was determined by drying of about 5 g at 150 C. for 20 min in an HR 83 Mettler Toledo halogen moisture analyzer. The quotient calculated from the dry content determined and the theoretical dry content was stated as conversion (in %).

[0206] Particle size: Particle size was determined by means of laser diffraction in a LS 13320 Beckman Coulter diffraction particle size analyzer. The d.sub.50 value determined on the equipment was stated as particle size (in nm).

[0207] Viscosity: Dynamic viscosity was determined at room temperature with a Brookfield DV-II+ viscometer at 20 rpm with RV spindle set (spindle 1) and stated in [mPas].

TABLE-US-00006 TABLE 6 Input weight [g] Methyl 2-Ethyl- Con- meth- hexyl HBVE + ver- Coag- Particle Viscos- acrylate acrylate 10PO sion ulate size ity (A) (B) (C) [%] [%] [nm] [mPas] 410 360 0 100 1.6 80 4310 410 180 180 96.5 2.6 91 343 590 0 180 98.6 1.1 95 216

TABLE-US-00007 TABLE 7 Input weight [g] Methyl 2-Ethyl- Con- Par- meth- hexyl HBVE + Meth- ver- Coag- ticle Viscos- acrylate acrylate 10PO acrylic sion ulate size ity (A) (B) (C) acid [%] [%] [nm] [mPas] 410 360 0 15 100 1.6 80 4310 410 180 180 15 96.5 2.6 91 343 590 0 180 15 98.6 1.1 95 216

[0208] Dynamic Scanning Calorimetry (DSC)

[0209] The sample/dispersion to be studied was cast and dried at room temperature overnight. The measurement used about 6-9 mg of the dried sample. Before the measurement, the sample was heated to temperatures of from 120 C. to 150 C. and rapidly cooled. The sample was then subjected to measurement at a heating/cooling rate of 20 K/min. The equipment used was a DSC Q2000 from TA Instruments.