THERMOPLASTIC ELASTOMERS THROUGH POLYMERIZATION OF TRIGLYCERIDES BY REVERSIBLE FRAGMENTATION-ADDITIO

专利摘要:
thermoplastic block copolymer, its method of preparation, its compositions and vehicle tire the present invention relates to a thermoplastic block copolymer comprising at least one pa block and at least one bp block. the pa block represents a polymer block comprising one or more monomer units a, and the pb block represents a polymer block comprising one or more units of monomer b. monomer a is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer, or a crosslinking monomer. monomer b is a radically polymerizable triglyceride or mixtures thereof, typically in the form of a vegetable or animal oil. the present invention also relates to a method of preparing a thermoplastic block copolymer or new statistical thermoplastic copolymers by polymerizing a radically polymerizable monomer with a radically polymerizable triglyceride or mixtures thereof by means of polymerization by addition fragmentation chain transfer reversible (raft) in the presence of a free radical initiator and a chain transfer agent.
公开号:BR112015028368B1
申请号:R112015028368-3
申请日:2014-05-20
公开日:2020-12-15
发明作者:Ronald Christopher Williams；Eric W. Cochran；Nacu HERNANDEZ；Andrew CASCIONE
申请人:Iowa State University Research Foundation, Inc.；
IPC主号:

专利说明:

[0001] This application claims the benefit of United States Provisional Patent Application Serial No. 61 / 825.241, filed on May 20, 2013, which is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION
[0002] The present invention relates to a new thermoplastic elastomeric composition and methods of preparing and using it in various applications. In particular, the present invention relates to the successful application of reversible fragmentation-addition chain transfer polymerization (RAFT) to prepare new thermoplastic homopolymers, thermoplastic elastomeric block copolymers, and statistical thermoplastic elastomeric copolymers. These polymers are derived from at least one radically polymerizable triglyceride or mixture of triglycerides, typically in the form of a vegetable oil, animal oil, or synthetic triglycerides. Thermoplastic copolymers additionally include at least one radically polymerizable monomer. BACKGROUND OF THE INVENTION
[0003] Styrene block copolymers (SBCs), most notably those of the DuPont's Kraton® family, such as styrene-butadiene polymers (eg, styrene-butadiene di-block, SB; styrene-butadiene tri-block) styrene, SBS), have historically served the asphalt and footwear industries for years, with markets also in the packaging industries, pressure sensitive adhesives, packaging materials, etc. Of these markets, the use of SBSs as bitumen modifiers is one of the largest and most tolerant in terms of material properties.
[0004] The global asphalt market is expected to reach 118.4 million metric tons in 2015, according to a January 2011 report by Global Industry Analysts, Inc. The asphalt paving industry represents the largest market segment in final use of asphalt. With increasing growth in the developing markets of China, India, and Eastern Europe, asphalt will be increasingly needed to build the roadway infrastructure over the next decade. The increased demand for asphalt, along with the need for improved asphalt materials / paving performance, creates the opportunity for an asphalt modifier.
[0005] The degree of asphalt governs the performance of paving mixtures at in-service temperatures. In many cases, the bitumen characteristics need to be changed to improve their elastic recovery / ductility at low temperatures for sufficient cracking resistance, as well as to increase their shear resistance for extended loads and / or at high temperatures for heating resistance. The physical properties of bitumen are typically modified with the addition of SBS polymers to produce an improved degree of asphalt that enhances the performance of asphalt pavement mixtures. Of the asphalt mixtures that are modified by polymer, approximately 80% of polymer-modified asphalt uses polymers of the SBS type.
[0006] Over the past few years, the price of butadiene, the main component of SBC polymers used for bitumen modification, has increased dramatically. In 2008, there was a shortage of SBS polymers for the asphalt industry. With the forecast of increasing demand for liquid asphalt for the next decade, in this context there remains a strong need for a new type of viable, environmentally friendly, inexpensive polymers that can be used as an asphalt modifier instead of styrene modifiers. -butadiene standard.
[0007] Vegetable oils have been considered as monomeric raw materials for the plastics industry for over 20 years. Vegetable oil polymers have gained increasing attention as policy makers and corporations have also been interested in replacing traditional petrochemical raw materials due to their environmental and economic impacts.
[0008] Until today, moderate success has been achieved through the application of traditional cationic and free radical polymerization routines for vegetable oils to produce thermosetting plastics (ie, plastics that, once synthesized, permanently retain their shapes and are not submitted to further processing). For example, a variety of polymers, ranging from soft to hard rubbers, hard plastics were prepared using cationic copolymerization of vegetable oils, mainly soybean oil (SBO), using boron triflouridediethyl etherate (BFE) as the initiator (Andjelkovic et al., " Novel Polimeric Materials from soybean oils: Synthesis, Properties, and Potential Applications, "ACS Symposium Series, 921: 67-81 (2006); Daniel & Larock," Thermophysical properties of conjugated soybean oil / corn stover biocomposites. "Bioresource Technology 101 ( 15): 6200 - 06 (2010)). Polyurethane films transported by water based on soy oil were synthesized with different properties ranging from elastomeric polymers to rigid plastics changing the polyol functionality and hard segment content of the polymers (Lu et al., "New Sheet Molding Compound Resins From Soybean Oil. I. Synthesis and Characterization, "Polimer 46 (1): 71 - 80 (2005); Lu et al.," Surfactant-Free Core-Shell Hybrid Latexes From Soybean oil-Based Waterborne Poliurethanes and Poli (Styrene-Butyl Acrylate ), "Progress in Organic Coatings 71 (4): 336 - 42 (2011)). In addition, soybean oil was used to synthesize different bio-based products, such as sheet-forming composites, elastomers, coatings, foams, etc. (Zhu et al., "Nanoclay Reinforced Bio-Based Elastomers: Synthesis and Characterization," Polimer 47 (24): 8106 - 15 (2006)). Bunker et al. (Bunker et al., "Miniemulsion Polimerization of Acrylated Methyl Oleate for Pressure Sensitive Adhesives," International Journal of Adhesion and Adhesives 23 (1): 29 - 38 (2003); Bunker et al., "Synthesis and Characterization of Monomers and Polimers for Adhesives from Methyl Oleate, "Journal of Polimer Sci-ence Part A: Polimer Chemistry 40 (4): 451-58 (2002)) pressure sensitive adhesives synthesized using acrylated methyloleate mini emulsion polymerization, an oil-derived monoglyceride soybean; the polymers produced were comparable to their oil counterparts. Zhu et al., "Nanoclay Reinforced Bio-Based Elastomers: Synthesis and Characterization," Polimer 47 (24): 8106 - 15 (2006), generated an elastic network based on methyl oleyl ester acrylated by means of mass polymerization using ethylene glycol as the crosslinker, obtaining a linear polymer of high molecular weight using miniemulsion polymerization. Lu et al., "New Sheet Molding Compound Resins From Soybean Oil. I. Synthesis and Characterization," Polimer 46 (1): 71 - 80 (2005), created thermosetting resins synthesized from soy oil that can be used in applications of leaf molding compound introducing acid functionality over soy and reacting acid groups with divalent metal oxides or hydroxides, forming the sheet. Bonnaillie et al., "Thermosetting Foam with a High Bio-Based Content From Acrylated Epoxidized Soybean Oil and Carbon Dioxide," Journal of Applied Polimer Science 105 (3): 1042-52 (2007), created a thermosetting foam system using a foaming process of pressurized carbon dioxide from acrylated epoxidized soybean oil (AESO). United States Patent No. 6,121,398 to Khot et al., Synthesized liquid molding resins that are capable of curing in high modulus thermoset polymers and composites using vegetable oil derived triglycerides.
[0009] However, uncontrolled chain branching and crosslinking are inevitable using these conventional polymerization routines due to the multifunctional nature of triglycerides, multiple initiation sites along the chain skeleton, and chain transfer / termination reactions. While these thermosetting materials can actually supplant several petrochemical derived thermosets, the vast majority of commodity polymers are highly processable thermoplastic materials. There is, therefore, a need in the art to develop a highly processable thermoplastic and elastomeric polymer from vegetable oils with a wide range of applications and physical properties.
[0010] The present invention aims to satisfy these needs in the art. SUMMARY OF THE INVENTION
[0011] One aspect of the present invention relates to a thermoplastic block copolymer comprising at least one PA block and at least one PB block. The PA block represents a polymer block comprising one or more units of monomer A, and the PB block represents a polymer block comprising one or more units of monomer B. Monomer A is a vial, acrylic, diolefin monomer , nitrile, dinitrile, acrylonitrile, a monomer with reactive functionality, or a crosslinking monomer. Monomer B is a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides. One end or both ends of the PA block or PB block in the thermoplastic block copolymer is functionalized with a thiocarbonylthio chain transfer group.
[0012] Another aspect of the present invention relates to a telekelic thermoplastic block copolymer having an architecture of (PA-PB) n-TCTA- (PB-PA) n or (PB-PA) n-TCTA- ( PA-PB) n, where n is an integer ranging from 1 to 10. TCTA is a portion in the PB block or PA block of a telekelic chain transfer agent used to produce the telekelic thermoplastic block copolymer. The PA block represents a polymer block comprising one or more units of monomer A, and the PB block represents a polymer block comprising one or more units of monomer B. Monomer A is a vinyl, acrylic, diolefin, nitrile monomer , dinitrile, acrylonitrile, a monomer with reactive functionality, or a crosslinking monomer. Monomer B is a radically polymerizable triglyceride or mixtures thereof, in the form of a plant oil, animal oil, or synthetic triglycerides.
[0013] Another aspect of the present invention relates to a thermoplastic statistical copolymer having a general formula of [Ai-Bj-Ck] q. In the formula, A represents monomer A, which is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer, or a crosslinking monomer. B represents monomer B, which is a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides. C represents monomer C, which is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer, or a crosslinking monomer; or a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, provided that monomer C is different from monomer A or monomer B. i, j, and k are the average number of units of repetition of monomer A, monomer B, and monomer C, respectively, such that iej are greater than 0 and less than 1, k is 0 less than 1, as long as i + j + k = 1. q represents the degree of average polymerization number and ranges from 10 to 100,000.
[0014] One aspect of the present invention also relates to a method of preparing a thermoplastic block copolymer. The method comprises providing a radically polymerizable monomer, represented by A, or a PA polymer block comprising one or more units of monomer A. A radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, represented by B, is also provided. Monomer A or polymer block PA is polymerized with monomer B by means of reversible fragmentation / addition chain transfer polymerization (RAFT), in the presence of a free radical initiator and a chain transfer agent, to form the copolymer thermoplastic block. The polymerization step is carried out under effective conditions to obtain a degree of average polymerization number (Nn) for the thermoplastic block copolymer of up to 100,000 without gelation.
[0015] Alternatively, the method of preparing a thermoplastic block copolymer comprises providing a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, represented by B, or a PB polymer block comprising one or more units of monomer B. A radically polymerizable monomer, represented by A, is also provided. Monomer B or polymer block PB is polymerized with monomer A by means of RAFT, in the presence of a free radical initiator and a chain transfer agent, to form the thermoplastic block copolymer. The polymerization step is carried out under effective conditions to obtain a degree of average polymerization number (Nn) for the thermoplastic block copolymer of up to 100,000 without gelation.
[0016] Another aspect of the present invention relates to a method of preparing a thermoplastic homopolymer. The method comprises providing a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides. This triglyceride-based monomer is then polymerized by means of RAFT, in the presence of a free radical initiator and a chain transfer agent, to form the thermoplastic homopolymer. The polymerization step is carried out under effective conditions to obtain a degree of polymerization average number (Nn) for the thermoplastic homopolymer of up to 100,000 without gelation.
[0017] Another aspect of the present invention relates to a method of preparing a statistical thermoplastic copolymer. The method comprises providing a radically polymerizable monomer, represented by A. A radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides, represented by B is also provided. Monomer A and monomer B are simultaneously polymerized, by means of RAFT, in the presence of a free radical initiator and a chain transfer agent to form the thermoplastic statistical copolymer. The polymerization step is carried out under effective conditions to obtain a degree of average polymerization number (Nn) for the thermoplastic statistical copolymer of up to 100,000 without gelation.
[0018] The present invention involves the successful application of reversible fragmentation-addition chain transfer polymerization (RAFT) in raw materials, such as soybean oil, comprised predominantly of triglyceride mixtures. The distinguishing feature of this chemistry is that it allows the design of the molecular architecture of the resulting polymers such that they are slightly branched or predominantly non-crosslinked linear chains that behave like elastomers / rubbers at room temperature, but reversibly melt and are susceptible to processing techniques common at high temperatures. RAFT has received a great deal of attention with respect to petrochemical raw materials, but has not been successfully applied to raw biomaterials, such as soybean oil. The success of technology in vegetable oils, such as soybean oil, is surprising, as conventional radical polymerization typically brings about the polymerization of triglycerides in thermoset materials, while the present invention successfully controls the polymerization of triglycerides so that it ends in a desired molecular weight and block the composition and produce thermoplastic poly-soy oil.
[0019] RAFT polymerization limits the number of initiation sites and drastically reduces the polymer-to-polymer chain transfer rate and termination reactions, and also introduces the ability to produce custom chain architectures such as block copolymers (BCPs) and statistical copolymers. This degree of control is superior to that offered by other controlled radical polymerization methods - that is, polymers of higher molar mass can be obtained over a shorter period of time with less rigorous purification.
[0020] Typical monomers for thermoplastic polymers derived from chain development are monofunctional, that is, the monomer contains only a simple polymerizable functional group. Triglycerides contain some double bonds (which vary greatly in the species of animal oil or plant oil origin and even between cultivars of the same species) and as well as triglyceride monomers for polymerization will exhibit at least two variation functionalities. Consequently, each polyitriglyceride repeat unit has the potential for crosslinking with at least one other polyitriglyceride; when approximately a fraction of 1 / N of such units have cross-linked (N denotes the number of repeating units in a polymer chain), polymers are referred to as their "gel point" at which an infinite polymer network has formed up and the material is a thermoset.
