Liquid Rosin (Tall Oil) Production, Uses, Extraction, Processing, Compositions and Formulations Hand Book

Description

• Introduction
• Composition
• Fatty acids
• Resin acids
• Unsaponifiables
• Uses of Liquid Rosins
• Tall oil
• Lignins
• Calcium ions
• Sulphide ions
• Factors affecting quality of CTO
• Dehydration
• Depitching
• Rosin separation
• Heads separation
• Fatty acid separation

• Experimental Procedures
• Results and Discussion

• Cationic Surfactants Experimental
• Preparation of maleopimaric acid (MPA)
• Preparation of rosin cationic surfactants (QRMAE)
• Electrochemical measurement
• Surface Activity of the prepared surfactants
• Esterification of rosin
• Esterification of RMA-MPEG 750
• Characterization of the prepared Surfactants
• Surface Activity of the prepared surfactants

• Sources, production and utilization of crude tall oil
• Tall oil as a wood protection agent
• Wood extractives and natural durability
• Effect of tall oil on the biological durability of wood
• Effect of tall oil on water repellency
• Reducing the amount of oil needed
• Enhancing the drying properties of crude tall oil
• Enhancing the wood protection properties of tall oil
• Biodegradability of tall oil-based wood preservatives

• Resin synthesis
• Materials
• Curing process
• Trial experiments for scheme 2 and scheme 3
• Characterization of resins
• Results and discussion of resins
• FTIR analysis of the synthesized thermoset resins
• Composite preparation
• Hand lay-up impregnation
• Characterization of composites
• Flexural testing
• Dynamic mechanical thermal analysis

• Copolymers, Drying Processese
• Introduction
• Alkyd resin
• Alkyd-acrylic copolymers
• The drying process
• Synthesis of copolymers
• Celluloses used as fillers
• Films and coatings
• Characterization
• Surface modification
• Degree of substitution
• Barrier properties

• Manufacturing
• Production of sterols from vegetable oil distillates
• Production of sterols from wood pulp/tall oil
• Production of phytostanols from phytosterols
• Production of phytosterol and phytostanol esters
• Free fatty acid route
• Methylester route
• Commercial suppliers
• Chemical Characterization
• Composition and properties
• Quality of phytosterols, phytostanols and their esters
• Analytical methods
• Regulatory status
• Reactions and fate in foods
• Stability at high temperatures

• The BUS model

• Materials and Methods
• Raw materials
• Formulation of long-chain alcohols in Pluronic® F-68
• Cell culture assays
• Statistical analysis

• Polyurethanes Based on Tall Oil
• Synthesis of polyols
• Preparation and characterization of polyurethanes
• Properties of polyols
• Structure of polyols and polyurethanes
• Properties of polyurethanes

• Ricinoleic Acid Modification
• Polyamine Modification
• Amino Alcohol Modification
• Imidazoline Modification
• Metal Chelate Modification
• Ester Modification
• Amino Acid Modification
• Polyfunctional Corrosion Inhibitors
• Sulfonate & Sulfate Modification
• General Considerations
• Maleation of Crude Tall Oil

• Detailed Description
• Odor Level Comparison Tests

• The Drawings
• Description

• Performance of Imidazoline and Amide
• Experimental
• Inhibitor Performance Evaluation
• The tests are conducted as follows

• Table 2.1 Gross Compositional Characteristics of American Distilled Tall Oilsa
• Table 2.2 Composition of Fatty and Resin Acids in American Distilled Tall Oils
• Table 2.3 GLC Retention and NMR Characteristics of the Methyl Secodehydroabietatesa
• Table 2.4 Composition of Pimaric-and Isopimaric-Type Acids Comprising Resin Acids of American Distilled Tall Oilsa
• Table 4. 1. Composition of CTO
• Table 4.2. Degree of water repellent efficiency (DEt) of tall oil-treated pine sapwood samples measured after 1 and 96 hours of water immersion
• Table 4.3. Properties of the tall oil emulsions
• Table 5.1: Different mass ratio of MA to HOTOFA
• Table 5.2: DSC analysis table of all uncured resin samples
• Table 5.3: TGA analysis for different cured resins
• Table  5.4: Summary of the DMTA result
• Table 5.5: Summary of charpy properties
• Table 6.1. Fatty acid composition of various oils used in coatings
• Table 6.2. Alkyd resins studied and used in copolymer synthesis
• Table 6.3. Generalized recipe for copolymerizations
• Table 6.4. Synthesized and studied copolymers
• Table 6.5. Synthesized copolymer dispersions, which
• were applied on paperboard
• Table 6.6 Relative proportions of each proton and proton group in the polyol region
• Table 6.7. Tg values of copolymer films and onset temperatures of the DMA measurements.The results are averages of five measurements
• Table 6.8. Comparison of the quantity of fatty acids attached based on the integrated cellulose and acyl peaks in the 13C CPMAS NMR spectra
• Table 6.9. Degree of substitution and O/C ratio calculated from XPS measurements
• Table 6.10. Mechanical properties of copolymer films studied with DMA, the results are averages from 3 to 8 measurements
• Table 7.1. Commercial suppliers of phytosterols, phytostanols and/or their esters; 1) TO: tall oil; VO: vegetable oil
• Table 7.2: Physical characteristics and composition of different commercial phytosterols, phytostanols and their esters; 1) from TO sterols; 2) from VO sterols; 3) mainly sitosterol and campesterol
• Table 7.3. Phytostanol concentrations in food products on the market, including portion sizes
• Table 8.1: Composition of test materials
• Table 8.2: Calculation of the MTT, PGE2, and (MTT + PGE2) combined score values
• Table 8.3: Results from the MTT assay and the PGE2 determination for tissue treated with a single application of tall oils
• Figure 8.1: Determination of the cytotoxicity of single and repeated applications of tall oils
• Table 8.4: Results from the MTT assay and the PGE2 determination for tissue treated with repeated applications of tall oils
• Table 9.1. Percentage of viability of CHO and melanoma cell cultures in the presence of long-chain aliphatic alcohols
• Table 10.1. Specifications of oils
• Table 10.2. Characteristics of polyols
• Table 10.3. Thermal stability of polyurethanes

