BLOCK COPOLYMER, ELASTOMERIC, ASPHALTIC AND ADHESIVE COMPOSITIONS, VEHICLE TIRE, METHODS FOR PREPARI

专利摘要:
block copolymer, elastomeric, asphalt and adhesive compositions, vehicle tire, methods for preparing a thermoplastic polymer or block copolymer, and thermoplastic polymer. the present invention relates to a block copolymer comprising at least one block of pa and at least one block of bp. the pa block represents a polymer block comprising one or more units of monomer a and the block d and pb represents a polymer block comprising one or more units of monomer b. monomer a is a vinyl, acrylic, diolefin, nitrile, dinitrile or acrylonitrile monomer. monomer b is a radically polymerizable plant oil containing one or more triglycerides. the present invention also relates to a method for preparing a thermoplastic block copolymer by radical polymerization of a radically polymerizable monomer with a radically polymerizable plant oil monomer containing one or more triglycerides in the presence of an initiator and a catalyst system transition metal to form the thermoplastic block copolymer. polymerized plant oil-based block copolymers are useful in a variety of applications, such as asphalt modifiers, rubber compositions, adhesives, tires, in the automotive industry, footwear, packaging, etc.
公开号:BR112014017476B1
申请号:R112014017476-8
申请日:2013-01-18
公开日:2021-03-30
发明作者:Eric William Cochran；Ronald Christopher Williams；Nacu HERNANDEZ；Andrew A. Cascione
申请人:Iowa State University Research Foundation, Inc；
IPC主号:

专利说明:

[0001] This applicant claims the benefit of US Provisional Patent Application Serial No. 61 / 587,816, filed on January 18, 2012, which is hereby incorporated by reference in its entirety. FIELD OF THE INVENTION
[0002] The present invention refers to a new composition of thermoplastic elastomer and methods of manufacturing and using it. In particular, the present invention relates to a copolymer in a thermoplastic block comprising a polymerisable monomer block and a polymerized plant oil block containing one or more polyglycerides, methods for preparing the thermoplastic copolymer, and use of the thermoplastic copolymer. BACKGROUND OF THE INVENTION
[0003] Styrene-containing oscopolymers (SBCs), principally those of the DuPont Kraton® family, with styrene-butadiene-type polymers (eg, styrene-butadiene-butadiene-SB, tri-block styrene-butadiene-styrene), asphalted asphalt industries. and shoes for years, with the markets also in the packaging, 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 should reach 118.4 million metric tons in 2015, according to a January 2011 report by Global Industry Analysts, Inc. The asphalt paving industry accounts for the largest asphalt end use market segment. With the increase in growth in the developing markets of China, India and Eastern Europe, asphalting is perhaps more necessary for the construction of road infrastructure for the next decade. The increased demand for asphalt, together with the need for better performance of asphalt / paving materials, creates the opportunity for an asphalt modifier.
[0005] The degree of asphalt governs the performance of pavement mixtures at temperatures in service. In many cases, the characteristics of the bitumen need to be changed to improve its elastic recovery / ductility below temperatures, for sufficient cracking resistance, as well as to increase its resistance to shearing for continuous loads and / or high temperatures for resistance in the groove. The physical properties of bitumen are typically modified with the addition of SBS polymers to produce better asphalt quality, which increases the performance of asphalt paving mixes. Of the polymer asphalt mixtures that are polymer-modified, approximately 80% of polymer-asphalt modified using SBS-type polymers.
[0006] Over the past few years, the price of butadiene, the main component of SBC polymers used for bitumen modification, has been dramatically increased. In 2008, there was a shortage of SBS polymers for the asphalt industry. With the forecast of increasing demand for asphalt liquid for the next decade, there is still a strong need for new low cost viable polymers in the environment that can be used as an asphalt modifier instead of a standard styrene-butadiene modifier.
[0007] Vegetable oils have been considered as monomeric raw materials for the plastics industry for over 20 years. Polymers from vegetable oils have been given more and more attention by public policy makers and companies are also interested in replacing traditional and petrochemical raw materials due to their environmental and economic impact. So far, successful success has been achieved through the application of traditional cationic pathways and polymerization by free radicals of vegetable oils to produce thermosetting plastics (ie, plastic that once synthesized remains its shape permanently and is not subjected to further treatment). Although these thermosetting materials can effectively replace a number of chemically derived thermosetting materials, the vast majority of basic products are highly processed thermoplastic polymer. There is, therefore, a technical need to develop a highly processed and elastomeric thermoplastic polymer from vegetable oils with a wide range of applications and physical properties.