[0021] In conventional RAFT polymerization, the classic Flory-Stockmeyer theory, as well as a more recent treatment of radical polymerizations controlled by GENNADY V. KOROLYOV AND MICHAEL MOGILEVICH, THREE-DIMENSIONAL FREE-RADICAL POLYMERIZATION CROSS-LINKED AND HYPER-BRANCHED POLIMERS (Springer, Berlin, 2009), which is incorporated here by reference in its entirety, predicts a freezing at a critical conversion rate αcr provided by αcr (Nw -1) = 1. According to this classic theory, the gel point is expected to occur at a critical conversion αcr <0.1 to multi-functional monomer; that is, freezing is expected to occur at the same time that the forming polymers are still in their oiligomeric stage. Thus, when the reactivity of a propagation chain for all functional sites in both free monomers and repeating units that are already incorporated into a chain are identical, the expectation is that the gel point will be reached in an extremely low conversion, in such a way that, before freezing, the polyglyceride has not yet activated a sufficient degree of polymerization for useful mechanical properties to develop. This expectation is maintained during the last two decades of reports of thermosets of vegetable oils produced by free radical polymerization and conventional catalyst. The expectation of early freezing would also extend to RAFT if the reactivity relationships between the propagation radials and all unreacted functional sites on triglycerides were strictly identical.
[0022] However, the RAFT method of the present invention allows for a monomer conversion (which is defined as the mass ratio of the polymers produced to the supplied monomers) of approximately 90%. In accordance with the present invention, preferences for free monomers can be exacerbated through the appropriate selection of a chain transfer agent and its relative relationship to the monomer; reaction temperature; and a solvent and its concentration. Under such conditions, it is possible to produce polymerized triglycerides with a targeted average number (Nn) degree of polymerization for the thermoplastic polymer up to 100,000 before the gel point. The use of high CTA agent excess promotes the incorporation of CTA fragments into the polymer backbone. This in turn causes hyper-branching to occur instead of crosslinking in the polymer. In this way, the triglycerides polymerized by means of RAFT of the present invention can reach a degree of polymerization of average number (Nn) for the thermoplastic polymer of up to 100,000 without gelation.
[0023] Polymerized triglycerides, such as those found in soybean oil, are intrinsically renewable, are environmentally friendly, and can also be shown to exhibit biodegradability. The elastomeric properties of the vegetable oil polymer appear to be competitive with modern amenities, such as polybutadiene (synthetic rubber). In addition, the cost of the vegetable oil monomer has become highly competitive in recent years. In many cases, biomonomers are more economical than petrochemical raw materials (for example, a ton of vegetable oil costs less than $ 1,200, while a ton of butadiene costs more than $ 4,000). In this way, the new thermoplastic homopolymers, block copolymers or statistical copolymers of the present invention provide affordable, environmentally friendly alternatives to conventional petrochemical derived polymeric materials.
[0024] These thermoplastic homopolymers based on polymerized triglyceride, block copolymers, or statistical copolymers are suitable in various applications, such as asphalt modifiers or viscosity modifiers for consumer care products, adhesives, sealants, rubber compositions , in the automotive, footwear, packaging industry, consumer electronics, etc. BRIEF DESCRIPTION OF THE FIGURES
[0025] Figure 1 is a schematic figure illustrating the preparation of bio-polymeric thermoplastic elastomers (TPE) from soybean oil by means of a RAFT polymerization mechanism, described in Moad and another, "Living Radical Polymerization by the Raft Process - the First Update, "Australian Journal of Chemistry 59: 669-92 (2006), which is incorporated herein by reference in its entirety.
[0026] Figure 2 is a schematic figure describing uses of thermoplastic elastomers based on animal oil or plant oil in various markets.
[0027] Figure 3 is a flowchart showing the process of mixing copolymer compositions in poly (styrene-SBO-styrene) block with asphalt binders and then testing their rheological properties.
[0028] Figure 4 shows the chemical structure of azobisisobutyronitrile (AIBN).
[0029] Figure 5 shows the chemical structure of 1-phenylethyl benzodithioate.
[0030] Figure 6 is a graph showing the increase in molecular weight (average number) of a styrene homopolymer as a function of time.
[0031] Figure 7 is a graph showing the increase in molecular weight (average number) of a poly diblock copolymer (styrene-b-AESO) as a function of time.
[0032] Figure 8 is a photographic image showing a poly (styrene-b-AESO) diblock at 130,000 kD / mol.
[0033] Figure 9 is a graph showing an increase in molecular weight of a monomer, for a homopolymer, and for a diblock copolymer.
[0034] Figure 10 is a photographic image showing a triblock of poly (styrene-b-AESO-styrene) after 24 hours in the vacuum oven.
[0035] Figure 11 is a graph showing the nuclear magnetic resonance (NMR) spectrum of the poly (styrene-b-AESO-styrene) triblock.
[0036] Figure 12 is a graph showing the results of differential scanning calorimetry (DSC) of a PS-PAESO-PS sample. A glass transition temperature is shown in the graph at -10 ° C; no apparent glass transition is present for the PS block.
[0037] Figure 13 is a graph showing the rheology curve of a PS-PAESO-PS sample.
[0038] Figure 14 is a graph showing the results of the tensile test of a poly triblock copolymer (styrene-b-AESO-styrene): the load (MPa) versus tensile force (mm / mm).
[0039] Figure 15 is a graph showing the stress versus% of stress curves for a PS-PAESO-PS triblock copolymer synthesized by RAFT continued loading (gray) to find the maximum stress.
[0040] Figure 16 is a TEM image of the PS-PAESO-PS # 1 sample, listed in table 2. The image shows a semi-ordered structure where the black islets are the styrene blocks and the clearest regions are the AESO blocks.
[0041] Figure 17 is a graph showing stress vs. stress. % voltage curves for PS-PAESO-PS # 1, listed in table 2. The first charge is shown by the blue line, which was followed by the first hysteresis cycle (black), the tenth cycle (red), and then also continued loading (gray) to find maximum stress.
[0042] Figure 18 is a graph showing the Young's modulus of PS-PAESO-PS # 1, listed in table 2, during the load and non-load cycles.
[0043] Figure 19 is a graph comparing the 1H-NMR spectrum of corn oil, epoxidized corn oil, and acrylated epoxidized corn oil.
[0044] Figure 20 is a graph comparing the 1 H-NMR spectrum of AECO monomer (top) and an AECO homopolymer with an average molecular weight of 6.512 Da after 9 hours of reaction (base).
[0045] Figure 21 is a graph showing the 1H-NMR spectrum of the PS-PAESO-PS triblock copolymer synthesized using a telehelic CTA, having a molecular weight of 426 kDa and polydispersity of 1.26.
[0046] Figure 22 is a graph showing the differential refractive index collected using gel permeation chromatography of a triblock copolymer containing PAESO synthesized with a telekelic CTA.
[0047] Figure 23 is a graph showing the GPC curves for the PAECO and PS homopolymers, and PS-PAECO-PS triblock copolymers synthesized using a telehelic CTA.
[0048] Figure 24 is a graph showing the differential refractive index collected using gel permeation chromatography of a statistical copolymer containing AESO.
[0049] Figure 25 is a graph showing the differential refractive index collected using gel permeation chromatography of a statistical copolymer containing acrylated epoxidized corn oil (AE-CO). DETAILED DESCRIPTION OF THE INVENTION
[0050] One aspect of the present invention relates to a thermoplastic block copolymer comprising at least one PA block and at least one PB block. The PA block represents a polymer block comprising one or more units of monomer A, and the PB block represents a polymer block comprising one or more units of monomer B. Monomer A is a vinyl, acrylic, diolefin monomer, nitrile, dinitrile, acrylonitrile, a monomer with reactive functionality, or a crosslinking monomer. Monomer B is a radically polymerizable triglyceride or mixture thereof, typically in the form of a plant oil, animal oil, or synthetic triglycerides. One end or both ends of the PA block or PB block in the thermoplastic block copolymer is / are functionalized with a thiocarbonyl chain transfer group. For example, the polymer chain can have one end or both ends with a thiocarbonylthio end derived from the thiocarbonylthio chain transfer group — similar (PnS (Z) C = S, 3), as shown in Figure 1. The thiocarbonylthio chain transfer group has been described here. A more extensive list of CTA agents for thiocarbonylthio (or RAFT agents) can be found in Moad and another, "Living Radical Polymerization by the Raft Process- a First Update," Australian Journal of Chemistry 59: 66992 (2006); Moad et al., "Living Radical Polymerization by the Raft Process- a Second Update," Australian Journal of Chemistry 62 (11): 1402-72 (2009); Moad et al., "Living Radical Polymerization by the Raft Process- a Third Update," Australian Journal of Chemistry 65: 985-1076 (2012); Skey and another, "Facile one pot synthesis of a rank of reversible addition-fragmentation chain transfer (RAFT) agents," Chemical Communications 35: 4183-85 (2008), which are hereby incorporated by reference in their entirety.
[0051] The thermoplastic block copolymer can be a linear or light branched copolymer, and can contain two or more blocks. Exemplary copolymer architecture includes, but is not limited to (PA-PB) n, (PA-PB) n-PA, and PB- (PA-PB) n. n is an integer greater than 0. For example, n ranges from 1 to 50, from 1 to 10, or from 1 to 5. The block copolymer typically has a diblock polymer architecture (PA-PB), architecture triblock polymer (PA-PB-PA or PB-PA-PB) or pentablock polymer architecture (PA-PB-PA-PB-PA or PB-PA-PB-PA-PB). The copolymer blocks are formed by sequential additions alternating between monomer A and monomer B until the desired multiblock architecture is activated. Each unit of monomer A or unit of monomer B in the architecture can be the same or different.
[0052] Another aspect of the present invention relates to a telekelic thermoplastic block copolymer having an architecture of (PA-PB) n-TCTA- (PB-PA) n or (PB-PA) n-TCTA- ( PA-PB) n, where n is an integer ranging from 1 to 10. TCTA is a portion in the PB block or PA block of a telekelic chain transfer agent used to produce the telekelic thermoplastic block copolymer. The PA block represents a polymer block comprising one or more units of monomer A, and the PB block represents a polymer block comprising one or more units of monomer B. Monomer A is a vinyl, acrylic, diolefin, nitrile monomer , dinitrile, acrylonitrile, a monomer with reactive functionality, or a crosslinking monomer. Monomer B is a radically polymerizable triglyceride or mixtures thereof, in the form of a plant oil, animal oil, or synthetic triglycerides. TCTA is a portion derived from a "telekeletal chain transfer agent", for example, a trithiocarbonate portion or any other portion of a telekelic CTA agent used to produce the telekeletal thermoplastic block copolymers. n is an integer ranging from 1 to 50, or from 1 to 10. The structures and mechanisms for preparing the telekeletal thermoplastic block copolymers have been described here.
[0053] The telekelic thermoplastic block copolymer may be a linear or light branched copolymer, and may contain three or more blocks. The block copolymer typically has symmetric triblock polymer architecture (PA-PB-TCTA-PB-PA or PB-PA-TCTA-PA-PB) or a pentablock polymer architecture (PA-PB-PA-TCTA-PA -PB- PA or PB-PA-PB-TCTA-PB-PA-PB). TCTA is a portion derived from a tele-chain transfer agent in the PB block (PB-TCTA-PB) or in the PA block (PA-TCTA-PA). Each unit of monomer A or unit of monomer B in the architecture can be the same or different, as long as the overall architecture is symmetrical, for example, PA1-PB-PA2-PB-PA1 (A1 andA2 refer to different types monomer to monomer unit A).
[0054] The PA block is made by polymerizing one or more radically polymerizable monomers, and has an average molecular weight of about 1 to about 1000 kDa, or about 10 to about 30 kDa. The PA block can comprise repeating units of monomer A. For example, the PA block can be a branched-chain monomer A or polymerized linear chain or radicals thereof. The PB block is made by polymerizing one or more triglycerides or mixtures of triglycerides, typically in the form of a plant oil, animal oil, or synthetic triglycerides, and has an average molecular weight of about 5 to about 1000 kDa, about 10 to about 500 kDa, about 40 to about 100 kDa, or about 80 to about 100 kDa. The PB block may comprise triglyceride repeating units or mixtures of triglycerides. For example, the PB block can be a branched-chain or polymerized linear chain monomeric animal oil or plant oil, or radicals thereof.
[0055] PA-PB diblock copolymers typically contain about 5% by weight to about 95% by weight of the polymerized block A and about 95% by weight to about 5% by weight of the polymerized triglyceride block. Triblock copolymers of PA-PB-PA or PB-PA-PB typically contain about 5% by weight to about 95% by weight of the polymerized block A and about 95% by weight to about 5% by weight of block polymerized triglyceride. Penta-block copolymers of PA-PB-PA-PB-PA or PB-PA-PB-PA-PB typically contain about 5% by weight to about 95% by weight of the polymerized block A and about 95% by weight. weight about 5% by weight of the polymerized triglyceride block. For example, the block copolymers above may contain about 10% by weight to about 90% by weight of the polymerized block A and about 90% by weight to about 10% by weight of the polymerized triglyceride block. Adjusting the relative percentage composition of the PA or PB block can improve the property of the block copolymer to make it more suitable for different applications. For example, block copolymers containing a relatively low concentration of PA blocks are suitable for elastomers / adhesives whereas a block copolymer containing a relatively high concentration of PA blocks is suitable for hardening engineering materials (eg type Plexiglas® or High-Impact Polystyrene).
[0056] The block copolymer PA block can be considered as a "hard" block, and has characteristic properties of thermoplastic substances in which it has the necessary stability for processing at high temperatures and still has good resistance below the temperature at which it softens. The PA block is polymerized from one or more radically polymerizable monomers, which may include a type of variety of monomers such as vinyl monomer (such as aromatic vinyl), acrylic (such as methacrylates, acrylates, methacrylamides, acrylamides , etc.), diolefin, nitrile, dinitrile, acrylonitrile, a monomer with reactive functionality, and a crosslinking monomer.