• Figure 1 .1  The tall oil process
• Figure 3.1. FTIR spectra of a) RMAE and b) QRMAE
• Figure 3.2. 1HNMR spectra of a) RMAE and b) QRMAE
• Figure 3.3 Relation between surface tension of QRMAE and time at different concentrations in a) water and b) 1M aqueous HCl solutions at 25°C.
• Figure 3.4. Adsorption isotherms of QRMAE at different concentrations in a) water and b) 1M aqueous HCl solutions at 25°C.
• Figure 3.5. FTIR Spectra of a) RMA and b) RMA-(MPEG 750)3
• Figure 3.6. Relation between surface tension of R-MPEG 750 and time different concentrations in 1M aqueous HCl solutions.
• Fig. 4.1. Simplified diagram of the tall oil distillation pr
• Fig. 4.2. Fatty acids.
• Fig. 4.3. Resin acids.
• Fig. 4.4 Degree of efficiency after the initial wetting and drying cycle, measured after 1 hour of water immersion
• Fig. 4.5 Degree of efficiency after the initial wetting and drying cycle, measured after 96 hours of water immersion
• Fig. 4.6. Degree of efficiency after six wetting and drying cycles, measured after 1 hour of water immersion
• Fig. 4.7. Degree of efficiency after six wetting and drying cycles, measured after 96 hours of water immersion
• Fig. 4.8. DSC diagrams (110°C air flow) indicating the oil oxidation rate
• Fig. 4.9. Water uptake by tall oil-treated pine sapwood in the seventh wetting and drying cycle
• Fig. 4.10. Amounts of oil pressed out of the samples during the compression test
• Fig. 4.11. Typical particle size distribution of a tall oil-based emulsion
• Figure 5.1: synthesis scheme 1
• Figure 5.2: synthesis scheme 2
• Figure 5.3: synthesis scheme 3
• Figure 5.4: Experimental set-up for synthesis of thermosetting resin
• Figure 5.5: the obtained resins with three different mass ratio of MA to HOTOFA
• Figure 5.6 : FTIR spectra comparison of TOFA and HOTOFA resins
• Figure 5.7: FTIR spectra comparison of HOTOFA, MHOTOFA 1:1, MHOTOFA 1.5: 1 and MHOTOFA 1.76:1resins
• Figure 5.8: DSC curve of uncured MHOTOFA 1to1 (no styrene) resin
• Figure 5.9: DSC curve for cured MHOTOFA 1to1 resin (no styrene, room T for 1h and post cure in 150°C for another 1h)
• Figure 5.10: Comparison of the DSC scan for cured and uncured MHOTOFA 1to1 (no styrene) resin
• Figure 5.11: TGA analysis of cured MHOTOFA 1:1 resin (no styrene)
• Figure 5.12: Viscose fiber and fiber mats lay-up orientation
• Figure 5.13: Six different composites from 3 different resins (with or without styrene) reinforced by viscose fiber
• Figure 5.14: Test specimens for flexural, DMTA, charpy, tensile
• Figure 5.15: Flexural strength comparison of the composites
• Figure 5.16: Flexural modulus comparison of the composites
• Figure 5.17: Strain at break% comparison of the composites
• Figure 5.18: variation in the storage modulus of the MHOTOFA composites
• Figure 5.19: Tan delta curves of the MHOTOFA composites
• Figure 5.20: the loss modulus curves of MHOTOFA composites
• Figure 5.21: Comparison of the storage modulus between the reinforced resin (composite) and the unreinforced resin, both blended with styrene
• Figure 5.22: Impact strength of the composites
• Figure 6.1. Structure of typical alkyd resin
• Figure 6.2. Miniemulsion and conventional emulsion polymerization
• Figure 6.3. Schematic presentation of the oxidative drying of alkyd resin
• Figure 6.5. SEC chromatograms of alkyd resins
• Figure 6.6. Monomer conversion of copolymers with different wt% of conjugated alkyd resin (BA-MMA ratio is 80:20) (copolymers11-15 in Table 6.4)
• Figure 6.7. Monomer conversion of copolymers with different wt% of nonconjugated Alkyd-TMP-3 and BA as monomer (copolymers 1-5 in Table 6.4)
• Figure 6.8. Particle-size distribution of emulsion and dispersion with various alkyd contents (copolymers 1, 3, 5 in Table 6.4)
• Figure 6.9. Grafting of acrylic macroradical to double bond (a-c) and bis-allylic site (d-f) in the fatty acid chain. a) Macroradical attacks DB in fatty acid chain. b) Grafting occurs and a new radical is formed. c) Polymerization continues at the new radical site. d) Macroradical attacks allylic hydrogen in fatty acid chain. e) Hydrogen is abstracted and a new radical is formed in fatty acid chain, where new radical approaches. f) Macroradical grafts to radical site in fatty acid chain