[0008] The present invention is aimed at fulfilling these technical needs. SUMMARY OF THE INVENTION
[0009] One aspect of the present invention relates to a copolymer assembled comprising at least one block of PA and at least one block of PB. 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, dinitrile, or acrylonitrile monomer. Monomer B is a radically polymerizable plant oil containing one or more polyglycerides.
[00010] Another aspect of the present invention relates to a method for preparing a copolymer containing thermoplastic. The method comprises of providing a radically polymerizable monomer, represented by A, or a PA-containing polymer comprising one or more units of monomer A. A radically polymerizable monomer of plant oil containing one or more polyglycerides, represented by B, is also provided. The PA polymer block or monomer A is then radically polymerized with monomer B, in the presence of an initiator and a transition metal catalyst system to form the copolymer emblocostermoplastic.
[00011] Alternatively, the method for preparing a copolymer in thermoplastic clusters is to provide a radically polymerizable monomer of plant oil containing one or more polyglycerides, represented by B, or a PB polymer comprising one or more B monomer units. Monomer B or polymer block PB is then radically polymerized with monomer A, in the presence of an initiator and a transition metal catalyst system, to form the copolymer emblocostermoplastic.
[00012] Another aspect of the present invention relates to a thermoplastic polymer that comprises one or more units of a radically polymerizable monomer of plant oil containing one or more polyglycerides.
[00013] Another aspect of the present invention relates to a method for preparing a block of polymer or thermoplastic polymer. The method comprises providing a radically polymerizable monomer of plant oil that contains an origlyceride. This plant oil monomer is then polymerized, in the presence of an initiator and a transition metal catalyst system to form the thermoplastic polymer block. This proper thermoplastic polymer can be used as a thermoplastic elastomer. Alternatively, this thermoplastic polymer can be used as a polymer block, and can be further polymerized with other monomers to form a thermoplastic copolymer based on polymerized plant oil.
[00014] The disclosure of the present invention involves the successful application of radical atom transfer polymerization (ATRP) to biological raw material, such as soybean oil. The distinguishing characteristic of this chemistry is that it allows the design of the molecular architecture of the resulting polymers in such a way that they are predominantly linear and non-linked or slightly modified chains that behave like elastomers / rubbers at room temperature, but are reversibly fused with very low temperature and non-reactive techniques. ATRP has received attention in relation to petrochemical raw materials, but has not been successfully applied to biological raw materials such as soybean oil. The success of vegetable oil technology such as soybean oil is surprising, as conventional radical polymerization usually leads to the polymerization of triglycerides in thermosetting materials, while the present invention successfully controls the polymerization of triglycerides thus ending with a desired molecular weight and composition of blocks and producing poly-oil from soybean oil. .
[00015] Typical monomers for chain-derived polymeric polymers are growing as functional, that is, the monomer contains only a single polymerizable functional group. Triglycerides contain a number of double bonds (which varies widely between related plant oil species and even between cultivars of the same species) and thus triglyceride monomers for polymerization will show at least two different functionalities. In this way, each polytriglyceride repetition unit has the potential to form reticulation with, at least, another polytriglyceride; when about a fraction of 1 / N of such a unit has reticulations (N indicates the number of repetition units in a polymer chain), the polymers are referred to as their "gel points", in which an infinite network of polymer formed and the material is a thermoset. Thus, when the reactivity of a propagation chain in the direction of all functional locations in both free monomers and repetition units that are already incorporated in an identical chain, the expectation is that the gel point will be reached in an extremely low conversion, in such a way that, before the gelation, the polydemand appropriate mechanical properties. This expectation is supported by the last two decades of thermosetting reports from plant oils produced by conventional cationic polymerization and free radicals. The expectation of early gelation would also extend to ATRP if the reactivity indices between spreading radials and all functional sites that did not react to the antiglycerides were rigorously identical. According to the present invention, the preferences of free monomers can be exacerbated through the appropriate selection of temperatures and the use of counter-catalysts; under such conditions, it is possible to produce polymerized triglycerides to target molecular weights of up to 500 kDa before the gel point.