[0057] Aromatic vinyl monomers are exemplary vinyl monomers that can be used in the block copolymer, and include any aromatic vinyls optionally having one or more substitutes on the aromatic portion. The aromatic portion can be mono or polycyclic. Exemplary aromatic vinyl monomers for the PA block include styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, heteroaromatic N-vinyl (such as 4-vinylimidazole (Vim), N -vinylcarbazole (NVC), N-vinylpyrrolidin, etc.). Other exemplary vinyls include vinyl esters (such as vinyl acetate (VAc), vinyl butyrate (VB), vinyl benzoate (VBz)), N-vinyl amides and imides (such as N-vinylcaprolactam (NVCL), N-vinylpyrrolidone (NVP), N-vinylphthalimide (NVPI), etc.), vinyl sulphonates (such as 1-butyl ethanesulfonate (BES), neopentyl ethanesulfonate (NES), etc.), vinylphosphonic acid (VPA), haloolefins (such such as vinylidene fluoride (VF2)), etc. Exemplary methacrylates include C1-C6 (meth) acrylate (i.e., methyl methacrylate, ethyl methacrylate, (meth) propyl acrylate, (butyl) acrylate, isobutyl methacrylate, (meth) acrylate, or (meth) acrylate, or hexyl acrylate), 2- (acetoacetoxy) ethyl methacrylate (AAEMA), 2-aminoethyl methacrylate (hydrochloride) (AEMA), allyl methacrylate (AMA), cholesteryl methacrylate (CMA), t-butyldimethylsilyl methacrylate ( BDSMA), (diethylene glycol monomethyl ether) methacrylate (DEGMA), 2- (dimethylamino) ethyl methacrylate (DMAEMA), (ethylene glycol monomethyl ether) methacrylate (EGMA), 2-hydroxyethyl methacrylate (HEMA), dodecyl methacrylate (LMA), methacryloyloxyethyl phosphorylcholine (MPC), (poly (ethylene glycol monomethyl) methacrylate (PEGMA), pentafluorophenyl methacrylate (PFPMA), 2- (trimethylammonium) methacrylate (TETH), ethyl methacrylate (TETH), 3- (trimethylammonium) propyl (TMAPMA), triphenylmethyl methacrylate (TPMMA), etc. Other exemplary acrylates include 2- (acryloyloxy) ethyl phosphate (AEP), butyl acrylate (BA), 3-chloropropyl acrylate (CPA), dodecyl acrylate (DA), 2-ethylhexyl ether acrylate (ethylene glycol) ) (DEHEA), 2- (dimethylamino) ethyl acrylate (DMAEA), ethyl acrylate (EA), ethyl a-acetoxyacrylate (EAA), ethoxy-ethyl acrylate (EEA), 2-ethylhexyl acrylate (EHA) , isobornyl acrylate (iBoA), methyl acrylate (MA), propargyl acrylate (PA), (poly (ethylene glycol) monomethyl acrylate) (PEGA), tert-butyl acrylate (tBA), etc. . Exemplary methacrylamides include N- (2-aminoethyl) methacrylamide (hydrochloride) (AEMAm) and N- (3-aminopropyl) methacrylamide (hydrochloride) (APMAm), N- (2- (dimethylamino) ethyl) acrylamide (DEAPMAm), N- (3- (dimethylamino) propyl) methacrylamide (hydrochloride) (DMAPMAm), etc. Other exemplary acrylamides include acrylamide (Am), 2-acrylamido-2-methylpropanesulfonic acid (AMPS) sodium salt, N-benzylacrylamide (BzAm), N-cyclohexylacrylamide (CHAm), (N- (1,1 acrylamide) -dimethyl- 3-oxobutyl)) diacetone acrylamide (DAAm), N, N-diethylacrylamide (DEAm), N, N-dimethylacrylamide (DMAm), N- (2- (dimethylamino) ethyl) acrylamide (DMAEAm) , N-isopropylacrylamide (NIPAm), N-octylacrylamide (OAm), etc. Exemplary nitriles include acrylonitrile, adiponitrile, metacrylonitrile, etc. Exemplary diolefins include butadiene, isoprene, etc. [0058] Radically polymerizable monomers suitable for use here also include those monomers with reactive functionality, for example, a 'clickable' functionality so that when the monomers are incorporated into blocks, these 'clickable' functional groups can be used as a precursor for a polymer brush or copolymerized to provide sites for linking functionality or for crosslinking. Exemplary reactive functionality includes functional groups suitable for cycloaddition of 1,3-dipolar azide-alkyne, such as azide functionality; "active ester" functional groups that are particularly active with primary amine functionality; functional groups with protected thiol, hydrazide or amino functionality; functional groups with isocyanate or isothiocyanate functionality, etc.
[0059] Radically polymerizable monomers suitable for use here may also include those cross-linked monomers that are typically used in both the synthesis of microgels and polymer networks (see below). Monomers can include degradable cross-links such as an acetal bond, or disulfide bonds, resulting in the formation of degradable cross-links. Exemplary crosslinking monomers include diethylene glycol dimethacrylate (DE-GDMA), triethylene glycol dimethacrylate (TEGDMA), ethylene glycol dimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA), methylene-bis-acrylamide , divinylbenzene (DVB), etc.
[0060] A more extensive list of exemplary methacrylate monomers, acrylate monomers, methacrylamide monomers, acrylamide monomers, styrenic monomers, diene monomers, vinyl monomers, reactive monomers, and monomers that are suitable for reticulation use as the radically polymerizable monomers here was described in Moad and another, "Living Radical Polymerization by the Raft Process- a Third Update," Australian Journal of Chemistry 65: 985-1076 (2012), which is hereby incorporated by reference into its full.
[0061] In addition, two or more different monomers can be used together in the formation of the PA block or different PA block in the copolymer. A typical radically polymerizable monomer A used here is styrene, and the resulting PA block is a styrene homopolymer. Another typical radically polymerizable monomer A used here is methyl acrylate, and the resulting PA block is a methyl acrylate homopolymer.
[0062] The block of PB of the block copolymer can be considered as a "soft" block, and has elastomeric properties that allow to absorb and dissipate an applied stress and then recover its shape. The PB block is polymerized from one or more monomeric triglycerides, typically derived from a plant oil, animal fat, or a synthetic triglyceride. This polymerized plant oil or animal oil can subsequently be partially or fully saturated by means of a postpolymerization of catalytic hydrogenation. The monomeric oils used in the block copolymer can be any triglycerides or mixtures of triglycerides that are radically polymerizable. These triglycerides or mixtures of triglycerides are typically vegetable oils. Suitable vegetable oils include, but are not limited to, a variety of vegetable oils such as soybean oil, peanut oil, walnut oil, palm oil, palm kernel oil, sesame oil, sunflower oil, safflower oil, rapeseed oil, rapeseed oil, linseed oil (flax seed oil), rapeseed oil (rapeseed oil), coconut oil, corn oil, cotton oil, olive oil, oil castor oil, fake linseed oil, hemp oil, mustard oil, turnip oil, ramile oil, rice bran oil, salicornia oil, tigernut oil, tung oil, etc., and mixtures thereof. Typical compositions of several exemplary vegetable oils are shown in table 1. Typical vegetable oils used here include soybean oil, linseed oil, corn oil, flax seed oil, or rapeseed oil oil), and the resulting PB block is polymerized triglyceride or triglyceride derivatives. Table 1: Typical vegetable oil compositions.

[0063] Vegetable oils and animal fats are mixtures of triglycerides. A representative structure of a triglyceride is shown as below:

[0064] A typical triglyceride structure contains some double bonds that can serve as candidates for polymerization. Various soy cultivars express a variety of triglyceride compositions in their oils. Different soybean species can be appropriately selected based on triglyceride compositions to enhance block copolymer production and properties.
[0065] Soy oil (SBO) is the most abundant vegetable oil, which accounts for almost 30% of the world's vegetable oil supply. SBO is particularly suitable for polymerization, because it has multiple carbon-carbon double bonds that allow modifications such as conjugation of the double bonds, etc.
[0066] In unprocessed oils, the double bonds contained in triglycerides are typically located in the middle of the alkyl chains, and have limited reactivity towards propagation reactions due to steric impediment and unfavorable free radical stability. This reactivity improves dramatically when the double bonds are conjugated (Li et al, "Soybean Oil-Divinylbenzene Thermosetting Polimers: Synthesis, Structure, Properties and their Relationships," Polimer 42 (4): 1567-1579 (2001); Henna and others, "Biobas Thermosets from Free Radical Copolymerization of Conjugated Linseed Oil," Journal of Applied Polimer Science 104: 979-985 (2007); Valverde and others, "Conjugated Low-Saturation Soybean Oil Thermosets: Free- Radical Copolimerization with Dicyclopentadiene and Divinylbenzene," Journal of Applied Polimer Science 107: 423-430 (2008); Robertson et al., "Toughening of Polilactide with Polymerized Soybean Oil," Macromolecules 43: 1807-1814 (2010), which are hereby incorporated by reference in their entirety). The conjugation of double bonds in triglycerides can be readily achieved in conversion of almost 100% with homogeneous Rh catalysis (Larock et al., "Preparation of Conjugated Soybean Oil and Other Natural Oils and Fatty Acids by Homogeneous Transition Metal Catalysis," Journal of the American Oil Chemists' Society 78: 447-453 (2001), which is hereby incorporated by reference in its entirety).
[0067] In any embodiment of the present invention, the triglyceride containing polymerizable plant oil monomer can be substituted with a polymerizable monomer containing one or more triglycerides from an animal source, for example, animal fats. Thus, the PB block in any embodiment of the present invention can instead be polymerized from one or more monomeric animal fat containing one or more triglycerides. Examples of suitable animal fats used in accordance with the present invention include, but are not limited to, beef or lamb fat such as beef tallow or sheep tallow, pig fat such as lard, poultry fat such as fat chicken and / or turkey, and fish oil / fat. Animal fats can be obtained from any suitable source including restaurants and meat production facilities.
[0068] "Triglycerides," as defined here, can refer to any unmodified triglycerides naturally found in plant oil or animal oil or animal fat as well as any unmodified triglyceride derivatives, such as synthetically derived triglycerides. The naturally occurring source oil may also contain triglyceride derivatives, such as free fatty acids. An unmodified triglyceride can include any glycerol-derived ester with three similar or different fatty acids. Triglyceride derivatives can include any modified triglycerides that contain conjugate systems (ie, a system of p-orbitals connected with electrons delocalized in triglycerides). Such conjugate systems increase the reactivity of triglycerides towards propagation reactions. Useful conjugated triglycerides include, but are not limited to, triglyceride derivatives containing conjugated double bonds or conjugated systems formed by acrylate groups.
[0069] The term "soybean oil" used here can refer broadly to any raw soybean oil or processed soybean oil that contains at least one form of triglyceride or its derivative suitable for the polymerization reaction of the present invention. The term "conjugated soybean oil" used herein refers to any raw soybean oil or processed soybean oil containing at least one triglyceride with at least one conjugated site. Similar definitions also apply to other vegetable oils, animal oils, conjugated vegetable oils, conjugated animal oils, or synthetically derived triglyceride based oils.
[0070] The conjugated triglyceride can contain one or more conjugated sites. For example, the conjugated triglyceride can contain a single conjugated site per triglyceride. Alternatively, each triglyceride fatty acid chain can contain one or more conjugated sites.
[0071] Exemplary conjugated triglycerides are:

[0072] Another description of soybean oil conjugation sites, soybean oil epoxidation, and soybean oil acrylation can be found at NACU BERNARDO HERNANDEZ-CANTU, "SUSTAINABILITY THROUGH BLOCKCOPOLIMERS - NOVEL ION EXCHANGE CATHODE MEMBRANES AND BASYBEANANANEANEY THERMOPLASTIC ELASTOMER, "(Iowa State University, Ames, Iowa 2012), which is incorporated herein by reference in its entirety.
[0073] In one embodiment, plant oil or conjugated animal oil is plant oil or acrylated epoxidized animal oil, such as acrylated epoxidized soybean oil or acrylated epoxidized corn oil; the conjugated triglyceride is acrylated epoxidized triglyceride.
[0074] In any embodiment of the present invention, the block copolymer is a thermoplastic elastomer. The mechanism for activating the dual properties of thermoplasticity and elasticity / toughness in the styrenic block copolymer based on plant oil or animal oil stems from polymer thermodynamics and the polymer chain architecture. The Flory-Huggins theory illustrates that almost all polymers are mutually immiscible, due to the drastic loss of mixture entropy. The chemically dissimilar monomer sequences found in block copolymers can be thought of conceptually as immiscible homopolymers covalently linked end to end. Due to this restriction, when a block copolymer phase separates, incompatible polymer types form meso-domains with a geometry dictated by the block composition and a size governed by the total molecular weight (Bates and another "Block Copolymers-Designer Soft Materials, "Physics Today 52 (2): 32-38 (1999), which is hereby incorporated by reference in its entirety). In block copolymers with modest polydispersity, these meso-domains have well-defined geometries and become statistical in nature when the polydispersity index increases beyond approximately 1.5 (Widin et al., "Unex-pected Consequences of Block Polidispersity on the Self-Assembly of ABA Triblock Copolymers ", Journal of the American Chemical Society, 134 (8): 3834-44 (2012), which is hereby incorporated by reference in its entirety).
[0075] In a typical SBS elastomer, the composition of styrene is about 10 to 30% by weight such that spherical or cylindrical styrene domains form in a butadiene matrix. When the temperature is below the transition temperature of polystyrene glass (Tg = 100 ° C), the polybutadiene matrix is liquid (Tg <-90 ° C), however it is bonded between the glassy polystyrene spheres, which serve as reti - physical culprits. When the temperature is above the polystyrene glass transition temperature, the entire elastomer system is melted and can be processed easily. Cross-linked poly (soybean oil) has been reported to have Tg values as low as -56 ° C (Yang et al., "Conjugation of Soybean Oil and It's Free-Radical Copolimerization with Acrylonitrile," Journal of Polimers and the Environment 1-7 (2010 ), which is hereby incorporated by reference in its entirety). Thus, poly (soy oil) is an excellent candidate to serve as the liquid component in thermoplastic elastomers based on styrenic block copolymers.
[0076] Consequently, in one embodiment of the present invention, the thermoplastic and elastomeric block copolymer has a PA-PB diblock polymer architecture, where the PA block is a linear chain polystyrene (PS) and the PB block it is a linear or light branched polymerized soybean oil (PSBO) or radicals thereof, or polymerized conjugated soybean oil (PCSBO) or radicals thereof. The PS-PSBO diblock copolymer has a molecular weight ranging from 5 to 10,000 kDa, for example, from 5 to 500 kDa, from about 15 to 300 kDa, from about 40 to about 100 kDa, or from about 80 to about 100 kDa. The PSBO block has a glass transition temperature (Tg) below -10 ° C, or below -15 ° C, for example, from about -60 ° C to about -12 ° C, or about -60 ° C to about -28 ° C.
[0077] In one embodiment of the present invention, the thermoplastic and elastomeric block copolymer has a PA-PB-PA triblock polymer architecture, where the PA block is a linear chain polystyrene (PS), and the PB is a linear or light branched polymerized soybean oil (PSBO) or radicals thereof, or polymerized conjugated soybean oil (PCSBO) or radicals thereof. This styrenic triblock copolymer based on soy oil (PS-PSBO-PS) thus has an elastomeric inner block PSBO and a thermoplastic outer block PS formed on both ends of the inner block PSBO. The PS-PSBO-PS triblock copolymer has a molecular weight ranging from 7 kDa to 10,000 kDa, for example, from 7 kDa to 1000 kDa, from about 7 to about 500 kDa, from about 15 to about 350 kDa, from about 80 to about 120 kDa, or from about 100 to about 120 kDa. The PSBO block has a Tg below - 10 ° C, or below -15 ° C, for example, from about -60 ° C to about - 12 ° C, or from about -60 ° C to about -28 ° C.