• Figure 6.10. Monomer conversion and acrylic degree of grafting. BA-MMA ratio (wt%) was 80:20 in samples with conjugated alkyd (copolymers 11-15 in Table 6.4) and 100:0 in samples with nonconjugated alkyd (copolymers 1-5 in Table 6.4
• Figure 6.11. a) Effect ofBA concentration on grafting site and efficiency. b) Effect of alkyd-acrylate ratio on various grafting sites (copolymers 16-20 in Table 6.4)
• Figure 6.12. DSC thermograms of alkyd resin and copolymers (copolymers 16-20 in Table 6.4)
• Figure 6.13. a) TG and b) DTG curves showing thermal stability of alkyd resin, alkyd-acrylic copolymers, and acrylic copolymer.
• Figure 6.14. Two parts of FTIR spectra of neat whiskers and fatty acid-modified whiskers.The carbonyl peak at app. 1740 cm-1 is marked with dotted line
• Figure 6.15. Thermal stability of neat whiskers and fatty acid-modified whiskers presented as TGA curves
• Figure 6.16. a) ssNMR spectrum of copolymer film and freeze-dried copolymer. b) FTIR spectra of copolymer film after various drying times showing the decreasing intensity of the cis H-C=CH peak (marked with dotted line)
• Figure 6.17. Stress-strain curves of copolymer films with various alkyd contents. One measurement of each film sample set is presented
• Figure 6.18. Storage modulus of copolymer films with various alkyd contents. One measurement of each film sample set is presented
• Figure 6.19. Figure 1 Water and oil absorbance of copolymer-coated cupboards (copolymers 30-37). Samples 34-37 were crosslinked with GMA
• Figure 6.20. Effect of TOFA-modified whiskers on mechanical properties of films
• Figure 6.21. Effect of various cellulose types on mechanical properties of the films
• Figure 6.22. Effect of TOFA-modified cellulose on a) oxygen barrier properties (copolymers 32 and 33) and b) water and oil absorbance (copolymer 32) of copolymer-coated paperboards.
• Figure 7.1. Steroid skeleton
• Figure 7.2. Molecular structure of some phytosterols, phytostanols and a fatty acid ester
• Figure 8.2: Determination of the irritancy potential of single and repeated applications of tall oils
• Figure 8.3: The combined cytotoxicity and irritancy potential of single and repeated applications of tall oils
• Fig. 9.1. Structure of long-chain aliphatic alcohol (polycosanols): docosanol and tetracosanol
• Fig. 9.2. Effect of long-chain aliphatic alcohol type on CHO-K1 cell growth
• Fig. 9.3. Effect of long-chain aliphatic alcohol type on melanoma cell growth
• Fig. 10.1. Chemical structure of the synthesized polyols and polyurethanes, where R1 – residue of saturated and unsaturated fatty acids (C16-C24) and R2 – residue of aromatic diisocyanate
• Fig. 10.2. IR-spectra of polyols (1, 2) and urethanes (3, 4), based on tall oil FOR2 esters (1, 3) and diethanolamides (2, 4)
• Fig. 10.3. IR-spectra of tall oil diethanolamides (1, 2) and esters (3, 4), containing 2 % (1, 3) and 20 % (2, 4) of rosin acids
• Fig. 10.4. IR-spectra of polyurethanes based on tall oil diethanolamides (1, 2) and esters (3, 4), containing 2 % (1, 3) and 20 % (2, 4) of rosin acids
• Fig. 10.5. Density of polyurethanes versus the content of rosin acids
• Fig. 10.6. Tg of polyurethanes versus the content of rosin acids
• Fig. 10.7. Modulus of elasticity of polyurethanes versus the content of rosin acids
• Fig. 10.8. Tensile strength of polyurethanes versus the content of rosin acids
• Fig. 10.9. Elongation at break of polyurethanes versus the content of rosin acids
• Fig. 10.10. Shear bond strength to wood (W) and aluminium (Al) for polyurethanes versus the content of rosin acids
• Fig. 10.11. TGA curves of polyurethanes with the content of rosin acids of 2 %
• Fig. 19.1 is a general flow scheme of one embodiment of the invention
• Fig. 19.2 is a more detailed flow scheme of one embodiment of the invention