[00016] Polymerized vegetable oil, such as soybean oil, is intrinsically biodegradable, renewable, and does not harm the environment. The elastomeric properties of the plant oil polymer appear to be competitive with modern amenities, such as polybutadiene (synthetic rubber). In addition, the cost of vegetable oil monomer is highly competitive. Thus, the new plastic or polymer polymers in the present invention provide cost-effective alternatives, which do not harm the environment, viable polymers for conventional petrochemical-derived materials.
[00017] These polymers or polymers in thermoplastics based on polymerized plant oil are suitable in various applications, asphalt modifiers, adhesives, rubber compositions, in the automotive industry, footwear, packaging, etc. BRIEF DESCRIPTION OF THE DRAWINGS
[00018] Figures 1A-1B are schematic drawings, illustrating the preparation of soybean oil biopolymer elastomeric (TPE) by radical atomic transfer polymerization (ATRP). Figure 1A illustrates the process for preparing poly (soybean oil) by soybean oil ATRP (SBO) which contains different triglyceride analogs. Figure 1B shows the process for preparing thermoplastic elastomeric biopolymers (ie, poly (styrene-SBO-styrene)) by styrene and SBO ATRP.
[00019] Figure 2 is a flowchart showing the process for mixing copolymer compositions of poly (styrene-SBO-styrene) with asphalt binders and then testing theirreological properties.
[00020] Figures 3A and 3B are graphs showing the gel permeation chromatography (GPC) of products resulting from the polymerization of acrylated epoxidated soybean oil (AESO) under different reaction times, starting with the samples with an AESO monomer mass for solvent of 0, 6. Figure 3C is a graph showing the GPC of products resulting from AESO polymerization under different reaction times, starting with samples with a 0.8 monomer to solvent mass ratio. Figures 3A-3C show that the molecular weight increases and the amount of monomer (i.e., the amount of product that has a lower molecular weight) decreases, as time increases.
[00021] Figure 3D shows the molecular weight distribution of AESO monomer. Figure 3E shows the molecular weight distribution of the poly-AESO polymer after 48 hours of reaction.
[00022] Figure 4 is a graph showing AESO's nuclear magnetic resonance (NMR) spectra (square more to the left) and a PAESO representative (the second square to the left) after 48 hours of reaction.
[00023] Figure 5 is a graph showing the NMR spectra of poly (styrene-AESO) (PAESO-PS). The highlighted region shows aromatic poly (styrene) hydrogens.
[00024] Figure 6 is a graph showing the results of differential scanning calorimetry (DSC) of a PAESO sample after 240 minutes of reaction. Two main glass transition temperatures are shown in the graph: at - 48 ° C and at - 29 ° C.
[00025] Figure 7 is a graph showing the DSC results of a PAESO-PS sample, after 72 hours of reaction. A glass transition is shown in the graph at -18 ° C; no apparent glass transition is present for the PS block.
[00026] Figure 8 is a graph showing the rheology graph of a PAESO-PS sample, after 72 hours of reaction.
[00027] Figure 9 is a graph showing the results of size exclusion chromatography (SEC) (calibrated with polystyrene standards) of poly (epoxidatedacrylated soybean oil) (PAESO) synthesized in accordance with the present invention.
[00028] Figure 10 is a graph showing the results of SEC (calibrated with polystyrene standards) of PS-CI, PS-PAESO-CI and PS-PAESO-PS synthesized in accordance with the present invention.
[00029] Figure 11 is a graph showing the storage and loss module G 'and G "depending on the bitumen temperature with 1% triblock poly (styrene-b-AESO-styrene) and bitumen with 1% Kraton®.
[00030] Figure 12 is a graph showing the molecular weight distribution of PAESO, PAESO-PS, and PS-PAESO characterized by the elution time determined using size exclusion chromatography.
[00031] Figure 13 is a graph showing PAESO temperature time overlap (TTS) with an average molecular weight of 45 kDa.
[00032] Figure 14 is a graph showing the change factors used to calculate TTS in Figure 13.
[00033] Figure 15 is a graph showing the results of the PS-PAESO-PS tensile test; the results were from the same sample.
[00034] Figure 16 is a graph showing the stress vs. strain curves for the petroleum-based triblock dobopolymers (SBR, and Kraton D1118) compared to PS-PAESO-PS # 1. The tests were carried out with an average speed of 50 mm / min.