[0078] In one embodiment, the triglyceride mixture to be radically polymerized is soybean oil, linseed oil, flax seed oil, corn oil, or rapeseed oil. In one embodiment, a mixture of acrylated epoxidized triglyceride, such as acrylated epoxidized soybean oil, is radically polymerized according to the method of the present invention.
[0079] Another aspect of the present invention relates to a thermoplastic statistical copolymer having a general formula of [Ai-Bj-Ck] q. In the formula, A represents monomer A, which is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer, or a crosslinking monomer. B represents monomer B, which is a radically polymerizable triglyceride or mixture thereof, in the form of a plant oil, animal oil, or synthetic triglycerides. C represents monomer C, which is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer, or a crosslinking monomer; or a radically polymerizable triglyceride or mixture thereof, typically in the form of a plant oil, animal oil, or synthetic triglycerides, provided that monomer C is different from monomer A or monomer B. i, j, and k are number average of repeating units of monomer A, monomer B, and monomer C, respectively, such that i and j are greater than 0 and less than 1, k is 0 less than 1, provided that i + j + k = 1. q represents the degree of average polymerization number and ranges from 10 to 100,000, for example, from 10 to 10,000, or from 500 to 1500.
[0080] The thermoplastic statistical copolymer can be linear or branched and can contain statistical sequences of monomer A, B, or C. A represents a unit of monomer A, which is radically polymerizable. Monomer unit A represents a "hard" segment that gives the thermoplastic statistical copolymer the stability required for processing at high temperatures and at the same time good resistance below the temperature at which it softens. B represents a unit of monomer B, which is a radically polymerizable triglyceride or mixtures of triglycerides. Monomer unit B represents a "soft" segment that gives the thermoplastic statistical copolymer the elastomeric characteristics that allow it to absorb and dissipate applied stress and then recover its shape. C represents a C monomer unit, which is also radically polymerizable. Monomer C can represent a similar "hard" segment like monomer A or represent a similar "soft" segment like monomer B, but it represents a different monomer than A or B. The average repeated sequence within the statistical copolymer is highly dependent on relative reactivity relationships for the addition of type j monomer to develop type i radical.
[0081] Monomer A or monomer C can each be independently a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, or monomer with reactive functionality, or crosslinking monomer. The exemplary modalities for monomer A and monomer C suitable for use in the statistical thermoplastic copolymer are the same as the exemplary modalities for monomer A, as described above in the thermoplastic block copolymer. Exemplary monomers A and C monomers include styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, vinyl acetate, N-vinyl pyrrolidone, methyl acrylate, C1-C6 (met) acrylate (i.e., methyl methacrylate, ethyl methacrylate, (meth) propyl acrylate, (meth) butyl acrylate, (meth) heptyl acrylate, or hexyl (meth) acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene , isoprene, or mixtures thereof. In one embodiment, monomer A and monomer C are each independently an aromatic vinyl monomer, for example, a styrene. In another embodiment, monomer A or monomer C is each independently an acrylate monomer, for example, a methyl (meth) acrylate.
[0082] Monomer B can be a monomeric triglyceride or mixture thereof derived from any plant oil, animal oil, or synthetic triglyceride that is radically polymerizable, particularly those containing one or more types of triglycerides. Suitable vegetable oils include, but are not limited to, a variety of vegetable oils such as soybean oil, peanut oil, walnut oil, palm oil, palm kernel oil, sesame oil, sunflower oil, safflower, rapeseed oil, linseed oil, linseed oil (flax seed oil), rapeseed oil (rapeseed oil), coconut oil, corn oil, cotton oil, olive oil , castor oil, fake linseed oil, hemp oil, mustard oil, turnip oil, ramtil oil, rice bran oil, salicornia oil, tigernut oil, tung oil, etc., and mixtures thereof . Exemplary plant oil monomer in the statistical copolymer is soybean oil, corn oil, linseed oil, flax seed oil, or rapeseed oil. In one embodiment, the polymerized plant oil is poly (soybean oil). Suitable animal fats include, but are not limited to, beef or lamb fat such as beef tallow or sheep tallow, pig fat such as lard, poultry fat such as chicken and / or turkey fat, and fish oil / fat. Animal fats can be obtained from any suitable source including restaurants and meat production facilities. The triglyceride in plant or animal oil can comprise one or more conjugated sites, as described above. In one embodiment, the triglyceride is an acrylated epoxidized triglyceride.
[0083] Monomer C can also be a radically polymerizable triglyceride or mixture of triglycerides, but of a different plant oil, animal oil, or synthetic triglyceride of monomer B, or the triglycerides of monomer C have a different degree of conjugation than that of monomer B. For example, the triglycerides of monomer C and monomer B can each independently have different degrees of acrylic functionality, ranging from 1 per molecule to 5 per molecule. The modalities and examples for monomer C as an animal oil monomer or radically polymerizable plant oil monomer are the same as the modalities described above for monomer B.
[0084] In one embodiment, monomer C is absent, monomer A is styrene, monomer B is soybean oil, linseed oil, corn oil, flax seed oil, or rapeseed oil.
[0085] In one embodiment, monomer A is styrene, monomer B is soybean oil, linseed oil, corn oil, flax seed oil, or rapeseed oil, and monomer C is a linear chain extension monomer, such as diene, a rubber monomer, such as n-butyl acrylate. A more extensive list of linear chain extension monomers can be found in Moad and another, "Living Radical Polymerization by the Raft Process- a Third Update," Australian Journal of Chemistry 65: 985-1076 (2012), which is at present incorporated by reference in its entirety.
[0086] Other aspects of the present invention relate to the use of thermoplastic block copolymers based on vegetable oil or polymerized animal oil or statistical thermoplastic copolymers in a variety of applications. The benefit of using the polymeric materials of the present invention is multifaceted. The statistical thermoplastic copolymers of block thermoplastic copolymers of the present invention are based on vegetable oils, such as soybean oil. Polymerized soybean oil is intrinsically biodegradable and the raw material is produced through a process of negative carbon emissions (that is, soybean cultivation). Thus, these polymeric materials are attractive from an environmental / bio-renewable perspective. In addition, the elastomeric properties of soybean oil polymers are competitive with modern amenities such as polybutadiene and polyisoprene (synthetic rubber). The cost of bio-monomer is highly competitive (in many cases more economical than peterochemically derived raw materials). In addition, with appropriate modification of soy oil (such as conjugation of triglycerides, or development of types of soy oil that are particularly suitable for polymerization), chemical properties, thermal properties, microstructure and morphology, and mechanical / rheology of soy oil-based polymers can be improved and refined to make these polymers highly useful in the plastics industry.
[0087] Exemplary applications of the thermoplastic block copolymers or statistical thermoplastic copolymers of the present invention include their use: as rubbers or elastomers; as hardened engineering thermoplastics; as components in consumer electronics, such as a shock / impact protection component or cover components; asphalt modifiers; as resin modifiers; as engineering resins; as leather and cement modifiers; in shoes, such as rubber heels, rubber shoe soles; in automobiles, such as tires, hoses, energy belts, conveyor belts, printing rollers, rubber squeezers, car mats, truck flaps, ball mill liners, and caulking strips; as sealants or adhesives, such as pressure sensitive adhesives; in aerospace equipment; as viscosity index improvers; as detergents; as diagnostic agents and supports, therefore; as dispersants; as emulsifiers; as lubricants and / or surfactants; as paper additives and coating agents; and packaging, such as beverage and food packaging materials. Exemplary applications of thermoplastic elastomers based on animal oil or plant oil in various markets are shown in Figure 2.
[0088] In some embodiments, the thermoplastic block copolymers based on vegetable oil or polymerized animal oil or thermoplastic statistical copolymers of the present invention can be used as a major component in the thermoplastic elastomeric composition, to improve the thermoplastic and elastic properties of composition. To form an elastomeric composition, the thermoplastic block copolymer can also be vulcanized, cross-linked, compatibilized, and / or composed with one or more other materials, such as another elastomer, additive, modifier and / or filler. The resulting elastomer can be used as a rubber splice composition in various industries such as footwear, automobiles, packaging, etc.
[0089] In one embodiment, the thermoplastic block copolymers based on vegetable oil or polymerized animal oil or thermoplastic statistical copolymers of the present invention can be used in an automobile, such as in vehicle tires, hoses, belts. energy, conveyor belts, printing rollers, rubber presses, car mats, truck flaps, ball mill liners, and caulking strips. Thermoplastic block copolymers can serve as a major component in the thermoplastic elastomeric composition, to improve the thermoplastic and elastic properties of automobile compositions (for example, vehicle tires). The resulting compositions can also be vulcanized, cross-linked, made compatible, and / or composed with one or more other materials, such as another elastomer, additive, modifier and / or filler.
[0090] In one embodiment, thermoplastic block copolymers based on vegetable oil or polymerized animal oil or thermoplastic statistical copolymers of the present invention can be used in an asphalt composition, as an asphalt additive, modifier and / or filler . The asphalt composition can also comprise a bitumen component. The asphalt composition can comprise a wide range of the block copolymer. For example, the asphalt composition comprises 1 to 5% by weight of the thermoplastic block copolymer or statistical thermoplastic copolymers.
[0091] In one embodiment, thermoplastic block copolymers based on vegetable oil or polymerized animal oil or statistical thermoplastic copolymers can be used in an adhesive composition. The adhesive composition can also comprise an adhesive and / or a plasticizer.
[0092] In one embodiment, thermoplastic block copolymers based on vegetable oil or polymerized animal oil or statistical thermoplastic copolymers can be used in a thermoplastic composition of resistant construction. The thermoplastic composition of hardened construction typically comprises predominantly a glassy or semi-crystalline component with a minority of rubber or elastomeric component to increase the hardness (reduce brittleness) of the material, for example, analogous to High Impact Polystyrene (HIPS) . To form the thermoplastic composition of hardened construction, the block copolymer of the present invention can be formulated in such a way that the vegetable oil block is a minority of component and serves to absorb energy that would otherwise lead to fracturing of the solid matrix. The block copolymer or the static copolymer in the thermoplastic composition of hardened construction can also be composed with other materials, such as other thermoplastics, additives, modifiers, or construction fillers.
[0093] In a modality, poly (styrene-block-SBO-block-stretch) (PS-PSBO-PS) or PS-PCSBO-PS is synthesized by means of RAFT.
[0094] The resulting PS-PSBO-PS or PS-PCSBO-PS polymer may contain ~ 25% by weight of polystyrene and be in the order of 100 kDa.
[0095] In one embodiment, PS-PSBO-PS polymers of the above modality are mixed with asphalt binders.
[0096] As the structure-property relationships for the PS-PSBO-PS system are built, composition and molecular weight ranges that should be better adapted as bitumen modifiers can be identified using the above-mentioned modality.
[0097] The developed biopolymers are mixed with two asphalts for subsequent testing. The asphalt binders used are derived from raw Canadian and Texas sources just as they are commonly used in the United States. The biopolymers are mixed with 3% by weight of the combined asphalt binder. A styrene-butadiene-type polymer is used as a reference polymer for subsequent techno-economic analysis. The mixture and subsequent rheological test are shown in Figure 3 and follow the American Association of State Highway and Transportation Officers (AASHTO) M 320 test to determine the degree of an asphalt binder (AASHTO M 320: Standard Specification for Performance-graded Asphalt Binder, American Association of State Highway and Transportation Officials, Washington, DC (2002), which is hereby incorporated by reference in its entirety).
[0098] Frequency scans are performed on a dynamic shear rheometer (DSR) and rotational viscometer (RV) at multiple temperatures. The flexion beam rheometer test is performed at multiple temperatures. A thin film laminating oven (RTFO) and pressure aging vessel (PAV) are used to conduct the simulated aging of binder mixtures representing the aging of binders that occur during the production of asphalt mixtures and aging in situ, respectively.
[0099] These tests allow the understanding of the effects of polymer content, effects of raw source, and the rheological behavior of the mixtures developed. Prior to the rheological test, the separation test is done to assess the ability of polymers to meet the standards of the American Society for Testing and Materials (ASTM) to maintain homogeneity, ASTM D7173 using a rotational viscometer (ASTM Standard C33: Standard Practice for Determining the Separation Tendency of Polimer from Polimer Modified Asphalt, ASTM International, West Conshohocken, PA (2003), which is hereby incorporated by reference in its entirety). Each test is carried out in triplicate on the same mixtures, which allows the analysis of variation (ANOVA) and subsequent regression analysis.
[00100] Statistical analysis of the data is performed using the chemical and physical data of the biopolymers and the rheological properties. The analysis also includes ANOVA to identify independent variables that are significant, for example, which variables affect the shear modulus of DSR test-derived binders. Once the significant variables are identified, regression analysis can be conducted using the significant variables to identify the interactions between the variables and understand their relative effect / magnitude on the dependent variable. Additional analysis of the data includes the development of master binder curves to compare the rheological properties of the binders over a temperature range.
[0100] Another aspect of the present invention relates to a method of preparing a thermoplastic block copolymer. The method comprises providing a radically polymerizable monomer, represented by A, or a PA polymer block comprising one or more units of monomer A. A radically polymerizable triglyceride or mixture thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides, represented by B, are also provided. Monomer A or polymer block PA is polymerized with monomer B by reversible fragmentation-addition chain transfer polymerization (RAFT), in the presence of a free radical initiator and a chain transfer agent, to form the copolymer thermoplastic block. The polymerization step is carried out under effective conditions to obtain a degree of polymerization of average number (Nn) for the thermoplastic block copolymer of up to 100,000 without gelation.
[0101] The polymerization step can be performed by a) polymerization of monomer A by means of RAFT in a suitable solvent to dissolve the PA block; and b) polymerization of monomer B by means of RAFT in a suitable solvent to dissolve the PA block and a PB polymer block comprising one or more units of monomer B. The PA block of step a) acts as a transfer agent for macro chain, which monomer B can add on, thereby forming a diblock copolymer PA-PB. The resulting di-block cup-polymer PA-PB from step b) can be used as a macro chain transfer agent for c) also polymerizing the PA-PB di-block with monomer A by means of RAFT. This adds an additional polymer block to the PA-PB di-block copolymer, forming a PA-PB-PA tri-block copolymer.
[0102] Step c) can be repeated multiple times, adding the desired polymer block (either PA or PB block) to form a desirable multiple block copolymer. For example, a PA-PB-PA-PB-PA penta-block copolymer can be formed by repeating Step c) three times, adding PA, PB and PA, at each step respectively, to the PA-PB di-block copolymer. formed from step b).
[0103] In addition, monomer A or monomer B in the polymerization of Step c) can each independently be the same or different monomer A or monomer B used in the polymerization step a) or b). For example, when adding a monomer A to the PA-PB di-block already formed to form a PA-PB-PA tri-block, this additional A monomer may be the same type of monomer A unit used in the di-block (for example, both are styrene), or a different type (for example, monomer unit A in di-block is styrene; and additional monomer A is methyl (meth) acrylate).
[0104] Using this method, repeating Step c) multiple times, and adding the desired polymer block each time, different block polymer architectures can be obtained, for example, multiple block copolymers having one architecture (PA-PB) n or architecture (PA-PB) n-PA, where n is an integer greater than 1, are produced; and each unit of monomer A or unit of monomer B in architecture can be the same or different.
[0105] When the chain transfer agent used at the beginning of the polymerization is a tele-chain transfer agent, the polymerization step can be carried out by a) polymerization of monomer A by means of RAFT in a suitable solvent to dissolve the PA block with the tele-chain transfer agent, thereby inserting the PA block into the tele-chain transfer agent, producing a symmetrical polymer PA block with a trithiocarbonate bond of the tele-chain transfer agent in the center of the chain outline: PA-TCTA-PA (see Scheme 1); and b) polymerization of monomer B by means of RAFT in a suitable solvent to dissolve the PA block and a PB polymer block comprising one or more units of monomer B. TCTA is a portion in the PA block, derived from the transfer agent of a telekeletal chain, for example, a portion of tritocarbonate or any other portion of a telekelic CTA agent used to produce the telekeletal thermoplastic block copolymers. The PA block (that is, the PA-TCTA-PA block) of step a) acts as a macro telekelic chain transfer agent, where monomer B can be symmetrically added inside the PA block following the same mechanism shown in Scheme 1, thereby forming a symmetric triblock copolymer PA-PB-PA (i.e., PA-PB-TCTA-PB-PA). The resulting triblock copolymer PA-PB-PA (PA-PB-TCTA-PB-PA) from step b) can be used as a telekelic chain transfer macro agent to c) also polymerize monomer A within the chain. PA-PB-PA tri-block symmetrically by means of RAFT. This adds additional symmetrical polymer blocks to the interior of the tri-block copolymer, forming a penta-block copolymer PA-PB-PA-PB-PA, i.e. PA-PB-PA-TCTA-PA-PB-PA.
Scheme 1. Schematic representation of the basic mechanism of polymerization by RAFT using a telekelic chain transfer agent. AIBN is an exemplary chain initiator, azobisisobutyronitrile; e ^ R is an exemplary monomer unit, a vinyl monomer (Tasdelen et al., "Telechelic Polimers by Living and Controlled / Living Polimerization Methods," Progress in Polimer Science 36 (4), 455-567 (2011) , which is hereby incorporated by reference in its entirety).
[0106] In addition, monomer A or monomer B in the polymerization of Step c) can each independently be the same or different monomer A or monomer B used in polymerization step a) or b). For example, when adding a monomer A to the PA-PB-PA tri-block already formed to form a PA-PB-PA-PB-PA penta-block, this additional A monomer can be the same type of monomer unit The one used in the tri-block (for example, both are styrene), or a different type (for example, the initially added monomer unit A in tri-block is styrene (S); and the additional monomer A is methyl (meth) acrylate (MMA), thereby forming PS-PB-PMMA-PB-PS).
[0107] Using this method, repeating Step c) multiple times, and adding the desired symmetrical polymer blocks each time, different block polymer architectures can be obtained, for example, multiple block copolymers having one architecture (PA- PB) n-PA or PB- (PA-PB) n architecture, where n is an integer greater than 2, are produced; and each unit of monomer A or unit of monomer B in the architecture can be the same or different.
[0108] Alternatively, the method of preparing a thermoplastic block copolymer comprises providing a radically polymerizable triglyceride or mixture thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides, represented by B, or a block of PB polymer comprising one or more monomer units B. A radically polymerizable monomer, represented by A, is also provided. Monomer B or polymer block PB is polymerized with monomer A by means of RAFT, in the presence of a free radical initiator and a chain transfer agent, to form the thermoplastic block copolymer. The polymerization step is carried out under effective conditions to obtain a degree of polymerization of average number (Nn) for the termoplastic block copolymer of up to 100,000 without gelation.
[0109] The polymerization step can be carried out by a) polymerization of monomer B by means of RAFT in a suitable solvent to dissolve the PB block; and b) polymerization of monomer A by means of RAFT in a suitable solvent to dissolve a block of PA polymer comprising one or more units of monomer A and the block of PB. The PB block from step a) acts as a macro chain transfer agent, which monomer B can add on, thereby forming a PB-PA diblock copolymer. The resulting b-block PB-PA copolymer from step b) can be used as a macro chain transfer agent to c) also polymerize the PB-PA di-block with monomer B by means of RAFT. This adds an additional polymer block to the PB-PA di-block copolymer, forming a PB-PA-PB tri-block copolymer.
[0110] Step c) can be repeated multiple times, adding the desired polymer block (or PB or PA block), to form the desired multiple block copolymer. For example, a PB-PA-PB-PA-PB penta-block copolymer can be formed by repeating Step c) three times, adding PB, PA, and PB, at each step respectively, to the PB-PA block copolymer. PA formed from step b).
[0111] In addition, monomer A or monomer B in the polymerization of Step c) can each independently be the same or different monomer A or monomer B used in the polymerization step a) or b). For example, when adding a monomer B to the already formed di-block PB-PA to form a tri-block PB-PA-PB, this additional monomer B may be the same type of monomer B unit used in the di-block (for example, both are soybean oil containing triglycerides with the same conjugation site and the same degree of conjugation), or a different type (for example, monomer unit B in di-block is soybean oil; and the additional monomer B is a different type of vegetable oil or animal oil, or soybean oil having triglycerides with different conjugation site and different degree of conjugation).
[0112] Using this method, repeating Step c) multiple times, and adding the desired polymer block each time, different block polymer architectures can be obtained, for example, multiple block copolymers having a PB- (PA- PB) n, where n is an integer greater than 1, are produced; and each unit of monomer A or unit of monomer B in architecture can be the same or different.
[0113] When the chain transfer agent used at the beginning of the polymerization is a tele-chain transfer agent, the polymerization step can be carried out by a) polymerization of monomer B by means of RAFT in a suitable solvent to dissolve the PB block with the tele-chain transfer agent, thereby inserting the PA block into the tele-chain transfer agent, producing a symmetrical polymer PB block with a trithiocarbonate bond of the tele-chain transfer agent in the center of the chain contour: PB-TCTA - PB (see Scheme 1); and b) polymerization of monomer A by means of RAFT in a suitable solvent to dissolve a block of PA polymer comprising one or more units of monomer A and the block of PB. TCTA is a portion in the PB block, derived from the telekelic chain transfer agent, for example, a trithiocarbonate portion or any other portion of a telekelic CTA agent used to produce the telekeletal thermoplastic block copolymers. The block of PB (that is, the block PB-TCTA -PB) of step a) acts as a transfer agent of macro telekelic chain, where monomer A can be symmetrically added inside the block of PB following the same mechanism shown in Scheme 1, thereby forming a symmetric triblock copolymer PB-PA-PB (i.e., PB-PA-TCTA-PA-PB). The resulting triblock copolymer PB-PA-PB (PB-PA-TCTA-PA-PB) from step b) can be used as a tele-chain transfer macro agent to c) also polymerize monomer B within the chain of the tri-block PB-PA-PB symmetrically by means of RAFT. This adds additional symmetrical polymer blocks within the tri-block copolymer, forming a penta-block copolymer PB-PA-PB-PA-PB, i.e., PB-PA-PB-TCTA-PB-PA-PB.
[0114] In addition, monomer A or monomer B in the polymerization of Step c) can each independently be the same or different monomer A or monomer B used in the polymerization step a) or b). For example, when adding a monomer B to the already formed tri-block PB-PA-PB to form a penta-block PB-PA-PB-PA-PB, this additional B monomer may be the same type of monomer B unit used in the tri-block (for example, both are soybean oil containing triglycerides with the same conjugation site and the same degree of conjugation), or a different type (for example, the initially added monomer unit B in tri-block is soy (SBO); and the additional B monomer is a different type of vegetable oil, animal oil, or synthetic triglycerides; or triglycerides or mixtures of triglycerides with different conjugation sites and different degree of conjugation (B2), thereby forming PSBO- PA-PB2-PA-PSBO).
[0115] Using this method, repeating Step c) multiple times, and adding the desired symmetrical polymer blocks each time, different block polymer architectures can be obtained, for example, multiple block copolymers having one architecture (PA-PB) n-PA or Architecture PB- (PA-PB) n, where n is an integer greater than 2, are produced; and each unit of monomer A or unit of monomer B in the architecture can be the same or different.
[0116] Another aspect of the present invention relates to a method of preparing a thermoplastic homopolymer. The method comprises providing a radically polymerizable triglyceride or mixture thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides. This triglyceride-based monomer is then polymerized by means of RAFT, in the presence of a free radical initiator and a chain transfer agent, to form the thermoplastic homopolymer. The polymerization step is carried out under effective conditions to obtain a degree of polymerization of average number (Nn) for the thermoplastic homopolymer of up to 100,000 without gelation. The modalities for the starting material (polymerizable triglyceride or mixtures of triglycerides), the reaction agents, the reaction mechanism, and the reaction parameters and conditions are the same as those described for the methods of preparing a thermoplastic block copolymer using or a regular chain transfer agent or a telekelic chain transfer agent.
[0117] The resulting thermoplastic homopolymer can itself be used as a thermoplastic elastomer, and has the same monomer unit, structures, and characteristics as the PB block described in the modalities for thermoplastic block copolymers. Consequently, this thermoplastic homopolymer can also be used as a polymer block, and can also be polymerized with other monomers or form a thermoplastic block copolymer based on polymerized vegetable or animal oil.
[0118] Another aspect of the present invention relates to a method of preparing a statistical thermoplastic copolymer. The method comprises providing a radically polymerizable monomer, represented by A. A radically polymerizable triglyceride or mixture thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides, represented by B is also provided. Monomer A and monomer B are simultaneously polymerized, by means of RAFT, in the presence of a free radical initiator and a chain transfer agent to form the thermoplastic statistical copolymer. The polymerization step is carried out under effective conditions to obtain a degree of polymerization of average number (Nn) for the thermoplastic statistical copolymer of up to 100,000 without gelation.
[0119] The method can be used to simultaneously polymerize three or more different monomer units. For example, another radically polymerizable monomer, represented by C, can also be supplied, in addition to monomer A and monomer C. Monomer C is different from monomer A or monomer B. Monomer A, monomer B, and monomer C are then polymerized simultaneously, by means of RAFT, in the presence of the free radical initiator and the chain transfer agent to form the statistical thermoplastic copolymer. The polymerization step is carried out under effective conditions to obtain a degree of polymerization of average number (Nn) for the thermoplastic statistical copolymer of up to 100,000 without freezing.
[0120] The polymerization of monomers A and B to form thermoplastic block copolymer or statistical thermoplastic copolymer is carried out by means of live free radical polymerization which involves controlled / live free radical polymerization as the active polymer chain termination (Moad et al., "The Chemistry of Radical Polymerization - Second Edition Fully Revised," Elsevier Science Ltd. (2006), which is hereby incorporated by reference in its entirety). This form of polymerization is a form of polymerization by addition where the ability of a growing polymer chain to terminate has been removed. The rate of chain initiation is thus much higher than the rate of chain propagation. The result is that polymer chains grow at a more constant rate than seen in traditional chain polymerization and their lengths remain very similar. One form of live free radical polymerization is Chain Transfer by Radical Addition-Fragmentation (RAFT).
[0121] Polymerization by chain transfer by addition-radical fragmentation (RAFT) is a type of live polymerization or controlled polymerization using a chain transfer agent (CTA). Conventional RAFT polymerization mechanism, consisting of a sequence of addition-fragmentation equilibria, is shown in Figure 1 (Moad et al., "Living Radical Polymerization by the Raft Process- a First Update," Australian Journal of Chemistry 59: 66992 (2006), which is incorporated here by reference in its entirety). As shown in figure 1, the RAFT polymerization reaction begins with initiation. Initiation is carried out by adding an agent capable of decomposing to form free radicals; the fragment of free radical decomposed from the primer attacks a monomer producing a propagation radical (P ^ n), in which additional monomers are added producing an increasing chain. In the propagation stage, the propagation radical (P ^ n) is added to a chain transfer agent (CTA), such as a thiocarbonylthio compound (RSC (Z) = S, 1), followed by fragmentation of the intermediate radical (2) forming a dormant polymer chain with a thiocarbonylthio terminus (PnS (Z) C = S, 3) and a new radical (R ^). This radical (R ^) reacts with a new monomer molecule forming a new propagation radical (P'm). In the chain propagation stage, (P'n) and (P'm) reach equilibrium and the dormant polymer chain (3) provides an equal probability for all polymer chains to develop in the same proportion, allowing the polymers to be synthesized with narrow polydispersity. Termination is limited in RAFT, and if they occur, it is insignificant. The targeting of a specific molecular weight in RAFT can be calculated by multiplying the ratio of the monomer consumed to the concentration of CTA used, by the molecular weight of the monomer.
[0122] Initiation agents are often referred to as "initiators." Suitable initiators depend greatly on the details of the polymerization, including the types of monomers being used, the type of catalyst system, the solvent system, and the reaction conditions. A typical radical initiator can be azo compounds, which provide a two-carbon center radical. Radical initiators, such as benzoyl peroxide, azobisisobutyronitrile (AIBN), 1,1'-azobis (cyclohexanecarbonitrile) or (ABCN), or 4,4'-Azobis (4-cyanovaleric acid) (ACVA); redox initiator such as benzoyl peroxide / N, N-dimethylaniline; microwave heating initiator; photoinitiator such as (2,4,6-trimethylbenzoyl) -diphenylphosphine oxide; gamma radiation initiator; or Lewis acids, such as scandium (III) triflate or yttrium (III) triflate, are typically used in RAFT polymerization.