[00035] Figure 17 is a graph showing the stress curves vs% deformation for PS-PAESO-PS # 1 on its first load represented by the blue line, followed by the first hysteresis cycle (black), followed by the cyclo cycle (red), and the load continues (gray) to find the maximum voltage. The black dots show the reduction of the maximal tension required to obtain 55% deformation with the progress of loading / unloading cycles. Young's modulus of charge cycles (gray squares) and discharge (red stars) of PS-PAESO-PS # 1. The tests were performed using an average speed of 50 mm / min and ranging from 0 to 55% deformation.
[00036] Figure 18 is a TEM image of the PS-PAESO-PS # 1 sample showing a semi-ordered structure, where the black islands are styrene and the most clear regions are AESO.
[00037] Figures 19A-19B are graphs that show results of the molecular weight (Mn) and polydispersity index (PDI) of polystyrene (PS) homopolymer (Figure 19A) and the poly (styrene-block-AESO) (P (Sb-AESO )) block copolymer (Figure 19B) with a time function.
[00038] Figure 20 is a graph showing the high temperature performance (PG) of asphalt-polymer mixtures. "RTFO" in the graph indicates that mixtures were aged in the thin film laminating oven (RTFO).
[00039] Figure 21 is a graph showing the low temperature performance (PG) of asphalt-polymer mixtures. "PAV-aged" in the graph indicates the mixtures were aged in the aging-pressure vessel.
[00040] Figure 22 is a graph showing non-recoverable creep compliance values (Jnr).
[00041] Figure 23 is a graph showing the percentage of recovery of asphalt-polymer mixtures.
[00042] Figure 24 is a graph showing the percentage of recovery versus the non-recoverable creep compliance of asphalt-polymer mixtures.
[00043] Figure 25 is a graph showing the percentage of recovery versus the non-recoverable creep compliance of asphalt-polymer mixtures.
[00044] Figure 26 is a graph showing the percentage of recovery versus the non-recoverable creep compliance of asphalt-polymer mixtures. DETAILED DESCRIPTION OF THE INVENTION
[00045] One aspect of the present invention relates to a copolymer assembled comprising at least one block of PA and at least one block of PB. 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, dinitrile, or acrylonitrile monomer. Monomer B is a radically polymerizable plant oil containing one or more polyglycerides.
[00046] The copolymer in thermoplastic blocks may be a lightweight or lightly modified linear copolymer, and may contain two or more blocks. Exemplary copolymer architecture includes, among others (PA-PB) n, (PA-PB) n-PA, and PB- (PA-PB) n. n is an integer greater than 0. For example, n ranges from 2 to 50, or from 2 to 10. The copolymer usually contains a di-block polymer architecture (PA-PB), tri-block polymer architecture (PA-PB-PA or PB- PA-PB) or penta-block architecture (PA-PB-PA-PB-PA or PB-PA-PB-PA-PB).
[00047] The PA block is made by polymerization of a radically polymerizable oumaismonomer, and has an average molecular weight of about 1 to about 300 kDa, or about 10 to about 30 kDa. The PA block may comprise repeating units of monomer A. For example, the PA block may be monomer A of a straight chain or branched chain polymerized or radicals thereof. The PB block is made by the polymerization of one or more monomeric plant oils that contains one or more triglycerides, and has an average molecular weight of about 5 to about 500 kDa, about 40 to about 80 kDa. The PB block can comprise repeating units of monomeric plant oil containing one or moreiglycerides. For example, the PB block can be a straight chain or branched chain monomeric plant oil, or the radicals thereof.
[00048] Di-block copolymers PA-PB normally contain about 5% by weight to about 95% by weight of polymerized block A and about 95% by weight to about 5% by weight of polymerized plant oil. PA-PB-PA or PB-PA-PB tri-block copolymers normally 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 oil block of polymerized plant. Copolymer spentabloco PA-PB-PA-PB-PA or PB-PA-PB-PA-PB typically contains about 5% by weight to about 95% by weight of the polymerized block A and about 95% by weight to about 5% in weight of polymerized plant oil block. For example, the preceding block polymers may contain about 10% by weight to about 90% by weight of the polymerized block A and from about 90% by weight to about 10% by weight of the polymerized plant oil block.
[00049] The copolymer PA block embedded can be considered as a "hard" block and has characteristic properties of the plastics substance named in which it has the necessary stability for processing at high temperatures and still has good resistance below the temperature which softens. The PA block is polymerized from a radically polymerizable ouismismomer, which can include a variety of monomer types, such as vinyl, acrylic, diolefin, nitrile, dinitrile, or acrylonitrile monomer. Aromatic vinyl monomers are exemplary vinyl monomers that can be used in the bulk copolymer, and include any aromatic vinyl compounds, optionally with one or more substitutes in the aromatic group. The aromatic fraction can be mono- or polycyclic. Exemplary monomers for the PA block include styrene, α-methylstyrene, t-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, divinylbenzene, methyl acrylate, C1-C6 (meth) acrylate (ie, methyl methacrylate, methyl acrylate, methyl acrylate) , butyl (meth) acrylate, heptyl (meth) acrylate, ouhexyl (meth) acrylate), acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, and mixtures thereof. In addition, two different monomers can be used together in the formation of the PA block. A typical radically polymerizable monomer A used here is styrene, and the resulting PA block is a styrene homopolymer.
[00050] The PB block of the copolymer embedded can be considered as a "soft" block, and it has elastomeric properties that allow it to absorb and dissipate an applied tension and, then, resume its shape. The PB block is polymerized from one or more monomeric plant oils containing one or moreiglycerides. The monomeric plant oils used in the embedded copolymer can be any plant oil that is radically polymerizable, in particular those that contain one or more triglyceride types. Suitable plant 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, linseed oil, oil flax seed, rapeseed oil, coconut oil, corn oil, cottonseed oil, olive oil, castor oil, linhofalso oil, hemp oil, mustard oil, turnip oil, rantil oil , rice bran oil, salicornia oil, tigernut oil, tung oil, etc., and mixtures thereof. The typical compositions of various vegetable oils are shown in Table 1. A typical plant oil used here is soybean oil, and the resulting PB block is polymerized triglyceride or derivative of triglycerides.Table 1: The typical vegetable oil compositions.

[00051] Vegetable oils are triglyceride mixtures. A representative structure of a triglyceride is shown below:

[00052] A typical structure of triglycerides contains a series of double bonds that can serve as candidates for polymerization. Several soybean cultivars express a variety of triglyceride compositions in their oils. Different types of soybeans can be appropriately selected based on the triglyceride compositions to improve the copolymer yield and properties.
[00053] In unprocessed oils, the double bonds contained in the antiglycerides are usually located in the middle of the alkyl chains, and have limited activity in the sense of propagation reactions, due to steric impediment and unfavorable stability of the free radical. Will be improved dramatically when duplex connections are conjugated (Li et al., "Soybean Oil- Divinylbenzene Thermosetting Polymers: Synthesis, Structure, Properties and their Relationships," Polymer 42 (4): 1567-1579 (2001); Henna et al., "Biobased Thermosets from Free Radical Copolymerization of Conjugated Linseed Oil, "Journal of Applied Polymer Science 104: 979-985 (2007); Valverde et al.," Conjugated Low-Saturation Soybean Oil Thermosets: Free-RadicalCopolymerization with Dicyclopentadiene and Divinylbenzene, "Journal of Applied Polymer Science 107: 423-430 (2008); Robertson et al., "Toughening of Polylactide with Polymerized Soybean Oil," Macromolecules 43: 1807-1814 (2010), which are here incorporated by reference in their totalities). The conjugation of double bonds in triglyceride can easily be achieved for 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)).
[00054] In any modality of the present invention, the monomer polymerizable from plant oil containing triglycerides can be replaced with a monomer polymerizable containing one or more glycerides from an animal source, for example, animal fats. Thus, the block of BP in any modality of the present invention, may instead be polymerized from one or more fats, animate anonomism, containing one or more glycerides. Examples of suitable animal fats used in accordance with the present invention include, but are not limited to, beef or mutton fat, such as beef fat and pork fat, lard such as lard, poultry fat, chicken and / or fat, and fish / oil fat. Animal fats can be obtained from any appropriate source including restaurants and meat production facilities.
[00055] "Triglycerides", as defined herein, may refer to any unmodified triglycerides naturally occurring in plant oil or animal fat, as well as any unmodified triglyceride derivatives. An unmodified triglyceride can include any glycerol-derived ester with three similarly different fatty acids. Derivatives of triglycerides can include any modified triglyceride that contains conjoined systems (ie, a system of p-orbitals connected with electrons dislocated in triglycerides). Such combined systems increase the reactivity of triglycerides in the direction of propagation reactions. Useful conjugated triglycerides include, but are not limited to, triglyceride derivatives that contain conjugated double bonds or conjugated systems formed by acrylate groups.