[0123] RAFT polymerization can use a wide variety of CTA agents. Suitable CTA agents must be able to initiate the polymerization of the monomers (styrene and AESO) and obtain a narrow polydispersity in the process. For RAFT polymerization to be efficient, the initial CTA agents and the polymer RAFT agent must have a reactive C = S double bond; the intermediate radical must quickly fragment without side reactions; the intermediary must divide in favor of products, and the expelled radicals (R *) must efficiently restart polymerization. Suitable CTA agent is typically only a thiocarbonylthio compound (ZC (= S) SR:
, where R is a free radical leaving group and Z is a group that modifies the RAFT polymerization addition and fragmentation rates. Exemplary CTA agents include, but are not limited to, a dithioester compound (where Z = aryl, heteraryl, or alkyl), a trithiocarbonate compound (where Z = alkylthio, arylthio, or heteroarylthio), a dithiocarbamate compound (where Z = arylamine or heterarylamine or alkylamine), and a xanthate compound (where Z = alkoxy, aryloxy, or heteroaryloxy), which are capable of reversible association with polymerizable free radicals. Z can also be sulfonyl, phosphonate, or phosphine. A more extensive list of suitable CTA agents (or RAFT agents) can be found in Moad et al., "Living Radical Polymerization by the Raft Process- a First Update," Australian Journal of Chemistry 59: 669-92 (2006); Moad et al., "Living Radical Polymerization by the Raft Process- a Second Update," Australian Journal of Chemistry 62 (11): 1402-72 (2009); Moad et al., "Living Radical Polymerization by the Raft Process- a Third Update," Australian Journal of Chemistry 65: 985-1076 (2012); Skey et al., "Facile one pot synthesis of a range of reversible addition-fragmentation chain transfer (RAFT) agents." Chemical Communications 35: 4183-85 (2008), which are hereby incorporated by reference in their entirety. The effectiveness of the CTA agent depends on the monomer being used and is determined by the properties of the free radical leaving group R and group Z. These groups activate and deactivate the thiocarbonyl double bond of the RAFT agent and modify the stability of the intermediate radicals (Moad et al., "Living Radical Polymerization by the Raft Process- a Second Update," Australian Journal of Chemistry 62 (11): 1402-72 (2009), which is hereby incorporated by reference in its entirety). Typical CTA agents used are 1-phenylethyl benzodithioate or 1-phenylethyl 2-phenylpropanoditioate.
[0124] In one embodiment, the chain transfer agent used is a telekelic chain transfer agent, which is typically based on the trithiocarbonate functionality. Polymers produced from the chain transfer agent based on a functional trithiocarbonate group retain CTA functionality at the chain's statistical center, as opposed to polymers produced by a dithiocarbonate CTA, which retain CTA functionality at the end of the chain polymeric. The telekelic chain transfer agent is able to add polymer blocks symmetrically from the interior where the trithiocarbonate functionality is located, that is, polymerization monomers at both ends, forming symmetrical architecture or polymer blocks. For example, the RAFT process begins with the chain transfer from a growing A radical to a functional trithiocarbonate:
The formed radical intermediate is stable against coupling or disproportion reactions with other free radicals. One of the thioate groups reversibly fragmented allowing the propagation of one of the three branches:
See also Scheme 1 for the basic mechanism of polymerization by RAFT using a tele-chain transfer agent. Suitable telekeletal CTA agents include any trithiocarbonate compound (for example,
, where Z = alkylthio, arylthio, or heteroarylthio and R is free radical leaving group). A more extensive list of suitable telekeletal CTA agents (tritio-carbonate compounds) can be found in Skey et al., "Facile one pot synthesis of a range of reversible addition-fragmentation chain transfer (RAFT) agents." Chemical Communications 35: 4183-85 (2008), which is hereby incorporated by reference in its entirety. A typical tele-chain transfer agent is benzyl carbonotrithioate

[0125] The radically polymerizable monomers used in this method include, but are not limited to, vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a monomer with reactive functionality, a crosslinking monomer, and mixtures thereof. Exemplary embodiments for monomer A according to the method of the present invention have been described above in exemplary embodiments for monomer A in the thermoplastic block copolymer. Monomers A radically polymerizable examples used in this method are styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, vinyl acetate, N-vinyl pyrrolidone, methyl acrylate, C1 -C6 (meth) acrylate (ie, methyl methacrylate, ethyl methacrylate, propyl (meth) acrylate, butyl (meth) acrylate, heptyl (meth) acrylate, or hexyl (meth) acrylate), acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, or mixtures thereof. In one embodiment, polymerizable vinyl monomer A is an aromatic vinyl monomer, for example, a styrene. In one embodiment, the polymerizable monomer A is an acrylate monomer, for example, a methyl (meth) acrylate.
[0126] The radically polymerizable vegetable oil monomers or animal oil monomers used in this method include, but are not limited to, the vegetable oil monomer such as soybean oil, peanut oil, nut oil, palm oil, seed oil palm oil, sesame oil, sunflower oil, safflower oil, rapeseed oil, linseed oil, linseed oil (flax seed oil), rapeseed oil, coconut oil, corn oil, oil cottonseed oil, olive oil, castor oil, false flax oil, hemp oil, mustard oil, turnip oil, ramtil oil, rice bran oil, salicornia oil, tigernut oil, oil tung, etc., and mixtures thereof. Exemplary vegetable oils used in the method are soybean oil, corn oil, linseed oil (flax seed oil), or rapeseed oil. In one embodiment, the polymerized vegetable oil monomer is poly (soybean oil). Suitable animal fats used in accordance with the present invention include, but are not limited to, beef or mutton fat such as beef tallow or mutton tallow, pork fat, such as lard, fat poultry such as turkey and / or chicken fat, and fish fat / oil. Animal fats can be obtained from any suitable source including restaurants and meat production facilities. The triglyceride in vegetable oil or animal oil can comprise one or more conjugated sites, as described above. In one embodiment, the triglyceride is an acrylated epoxidized triglyceride.
[0127] Consequently, in one embodiment, the present invention relates to methods of preparing a thermoplastic and elastomeric block copolymer having a poly (styrene-soy oil) (PS-PSBO) or tri-block copolymer architecture (PS-PSBO) or a poly (styrene-soy oil-styrene) (PS-PSBO-PS) triblock polymer architecture, via RAFT reaction. The method comprises the following steps: a) RAFT polymerization of styrene homopolymer (PS), to reach a molecular weight of 1 to 1000 kDa, 1 to 300 kDa, or 10 to 30 kDa, optionally followed by purification; b) RAFT polymerization of SBO or CSBO using PS as a macro chain transfer agent, in a solvent suitable for the mutual dissolution of PS and polySBO or polyCSBO, to produce the PS-PSBO or PS diblock copolymer -PCSBO having a molecular weight of 5 to 10,000 kDa, 5 to 500 kDa, 15 to 300 kDa, 40 to 100 kDa, or 80 to 100 kDa; and c) optionally RAFT polymerization of styrene using PS-PSBO or PS-PCSBO as the macrochain transfer agent, to produce PS-PSBO-PS or PS-PCSBO-PS tri-block copolymer having a molecular weight of 7 to 10,000 kDa, 7 at 1000 kDa, 7 to 500 kDa, 15 to 350 kDa, 80 to 120 kDa or 100 to 120 kDa.
[0128] Alternatively, the method of the present invention may comprise the following steps: a) RAFT polymerization of SBO or CSBO to achieve a molecular weight of 1 to 1000 kDa, 1 to 300 kDa, or 10 to 30 kDa, optionally followed by purification; b) RAFT polymerization of styrene homopolymer (PS), using PSBO or PCSBO as a macrochain transfer agent, in a solvent suitable for the mutual dissolution of PS and PSBO or PCSBO, to produce the PS-diblock copolymer PSBO or PS-PCSBO having a molecular weight of 5 to 10,000 kDa, 5 to 500 kDa, 15 to 300 kDa, 40 to 100 kDa, or 80 to 100 kDa; and c) optionally RAFT polymerization of styrene to terminate PSBO or PCSBO using PS-PSBO or PS-PCSBO as the macrochain transfer agent, to produce PS-PSBO-PS or PS-PCSBO-PS triblock copolymer having a molecular weight of 7 to 10,000 kDa, 7 to 1000 kDa, 7 to 500 kDa, 15 to 350 kDa, 80 to 120 kDa or 100 to 120 kDa.
[0129] In one embodiment, the method of the present invention may also comprise the following steps: a) RAFT polymerization of styrene homopolymer using a tele-chain transfer agent to achieve a molecular weight of 1 to 1000 kDa, 1 to 300 kDa, or 10 to 30 kDa, optionally followed by purification; b) RAFT polymerization of PSBO or PCSBO, using the styrene homopolymer (PS) as the macro chain transfer agent, in a solvent suitable for the mutual dissolution of PS and PSBO or PCSBO, to produce a PS- PSBO-PS or PS-PCSBO-PS having a molecular weight of 7 to 10,000 kDa, 7 to 1000 kDa, 7 to 500 kDa, 15 to 350 kDa, 80 to 120 kDa or 100 to 120 kDa.
[0130] A typical vegetable oil or conjugated animal oil used in accordance with the method of the present invention is acrylated epoxidized vegetable oil or animal oil, such as acrylated epoxidated oil, which contains one or more acrylated epoxidized triglycerides.
[0131] In RAFT polymerization, reaction time, temperature, and solvent concentration must be chosen appropriately to guarantee the production of non-crosslinked thermoplastic elastomers. The reaction time is closely related to the temperature at which the reaction is carried out: higher temperature requires shorter reaction times and lower temperature requires longer reaction times. Monitoring the polymerization time of the AESO block is crucial when the reaction of the vegetable oil for a long time causes the polymer to crosslink; while reacting the vegetable oil for a very short period of time makes the polymer conversion very slow. Temperatures for polymerization by RAFT in reaction of vegetable oil or animal oil can vary from room temperature up to 180 ° C.
[0132] A RAFT reaction of styrene and soybean oil to prepare thermoplastic elastomers, polymerization can be carried out at a temperature of 200 ° C or lower. The ideal temperature is the minimum at which polymerization can occur at reasonable time scales, for example, 6 to 48 hours. In a RAFT reaction of SBO or CSBO to prepare thermoplastic elastomers based on PSBO or PCSBO, it is desirable to produce PSBO or PCSBO with high molecular weight and low glass transition temperature (Tg), and with the retention of the terminal halogen, which allows the subsequent addition of a polystyrene block. Thus, high reaction temperatures as in conventional radical polymerizations are undesirable in a RAFT reaction involving SBO or CSBO. Typical reaction temperatures for a RAFT reaction between styrene and soybean oil is 150 ° C or lower, for example, from 0 to 150 ° C, from 40 ° C to 150 ° C, from 80 ° C to 150 ° C, from 40 ° C to 100 ° C, from 50 ° C to 85 ° C, or from 0 ° C to 50 ° C.
[0133] In a conventional RAFT polymerization process, an N: 1 molar ratio (monomer to CTA ratio) would produce polymers with an average of N repeating units where the ratio of monomer to CTA agent generally ranges from 1000: 1 to 1: 1. In the RAFT ratio of vegetable oil or animal oil of the present invention, however, a 10: 1 molar ratio of monomer to CTA is used to obtain a thermoplastic elastomer. This ratio of monomer to CTA represents an excess of CTA compared to a conventional RAFT synthesis. In AESO polymerization, however, the multifunctional character of the monomer tends to crosslink. This cross-linking can be mitigated by the use of excess CTA.
[0134] In one embodiment, polymerization by RAFT is performed in a molar ratio of the chain transfer agent to the monomer ranging from 1: 1 to 50: 1.
[0135] The solvent is selected based on the mutual solubility requirements of polySBO / polystyrene and a normal boiling point compatible with the polymerization temperature. The solvent used in RAFT polymerization of styrene and soybean oil can be toluene, dioxane, THF, chloroform, cyclohexane, dimethyl sulfoxide, dimethylformamide, acetone, acetonitrile, n-butanol, n-pentanol, chlorobenzene, dichloromethane , diethyl ether, tert-butanol, 1,2, -dichlorethylene, diisopropylether, ethanol, ethyl acetate, ethyl methyl ketone, heptane, hexane, isopropyl alcohol, isoamyl alcohol, methanol, pentane, n-propyl alcohol, pentachloroethane , 1,1,2,2, -tetrachloroethane, 1,1,1, -trichloroethane, tetrachlorethylene, tetrachloromethane, trichlorethylene, water, xylene, benzene, nitromethane, or the mixture thereof. The typical solvent used for ATRP of styrene and soybean oil is dioxane. The monomer concentrations in the reactions partially depend on the solubility of the monomer and the polymer products, as well as the evaporation temperature of the solvent. The solvent concentration can affect the polymer's gelation. In conventional RAFT, the concentration of monomer in solvent during polymerizations can vary from 100% by weight (no solvent) to 33.3% by weight. However, insufficient solvent in the RAFT reaction can cause the polymer to cross-link over a longer period of time, without ever reaching sufficient high conversions. Therefore, the solvent is typically added in excess to allow the polymer chains to develop and achieve a conversion rate of up to 80%, without the risk of the polymer reaching the gel point. The concentration of monomers dissolved in the solvent in the RAFT reactions can vary from 5% to 100% by weight of monomer percentage. Typically, a monomer concentration of less than 40% by weight is adequate to ensure the solubility of the resulting polymers and additionally prevent premature freezing.
[0136] In one embodiment, the method is carried out in the presence of a solvent, at a temperature ranging from 50 to 85 ° C. The concentration of monomer B in the solvent can vary from 5% to 100% by weight, for example, from 10% to 40% by weight.
[0137] After radical polymerization, the block copolymer based on vegetable oil or polymerized animal oil can also be vegetable oil block or catalytically hydrogenated to partially or fully saturated animal oil block. This process removes reactive unsaturation from the rubber component, producing improved resistance to oxidative degradation, reduced crosslinkability and increased resistance to chemical attack. In addition, hydrogenation prevents freezing in subsequent block additions.
[0138] RAFT experiments can be performed by varying the following parameters: Temperature
[0139] Conventional free radical polymerization (CFRP) of CSBO has been reported at temperatures ranging from 60 to 150 ° C. In CFRP, the temperature dependence of polymerization kinetics is dominated by the initiator decomposition reaction. High temperature compensation is a higher polymerization rate with lower molecular weight and increased chain transfer reactions. The increasing chain transfer reaction is desirable in the production of interchangeable polymers, where the polySBO eventually gels and solidifies when the chains begin to crosslink (Valverde et al., "Conjugated Low-Saturation Soybean Oil Thermosets: Free-Radical Copolymerization with Dicyclopentadiene and Divinilbenzene, "Journal of Applied Polimer Science 107: 423-430 (2008); Robertson et al.," Toughening of Polilactide with polymerized soybean oil, "Macromolecules 43: 1807-1814 (2010), which are hereby incorporated by reference in its entirety).