[00056] The term "soybean oil" used here can generally refer to any embryosaturated soybean oil or processed soybean oil that contains at least one form of triglycerides, or its derivative suitable for the polymerization reaction of the present invention. The term "conjugated soybean oil" used herein refers to any embryo soy oil or processed soy oil, containing at least one triglyceride with at least one conjugate site. Similar definitions also apply to other plant oils or conjugated plant oil.
[00057] The triglyceride conjugate can contain one or more local conjugates. For example, the triglyceride conjugate may contain a single triglyceride conjugate site. Alternatively, each triglyceride acid chain can contain one or more conjoined locations.
[00058] Examples of conjugated triglycerides are:

[00059] A more detailed description of the conjugation sites in soybean oil, soybean oil epoxidation and soybean oil acrylation can be found at NACU BERNARDO HERNANDEZ-CANTU, "SUSTAINABILITY THROUGH BLOCKCOPOLYMERS - NOVEL ION EXCHANGE CATHODE MEMBERSHESEANEAN SHEETS AND SHANTS" (Iowa State University, Ames, Iowa 2012),.
[00060] In a modality, the conjugated plant oil is epoxidatedacrylated plant oil, like epoxidatedacrylated soybean oil; Conjugated triglyceride is epoxidatedacrylated triglyceride.
[00061] In any form of the present invention, the embedding copolymer is a thermoplastic elastomer. the mechanism for achieving the dual properties of thermoplasticity and elasticity in the plant oil-based styrene copolymer stems from polymer thermodynamics and the architecture of the polymer chain. Flory-Huggins theory shows that almost all polymers are mutually immiscible, due to the loss of entropy mixture. The sequences of chemically different monomers found in block polymers can be thought of as conceptually immiscible polymers that are covalently linked from end to end. Due to this restriction, when a copolymer phase is separated, the incompatible polymer types form meso-domains with a defined geometry, depending on the composition of the block and with a size governed by the total molecular weight (Bates et al. "Block Copolymers-Designer Soft Materials," Physics Today 52 (2 ): 32-38 (1999),).
[00062] In a typical SBS elastomer, the styrene composition is about 10-30% by weight so that the spherical or oscillometric domains are formed in a butadiene array. When the temperature is below the polystyrene glass transition temperature (Tg = 100 ° C), the matrix is polybutadienoliquid (Tg <- 90 ° C) but is connected between the polystyrene-vitreous spheres, which serve as physical corticosteroids. When the temperature is above the polystyrene glass transition temperature, the entire elastomer system is melted and can be easily processed. Poly (soybean oil) crosslinked with fatty acids that are as low as -56 ° 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),). Thus, poly (soybean oil) is an excellent candidate to serve as the liquid-elastomer component in plastics based on styrene copolymers.
[00063] Thus, in a modality of the present invention, the copolymer emblocostermoplastic and elastomeric and has a PA-PB di-block polymer architecture, where the PA block is a linear chain polystyrene (PS) and the PB block is a linear polymerized soybean oil ouramificadoleve (PSBO) ouradicals, or polymeric conjugated soybean oil (PCSBO) ouradicals. The PS-PSBO di-block copolymer has a molecular weight ranging from 5 to 500 kDa, for example, 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 -15 ° C, for example, from about -60 ° C to about -28 ° C.
[00064] In a modality of the present invention, the copolymer in thermoplastic and elastomeric envelopes has a PA-PB-PA polymer tri-block architecture, where the PA is a linear chain polystyrene (PS) block, and the PB block is a light-cured linear polymerized soy oil (PSBO ) ouradicals, or polymerized soybean oil (PCSBO) ouradicals. This soy oil-based styrene copolymer (PS-PSBO-PS) therefore has an elastomeric PSBO inner block, and a PS thermoplastic outer block formed at both ends of the inner PSBO block. The PS-PSBO-PS tri-block copolymer has a molecular weight ranging from 7 kDa to 1000 kDa, for example, 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 of less than -15 ° C, for example, from about -60 ° C to about -28 ° C.
[00065] In a modality, the polymerization of radicals is carried out by radical polymerization by atom transfer. In a modality, the traditionally polymerized plant oil is soybean oil, flaxseed oil, flax seed oil, or rapeseed oil. In one modality, epoxy oxidized plant oil, such as epoxy oxidized soybean oil, is radically polymerized according to the method of the present invention.