[0140] For the method of preparing CSBO-based thermoplastic elastomers, the ideal temperature is the minimum at which polymerization can occur at reasonable time scales, for example, 1-48 hours. Unlike conventional free radical polymerization, the primary role of temperature in a RAFT reaction is to shift the balance to a higher concentration of free radical and increase the rate of propagation. These are desirable to a certain extent; however, when the free radical concentration increases then the rate of termination and transfer reactions increases. In CSFT RAFT to prepare thermoplastic elastomers based on PCSBO, it is desirable to produce PCSBO with a high molecular weight and a low glass transition temperature (Tg), and with the retention of the terminal halogen, which allows the subsequent addition of a block of polystyrene. Thus, the increased rate of termination and transfer reactions (ie, high reaction temperature) is undesirable in CSBO ATRP. Solvent
[0141] Mass polymerization is the starting point when the solvent directly places limits on the polymerization temperature and also influences the RAFT balance. The synthesis of polySBO from a polystyrene macroinitiator requires a solvent. The solvent is selected based on the mutual solubility requirements of polyS-BO / polystyrene and a normal boiling point compatible with the polymerization temperature. Time
[0142] The reactions are allowed to progress for 12 hours, and gel permeation chromatography is used to assess the degree of polymerization. The polymerization kinetics are subsequently evaluated and the parameters are improved, so that the polySBO compounds can be reproducibly prepared with minimal polydispersity and of a targeted molecular weight. Differential scanning calorimetry is used to evaluate the Tg of polySBO materials, which are expected to be in the range of -50 ° C (Yang et al., "Conjugation of Soybean Oil and It's Free-Radical Copolymerization with Acrylonitrile," Journal of Polymers and the Environment 1-7 (2010); Robertson et al., "Toughening of Polilactide with Polymerized Soybean Oil," Macromolecules 43: 1807-1814 (2010), which are hereby incorporated by reference in their entirety). EXAMPLES
[0143] The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention in any way. Example 1 - Synthesis of Poly (styrene) (PS), epoxidized soybean oil (acrylated) (PAESO), Poly (acrylated) -block-styrene (PAESO-PS), epoxidized soybean oil (PAESO-PS), and poly (styrene) -black-acrylated epoxidized soybean oil- Block-Styrene) (PS-PAESO-PS) by means of reversible addition fragmentation chain transfer polymerization (RAFT)
[0144] Acrylated epoxidized soybean oil (AESO) was published in Fisher Scientific and was used as received. High performance liquid chromatography grade (HPLC) toluene has been published in Fisher Scientific and used without further purification. Styrene was purchased from Fisher Scientific and purified on basic alumina followed by three freeze-pump-thaw cycles. RAFT synthesis was performed in a manner similar to the procedure described in Moad and another, "Living Radical Polymerization by the Raft Process- a First Update," Australian Journal of Chemistry 59: 669-92 (2006); Moad and another, "Living Radical Polymerization by the Raft Process-a Second Update," Australian Journal of Chemistry 62 (11): 1402-72 (2009), which are hereby incorporated by reference in their entirety. In short, azobisisobutyronitrile (AIBN, as shown in figure 4) was used as the initiator. 1-Phenylethyl benzodithioate (as shown in figure 5) was used as the chain transfer agent (CTA), and was synthesized according to stabilized procedures. Reversible addition fragmentation chain transfer (RAFT) polymerization of styrene
[0145] Monomer (styrene), initiator, CTA, and solvent were mixed under argon in a round flask with various mass ratios of monomer: solvent, 1: 5 molar ratio of initiator to CTA, and a molar ratio of 10 : 1 monomer for CTA. The reaction flask was bubbled with argon for 30 minutes to remove oxygen from the system before the temperature was raised. The reaction was carried out at 100 ° C and a reaction time varied according to the desired molecular weight (Mn). The molecular weight (mean number) increases of the styrene homopolymer as a function of time is shown in figure 6. RAFT of acrylated epoxidized soybean oil
[0146] Monomer (AESO), initiator, CTA, and solvent (1,2-dioxane) were mixed under argon in a 100 mL flask of round base with various mass ratios of monomer: solvent, 1: 5 molar ratio of initiator for CTA, and 10: 1 molar ratio of monomer to CTA. This ratio of monomer to CTA represents an excess of CTA compared to a typical RAFT synthesis. In a typical RAFT reaction, an N: 1 ratio would produce polymers with an average of N repeat units. In AESO RAFT polymerization, however, the multifunctional character of the AESO monomer tends to crosslink, which is mitigated by use of excess CTA, as described here. The reaction flask was bubbled with argon for 30 minutes to remove oxygen from the system before the temperature was raised. The reaction was carried out at 70 ° C and the reaction time varied according to the desired molecular weight (Mn). Synthesis of P (Styrene-B-AESO)
[0147] For the synthesis of P (styrene-b-AESO), AESO monomer dissolved in toluene (or dioxane) was transferred to a reaction vessel containing the styrene homopolymer. The reaction proceeded for 5 to 6 hours, and the product was cooled and precipitated three times in excess of methanol and water. Mn was monitored as a function of time for the diblock copolymer (Figure 7). The product was stirred in a volume ratio of 2: 1 methanol to ethanol solution to remove unreacted AESO monomer. The final product (Figure 8) was vacuum dried for 24 hours at room temperature. Figure 9 shows the increase in molecular weight of the monomer for the homopolymer, and for the diblock copolymer. Synthesis of P (Styrene-B-AESO-B-Styrene)
[0148] For P (styrene-b-AESO-b-styrene), the P diblock (styrene-b-AESO) was redissolved in toluene (or dioxane), styrene, and AIBN. The vessel reaction was bubbled with argon for 1 hour and the reaction proceeded for 1 to 2 hours at 70 ° C. The final product was precipitated twice in excess of methanol and water. The product was then stirred in a 2: 1 volume ratio of methanol to ethanol solution for 15 minutes to remove the unreacted AESO monomer. The product was filtered and vacuum dried at room temperature for 24 hours (Figure 10). Reaction time
[0149] The reaction times of RAFT were varied according to the desired molecular weight Mn. See Figure 7. Most reactions were stopped after 24 hours. Poly (styrene-b-AESO) mn was also monitored as a function of time, as shown in figure 6. Figure 9 shows the gel permeation chromatography (GPC) curve, in which a decrease in elution time ( increase in molecular weight) of the monomer, for homopolymer, for the diblock can be observed. After adding the final styrene block, the final product p (styrene-b-AESO-b-styrene) was subjected to different characterization techniques. Polymers characterizations
[0150] 1H-NMR was performed to prove the presence of polystyrene and to show the percentage of polystyrene in the product. The results show a styrene content of 22.4% in the product. See Figure 11.
[0151] Differential scanning calorimetry (DSC) showed a glass transition temperature for PAESO at -10 ° C; no apparent glass transition is present for the polystyrene block. See figure 12,
[0152] Isothermal frequency sweeps with a frequency ranging from 0.1-100 rad / s were conducted in the linear viscoelastic regime using a 2.5% lineage. The initial temperature was set at 120 ° C, and the final temperature was set at 220 ° C. The temperature was changed in decreases of 20 ° C, allowing 3 minutes as an equilibrium time. The elastic module, G '', shows no apparent change with a change in frequency or temperatures below about 200 ° C. The rheology result is shown in figure 13.
[0153] The tensile test was performed on an Istron 5569 using a speed of 60 mm / minute (Figure 14). The results show that the maximum stress that can be applied to the RAFT synthesized triblock copolymer was about 1.3 MPa (Figure 15). Example 2 - Synthesis and Characterization of PAESO, PAESO-PS, PS-PAESO, and PS-PAESO-PS by means of RAFT Polymerization.
[0154] Materials, synthetic procedures, and characterization experiments for PAESO, PAESO-PS, PS-PAESO, and PS-AESO-PS by means of RAFT polymerization were described in example 1. The polymers synthesized and subsequently used for characterizations are listed in Table 2. The results are shown in figures 16-18. Table 2.- List of polymers used for characterization.
a Total molecular weight of BCP bPolidispersity cPercent of styrene in BCP dMolecular weight of styrene in the first block eMolecular weight of styrene in the second block Example 3 - Synthesis and Characterization of Poly (Epoxidized) Corn Oil Homopolymers (PAECO) Through RAFT Polymerization
[0155] Materials, synthetic procedures, and characterization experiments for PAECO homopolymer by RAFT polymerization are like those described in Example 1, except that the monomer used in the polymerization of RAFT in this example is corn oil instead of soy oil. The results are shown in figures 19-20. Example 4 - Synthesis and characterization of PS-PAESO-PS and PS-PAECO-PS triblock copolymers using chain transfer telekelic agent by RAFT polymerization
[0156] Monomer (styrene), initiator, telekelic CTA, and solvent were mixed under argon in a round flask with various mass ratio of monomer: solvent, 1: 5 molar ratio of initiator to CTA, and 10: 1 molar ratio of monomer to CTA. The reaction flask was bubbled with argon for 30 minutes to remove oxygen from the system before the temperature was raised. The reaction was carried out at 100 ° C and the reaction time varied according to the desired molecular weight (Mn).
[0157] For P (styrene-b-AESO-b-styrene) or P (styrene-b-AECO-b-styrene) triblock, styrene polyhomopolymer was redissolved in toluene (or dioxane), AESO (or AECO ), and AIBN. The reaction vessel was bubbled with argon for 1 hour and the reaction proceeded for 4 to 6 hours at 70 ° C. The final product was precipitated twice in excess of methanol and water. The product was then stirred in a 2: 1 volume ratio of methanol to ethanol solution for 15 minutes to remove the unreacted AESO monomer.
[0158] Characterization experiments for the PS-PAESO-PS and PS-PAECO-PS block copolymer by RAFT polymerization are otherwise as described in examples 1-2. The results are shown in figures 21-23. Example 5 - Synthesis and Characterization of Statistical Copolymer of AESO Monomer or AECO Monomer by RAFT Polymerization.
[0159] Materials and characterization experiments for RAFT polymerization have been described in examples 1 and 3. Synthetic procedures and RAFT agents are otherwise the same as those described in examples 1 and 3, except that a statistical copolymer was synthesized by simultaneous polymerization of the styrene monomer and the AESO / AECO monomer by means of RAFT polymerization. The results are shown in figures 24-25. Example 6 - Post-Polymerization Modification of P (Styrene-b-AESO-b- Styrene)
[0160] After the different triblocks of p (styrene-b-AESO-b-styrene) were synthesized, the polymers were redissolved in solvent, and CuIICl2 was added (0.1% by mass of CuIICl2 to the polymer) to the solution . This procedure changed the ends of the polymer chain from a group terminated by the CTA functional group to a group terminated by halogen, which also improves their chemical interactions when the polymers are mixed with asphalt or other additives: P- + XS CuIIci2 ^ PCl + CuICl. Example 7 - Modification of Asphalt with Biopolymers Derived from Soybean Oil RAFT Polymerization
[0161] Kraton® D1101, a SBS polymer, is commonly mixed with liquid asphalt, in two to five percent polymer by weight of asphalt, to enhance the properties of asphalt pavements. Asphalt modification with Kraton® increases its hardness or elasticity at high temperatures, which improves the resistance of the asphalt pavement to deformation caused by high temperature transport loads. A material that hardens asphalt at high temperatures typically hardens asphalt at low temperatures, thereby increasing the susceptibility of the asphalt pavement to cracking at low temperature. However, due to the properties of Kraton® rubber, the modification of asphalt with Kronon® generally does not affect the susceptibility to cracking asphalt at low temperatures. Therefore, Kraton® essentially extends the temperature range over which an asphalt pavement will function properly.
[0162] Pavement grade liquid asphalt is most commonly purchased and sold in the United States using the Grade of Performance (PG) specification. PG grade liquid asphalt with two numbers, a high temperature degree and a low temperature degree. These degrees correspond to the temperature in degrees Celsius at which the asphalt will work properly on a pavement. An example of a grade is a PG 64-22. The first number, 64, is the high degree of temperature. This means that asphalt has adequate physical properties up to at least 64 ° C. The higher the high PG temperature of liquid asphalt, the greater resistance it will have to permanent deformation in an asphalt pavement. The second number, -22, is the low temperature degree and means that the asphalt has sufficiently low deformation-hardening properties to resist cracking by shrinking at low temperature at -22 degrees Celsius. The lower the low PG temperature of liquid asphalt, the greater resistance it will have to cracking at low temperature.
[0163] The low PG temperature subtracted from the high PG temperature is the operating temperature range over which an asphalt will operate. A PG 64-22, for example, has an operating temperature range of 86 degrees. Typically, liquid asphalt producers are limited to the production of unmodified asphalt with an operating temperature range of up to 92 degrees Celsius. Producers need to modify the asphalt with a polymer to produce asphalt with an operating range greater than 92.
[0164] The table below summarizes the results of the PG test that compared an asphalt mixed with Kraton® D1101 (commercial SBS polymer) to the same asphalt, but mixed with the PS-PAESO-PS biopolymer.

SBS (Kraton®) mixing with unmodified asphalt S-PAESO-S mixed with unmodified asphalt Mixed 3% Kraton®D1101 to liquid asphalt with an elevated PG temperature of 51.3 degrees Celsius increased its elevated PG temperature to 61.4 degrees Celsius. Mixed 3% S-PAESO-S with liquid asphalt with a high PG temperature of 51.3 degrees Celsius increased its high PG temperature to 62.1 degrees Celsius. Mixed 3% Kraton®D1101 to liquid asphalt with a low PG temperature of -36.3 degrees Celsius changed its low PG temperature to -34.1 degrees Celsius. Mixed 3% S-PAESO-S with liquid asphalt with a low PG temperature of -36.3 degrees Celsius changed its low PG temperature to -33.1 degrees Celsius. Mixed 3% Kraton®D1101 to liquid asphalt increased its PG temperature range from 87.6 to 95.5 degrees Celsius. Mixed 3% S-PAESO-S with liquid asphalt increased its PG temperature range from 87.6 to 95.2 degrees Celsius.
[0165] Although preferred modalities have been represented and described in detail here, it will be apparent to those skilled in the relevant technique that various modifications, additions, substitutions, and the like can be made without departing from the spirit of the present invention and these are therefore, considered to be included in the scope of the present invention as defined in the claims that follow.

权利要求:
Claims (37)
[0001]
1. Thermoplastic block copolymer, characterized by the fact that it comprises at least one PA block and at least one PB block, where PA represents a polymer block comprising one or more units of monomer A and PB represents a polymer block comprising a or more units of monomer B, with monomer A being a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer, or a crosslinking monomer, and monomer B being a radically polymerizable triglyceride or mixtures thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides, and optionally (a) in which one end or both ends of the PA block or PB block is functionalized with a thiocarbonylthio chain transfer group; or (b) where the block copolymer is a telekelic thermoplastic block copolymer with an architecture of (PA-PB) n-TCTA- (PB-PA) n or (PB-PA) n-TCTA- (PA-PB ) n, where: n is an integer ranging from 1 to 10, and TCTA is a portion in the PB block or PA block of a telekelic chain transfer agent used to produce the telekelic thermoplastic block copolymer.
[0002]
2. Thermoplastic block copolymer according to claim 1, characterized by the fact that the block copolymer features: PA-PB-PA or PA-PB-TCTA-PB-PA or PB-PA triblock polymer architecture -PB or PB-PA-TCTA-PA-PB; or a PA-PB-PA-PB-PA or PA-PB-PA-TCTA-PA-PB-PA or PB-PA-PB-PA-PB or PB-PA-PB-TCTA- pentablock polymer architecture PB-PA-PB.
[0003]
3. Thermoplastic block copolymer according to claim 1, characterized by the fact that (a) the block copolymer has: an architecture (PA-PB) n, where n is an integer ranging from 1 to 10; or an architecture (PA-PB) n-PA, where n is an integer ranging from 1 to 10; or a PB- (PA-PB) n architecture, where n is an integer ranging from 1 to 10.
[0004]
4. Thermoplastic block copolymer according to claim 1, characterized in that the PA block comprises repeating units of monomer A and the PB block comprises repeating units of monomer B.
[0005]
5. Thermoplastic block copolymer according to claim 1, characterized by the fact that the PA block comprises a monomer A of straight chain or polymerized branched chain, or radicals thereof.
[0006]
6. Thermoplastic block copolymer according to claim 1, characterized by the fact that monomer A is selected from the group consisting of styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, methyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, heptyl (meth) acrylate, hexyl (meth) acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene , and mixtures thereof.
[0007]
7. Thermoplastic block copolymer according to claim 1, characterized in that the PB block comprises an animal oil or vegetable oil of straight chain or polymerized branched chain, or radicals thereof, optionally: wherein the PB block comprises triglyceride polymerized or mixtures thereof, optionally the polymerized triglyceride or mixtures thereof comprises one or more conjugated sites, optionally wherein the conjugated site is formed by acrylate groups; or where the triglyceride is acrylated epoxidized triglyceride, optionally where the triglyceride is:
[0008]
8. Thermoplastic block copolymer according to claim 1, characterized in that the PB block is polymerized vegetable oil or animal oil which is subsequently partially or fully saturated by means of postpolymerization by catalytic hydrogenation.
[0009]
9. Thermoplastic block copolymer according to claim 1, characterized by the fact that monomer B is a radically polymerizable vegetable oil monomer selected from the group consisting of soybean oil, linseed oil, corn oil , flax seed oil, and rapeseed oil.
[0010]
10. Thermoplastic block copolymer according to claim 1, characterized in that the block copolymer has a PA-PB-PA or PA-PB-TCTA-PB-PA triblock polymer architecture, with the PA block being a polystyrene of linear chain or radicals thereof, and the PB block being a polymerized vegetable oil of linear or branched chain or radicals thereof, optionally: in which the vegetable oil is acrylated epoxidized vegetable oil, in which the vegetable oil is oil soy, linseed oil, corn oil, flax seed oil, or rapeseed oil; or wherein the block copolymer has a molecular weight ranging from 7 kDa to 10,000 kDa; or where the PB block has a glass transition temperature (Tg) below -15 ° C, optionally where the PB block has a Tg ranging from -60 ° C to -28 ° C; Note that the block copolymer comprises 5% by weight to 95% by weight of PA block and 95% by weight to 5% by weight of PB block.
[0011]
11. Elastomeric composition, characterized by the fact that the improvement comprises the thermoplastic block copolymer as defined in claim 1, optionally in which the block copolymer is vulcanized, cross-linked, compatibilized, and / or composed with one or more other elastomer, additive , modifier and / or load.
[0012]
12. Thermoplastic composition of resistant construction, characterized by the fact that the improvement comprises the thermoplastic block copolymer as defined in claim 1.
[0013]
13. Asphalt composition, characterized by the fact that the improvement comprises the thermoplastic block copolymer as defined in claim 12 as an additive, modifier, and / or asphalt load, optionally: wherein the asphalt composition comprises 1 to 5% by weight of the thermoplastic block copolymer; or where it also comprises a bitumen component.
[0014]
14. Adhesive composition, characterized by the fact that it comprises: the thermoplastic block copolymer as defined in claim 1 and an adherent and / or a plasticizer.
[0015]
15. Vehicle tire, characterized by the fact that the improvement comprises the thermoplastic block copolymer as defined in claim 1, in which the tire is vulcanized, cross-linked, made compatible, and / or composed with one or more other material.
[0016]
16. Method of preparing a thermoplastic block copolymer, characterized by the fact that said method comprises: (a) providing a radically polymerizable monomer, represented by a block of polymer A, or PA, comprising one or more units of monomer A ; providing a radically polymerizable triglyceride or mixture thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides, in the form of a vegetable or animal oil, represented by B; or (b) providing a radically polymerizable triglyceride or mixture thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides, represented by B, or a block of polymer PB comprising one or more units of monomer B; providing a radically polymerizable monomer, represented by A; and polymerize monomer A or polymer block PA with monomer B by means of reversible addition fragmentation chain transfer (RAFT) polymerization, in the presence of a free radical initiator and a chain transfer agent, to form the thermoplastic block copolymer, in which said polymerization is carried out under effective conditions to obtain a degree of polymerization of average number (Nn) for the thermoplastic block copolymer of up to 100,000 without gelation.
[0017]
17. Method according to claim 16, characterized by the fact that said polymerization comprises: i)) a) polymerize monomer A by means of RAFT in a suitable solvent to dissolve PA, optionally in which said polymerization step of step (a) forms a PA block having a molecular weight of 1 to 1000 kDa; and b) polymerize monomer B by means of RAFT in a suitable solvent to dissolve PA and a block of polymer PB comprising one or more units of monomer B, with PA from step (a) being a macro chain transfer agent, to form a PA-PB diblock copolymer, optionally wherein the PA-PB diblock copolymer has a molecular weight of 5 to 10,000 KDa; or is a tele-chain transfer agent, to form a symmetrical triblock copolymer PA-PB-TCTA-PB-PA, where TCTA is a fraction in the PB block derived from the tele-chain transfer agent, optionally where the telekeletal chain transfer is dibenzyl carbonotrithioate; or (ii) j) polymerize monomer B by means of RAFT in a suitable solvent to dissolve PB; and k) polymerize monomer A by means of RAFT in a suitable solvent to dissolve a block of polymer PA comprising one or more units of monomer A and PB, with PF from step (a) being a macro chain transfer agent, to form a PA-PB diblock copolymer, optionally wherein the PA-PB diblock copolymer has a molecular weight of 5 to 10,000 KDa; or a tele-chain transfer agent, to form a symmetrical triblock copolymer PA-PB-TCTA-PB-PA, wherein TCTA is a fraction in the PB block derived from the tele-chain transfer agent, optionally in which the transfer agent tele-chain chain is dibenzyl carbonotrithioate; optionally wherein said polymerization further comprises a step (c), wherein step (c) comprises: (ci) polymerizing monomer A or monomer B by means of RAFT with the block copolymer formed in step (b) as a macro chain transfer agent, thus adding an additional polymer block to the block copolymer formed in step a (b), optionally wherein said polymerization of step (c) forms a PA-PB-PA block copolymer having a weight molecular from 7 to 10,000 kDa; or (cii) polymerize monomer A or monomer B by means of RAFT with the block copolymer formed in step (b) as a tele-chain transfer agent, thus adding additional symmetrical polymer blocks to the triblock copolymer formed in step (b ).
[0018]
Method according to claim 17, characterized in that monomer A or monomer B in said polymerization step c) is each monomer equal to or different from monomer A or monomer B used in said polymerization step a) or B).
[0019]
19. Method according to claim 17, characterized in that it further comprises: d) repeating said polymerization step c) to form a multiple block copolymer.
[0020]
20. Method according to claim 16, characterized in that said polymerization is carried out in a molar ratio of the chain transfer agent to the monomer ranging from 1: 1 to 50: 1.
[0021]
21. Method according to claim 16, characterized by the fact that it further comprises: catalytically hydrogenating the reactive unsaturated sites in the PA or PB block to partial or total saturation after said polymerization.
[0022]
22. The method of claim 16, characterized in that monomer A is a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, a reactive functionality monomer, or a crosslinking monomer; or optionally in which monomer A is selected from the group consisting of styrene, α-methyl styrene, t-butyl styrene, vinyl xylene, vinyl naphthalene, vinyl pyridine, divinyl benzene, vinyl acetate, N-vinyl pyrrolidone, methyl acrylate, methyl ( met) acrylate, ethyl (met) acrylate, propyl (met) acrylate, butyl (meth) acrylate, hepty (meth) acrylate, hexyl (meth) acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, and mixtures thereof, optionally wherein monomer A is styrene or methyl (meth) acrylate.
[0023]
23. Method according to claim 16, characterized in that monomer B is a radically polymerizable vegetable oil monomer selected from the group consisting of soybean oil, corn oil, linseed oil, linseed oil flaxseed (flax seed oil), and rapeseed oil.
[0024]
24. The method of claim 165, characterized in that the triglyceride comprises one or more conjugated sites; optionally (a) in which one or more conjugated sites are formed by acrylate groups; or (b) where the triglyceride is an acrylated epoxidized triglyceride, optionally where the triglyceride is:
[0025]
25. Method according to claim 16, characterized in that the monomer A is styrene, and the monomer B is soybean oil, linseed oil, corn oil, flax seed oil , or rapeseed oil.
[0026]
26. Method according to claim 16, characterized by the fact that said polymerization is carried out at a temperature of 0 to 150 ° C.
[0027]
27. The method of claim 16, characterized in that said polymerization is carried out in a solvent at a temperature of 50 to 85 ° C; optionally wherein the solvent is toluene, THF, chloroform, cyclohexane, dioxane, dimethyl sulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol, n-pentanol, chlorobenzene, dichloromethane, diethylether, tert-butanol, 1,2, -dichlorethylene, diisopropylether, ethanol, ethylacetate, ethylmethylketone, heptane, hexane, isopropyl alcohol, isoamyl alcohol, methanol, pentane, n-propyl alcohol, pentachloroethane, 1,1,2,2, -tetrachloroethane, 1,1,1 , -trichloroethane, tetrachlorethylene, tetrachloromethane, trichlorethylene, water, xylene, benzene, nitromethane, or a mixture thereof; optionally wherein monomer B has a concentration, when dissolved in the solvent, ranging from 5% to 100% by weight; optionally ranging from 10% to 40% by weight.
[0028]
28. The method of claim 16, characterized in that the initiator is benzoyl peroxide or azobisisobutyronitrile.
[0029]
29. The method of claim 16, characterized in that the chain transfer agent is a thiocarbonylthio compound, a dithioester compound, a trithiocarbonate compound, a dithiocarbamate compound, or a combination xanthate compound reversible with polymerizable free radicals; optionally wherein the chain transfer agent is 1-phenylethyl benzodithioate or 1-phenylethyl 2-phenylpropanedithioate.
[0030]
30. Method of preparing a thermoplastic homopolymer, characterized by the fact that said method comprises: providing a radically polymerizable triglyceride or mixture thereof, in the form of a vegetable oil, animal oil, or synthetic triglycerides; and polymerizing said vegetable monomer oil or animal monomer oil by means of reversible addition fragmentation chain transfer (RAFT) polymerization, in the presence of a free radical initiator and a chain transfer agent, to form the thermoplastic homopolymer, wherein said polymerization is carried out under effective conditions to obtain a degree of polymerization of average number (Nn) for the thermoplastic homopolymer of up to 100,000 without gelation.
[0031]
31. Method according to claim 30, characterized in that the molar ratio of the chain transfer agent to the monomer ranges from 1: 1 to 50: 1.
[0032]
32. Method according to claim 30, characterized in that it also comprises: catalytically hydrogenating reactive unsaturated sites in the thermoplastic homopolymer for partial or total saturation after said polymerization.
[0033]
33. Method according to claim 30, characterized in that the monomer is a radically polymerizable vegetable oil monomer selected from the group consisting of soybean oil, linseed oil, corn oil, linseed oil (flax seed oil), and rapeseed oil.
[0034]
34. The method of claim 30, characterized in that the triglyceride comprises one or more conjugated sites or wherein the triglyceride is an acrylated epoxidized triglyceride.
[0035]
35. Method according to claim 30, characterized in that said polymerization is carried out at a temperature of 0 to 150 ° C; or wherein said polymerization is carried out in a solvent at a temperature of 50 to 85 ° C; or wherein said polymerization is carried out in a solvent with the solvent being toluene, THF, chloroform, cyclohexane, dioxane, dimethyl sulfoxide, dimethyl formamide, acetone, acetonitrile, n-butanol, n-pentanol, chlorobenzene, dichloromethane, diethyl ether , tert-butanol, 1,2, - dichlorethylene, diisopropyl ether, ethanol, ethyl acetate, ethyl methyl ketone, heptane, hexane, isopropyl alcohol, isoamyl alcohol, methanol, pentane, n-propyl alcohol, pentachloroethane, 1,1,2,2 , -tetrachloroethane, 1,1,1, -trichloroethane, tetrachlorethylene, tetrachloromethane, trichlorethylene, water, xylene, benzene, nitromethane, or the mixture thereof; or wherein said polymerization is carried out in a solvent with the monomer having a concentration, when dissolved in the solvent, ranging from 5% to 100% by weight or said polymerization is carried out in a solvent with the monomer having a concentration, when dissolved in the solvent, ranging from 10% to 40% by weight.
[0036]
36. The method of claim 30, characterized in that the initiator is benzoyl peroxide or azobisisobutyronitrile.
[0037]
37. The method of claim 30, characterized in that the chain transfer agent is a thiocarbonylthio compound, a dithioester compound, a trithiocarbonate compound, a dithiocarbamate compound, or an xanthate compound capable of association reversible with polymerizable free radicals; optionally wherein the chain transfer agent is 1-phenylethyl benzodithioate, 1-phenylethyl 2-phenylpropanedithioate, or dibenzyl carbonotrithioate.

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-20| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 20/05/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361825241P| true| 2013-05-20|2013-05-20|

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US61/825,241|2013-05-20|

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PCT/US2014/038799|WO2014189939A2|2013-05-20|2014-05-20|Thermoplastic elastomers via reversible addition-fragmentation chain transfer polymerization of triglycerides|BR122017010545-0A| BR122017010545B1|2013-05-20|2014-05-20|statistical thermoplastic copolymer, its preparation method, its compositions and vehicle tire|