[00066] Another aspect of the present invention relates to a method for preparing a copolymer in thermoplastic packaging. The method comprises of providing a radically polymerizable monomer, represented by A, or a PA-containing polymer comprising one or more units of monomer A. A radically polymerizable monomer of plant oil containing one or more polyglycerides, represented by B, is also provided. The PA polymer block or monomer A is then radically polymerized with monomer B, in the presence of an initiator and a transition metal catalyst system to form the copolymer emblocostermoplastic.
[00067] The radical polymerization step can be carried out by a) radical polymerization of monomer A in a suitable solvent to dissolve PA; and b) radical polymerization of monomer B in a suitable solvent to dissolve PA and PB. PA from step a) acts as the initiator to form a di-block copolymer PA-PB. The di-blocking copolymer resulting from PA-PB from step b) can be used as the initiator for c) to still polymerize radically with monomer A. This adds an additional polymer block to the PA-PB di-block copolymer, forming a tri-copolymer block PA-PB-PA.
[00068] Step c) can be repeated several times, adding the desired bloc polymer (or the PA or PB block), to form a desired multiple-copolymer. For example, a penta-block copolymer -PA-PB-PA-PB-PA can be formed by repetition c) three times, the addition of PA, PB and PA, in each step, respectively, for the di-block copolymer of PA-PB formed from step b).
[00069] Using this method, repeating c) several times, and adding the desired polymer block each time, the different copolymer architectures can be achieved, for example, multiple polopolymer assemblies with one architecture (PA-PB) n or architecture (PA-PB) n-PA, in which n is an integer greater than 1.
[00070] Alternatively, the method for preparing a copolymer in thermoplastic clusters may comprise providing a radically polymerizable plant oil monomer that contains one or more polyglycerides, represented by B, or a PB polymer comprising one or more B monomer units. Monomer B or polymer block PB is then radically polymerized with monomer A, in the presence of an initiator and a transition metal catalyst system, to form the copolymer emblocostermoplastic.
[00071] The radical polymerization step can be performed by a) radical polymerization of monomer B in a suitable solvent to dissolve PB; and b) radical polymerization of monomer A, in a suitable solvent to dissolve PA and PB. PB from step a) acts as the initiator to form the PB-PA di-block copolymer. The PB-PA di-blocoresultant copolymer from step b) can be used as the initiator for c) to further polymerize radically with monomer B. This adds a polymer block to the PB-PA di-block polymer, forming a PB-PA tri-block copolymer PA-PB.
[00072] Step c) can be repeated several times, adding the desired polymer block (either PB or PA block), to form a desired multiple-copolymer. For example, a penta-block copolymer PB-PA-PB-PA-PB can be formed by repetition c) three times, adding PB, PA and PB, in each step, respectively, to the di-block copolymer of PB-PA formed from from step b).
[00073] Using this method, repeating c) several times, and adding the desired polymer block each time, the different copolymer architectures can be achieved, for example, multiple copolymers with a PB- (PA-PB) n architecture, where n is a number greater than 1.
[00074] Radical polymerization of monomers A and B to form thermoplastic polymercopolymer can be performed through live free radical polymerization that involves live / controlled polymerization with free radicals as the polymeric chain end (Moad et al., "The Chemistry of Radical Polymerization - Second Fully Revised Edition, "Elsevier Science Ltd. (2006),). This form of polymerization is a form of polymerization by adding that the capacity of a growing polymer chain has been removed. The rate of initiation of the chain is therefore much higher than the rate of propagation of the chain. The result is that the polymer chains grow at a more constant speed than that observed by the additional polymerization of the chain and their lengths remain very similar. One form of polymerization by living free radicals is radical polymerization by atom transfer.
[00075] Radical polymerization by atom transfer (ATRP) is a catalyzed, reversible redox process that achieves controlled polymerization through easy transfer of labile radicals (eg, radicals) between the growing polymer chains and a catalyst (Davis et al., "Atom Transfer Radical. Polymerization of tert-Butyl Acrylate and Preparation of Block Copolymers, "Macromolecules 33: 4039-4047 (2000); Matyjaszewski et al.," Atom Transfer Radical Polymerization, "Chemical Reviews 101: 2921-2990 (2001), which are here incorporated by reference in their totality ). In ATRP, chain termination and transfer reactions are essentially eliminated, keeping the concentration of free radicals small. Briefly, the mechanism by which ATRP operates can be summarized as

[00076] In equation (1), the labile radical X can be a halogen (for example, Br, Cl) attached to the end of a polymer P. The catalyst, CuIBr, reversibly absorbs this halogen, forming a polymer of free radicals (P *) . The balance achieved between inert polymers and free radicals of active polymers strongly favors the left side. The balance achieved between inert polymers and free radicals of active polymers strongly favors the left side (K << 10-8). Equation (2) is the standard free radical propagation reaction between a polymer of lengthi and a monomer M. The small free radical concentration guaranteed by equation (1) eliminates termination reactions, and the halogen functionality is retained in the polymers produced, the which allows the production of block copolymers from almost any conventional free radical polymerization monomer.
[00077] The ATRP polymerization reaction begins with initiation. Initiation is carried out by adding a decomposing agent capable of forming free radicals; the fragment of decomposed free radicals from the initiator attacks a monomer generating a monomer free radical, and finally produces an intermediate polymerization capacity by propagation. These agents are often referred to as "initiators". Initiation is usually based on the formation of reversible growth radicals in a redox reaction between the various transition metal compounds and an initiator. Adequate initiators depend largely on details of the polymerization, including the types of monomers to be used, the type of catalyst system, the solvent system and the reaction conditions. Simple organic halides are typically used as model halogen atom transfer initiators.
[00078] For the polymerization of plant oil blocks, the initiators can be compounds that have a structural similarity to the polystyrene repeating unit. Exemplary initiators are aralkyl or aryl halide halides, such as benzyl bromide or benzyl chloride. Similar initiators can also be used for the polymerization of the PA block, such as the vinilaromatic block. In addition, for vinyl-aromatic blocks such as styrene, thermal self-initiation may occur without the need for additional initiators.
[00079] In ATRP, the introduction of a catalyst system for the reaction medium is necessary to establish the balance between active states (free radicals of polymeric agents for the growth of the polymer) and dormant states (the polymer formed). The catalyst is typically a transition metal compound capable of participating in a redox cycle with the initiator and the polymer chain. The transition metal compound used here is a transition metal halide. Any transition metal that can participate in a redox cycle with the initiator and polymer chain, but does not form a direct connection of C-metal with the polymer chain, is suitable in the present invention. The exemplary transition metal includes Cu1 +, Cu2 +, Fe2 +, Fe3 +, Ru2 +, Ru3 +, Ru4 +, Ru5 +, Ru6 +, Cr2 +, Cr3 +, Mo0, Mo +, Mo2 +, Mo3 +, W2 +, W3 +, Mn3 +, Mn4 +, Rh +, Rh2 +, Rh3 +, Rh4 +, Re2 +, Re3 +, Re4 +, Co +, Co2 +, Co3 +, V2 +, V3 +, V4 +, V5 +, Zn +, Zn2 +, Au +, Au2 +, Au3 +, Hg +, Hg2 +, Pd0, Pd +, Pd2 +, Pt0, Pt +, Pt +, Pt4 +, Ir0, Ir +, Ir2 +, Ir3 +, Ir4 +, Os2 +, Os3 +, Os 4+, Nb2 +, Nb3 +, Nb4 +, Nb5 +, Ta3 +, Ta4 +, Ta5 +, Ni0, Ni +, Ni2 +, Ni3 +, Nd0, Nd +, Nd2, Ag +, and Ag2 +. A typical transition metal catalyst system used here is CuCl / CuCl2.
[00080] The binder serves to coordinate with the transition metal compound so that the direct bonds between the transition metal and growing polymer radicals are not formed, and the formed polymers are isolated. The linker can be any one of N-, O-, P- or S-, containing the compound that coordinates with the transition metal to form a bond to, any compound that contains C, which coordinates with the transition metal to form a π bond, or any compound containing C, which coordinates with the transition metal to form an α-transition metal-C bond, but does not form a CC bond with osmonomers according to the polymerization conditions. A typical ligand used here is pentamethyldiethylene triamine (PMDETA).
[00081] The state of the art of ATRP was reviewed by Matyjaszewski (Matyjaszewski et al., "Atom Transfer Radical Polymerization," Chemical Reviews 101: 2921-2990 (2001),). More details for the selection of the initiators, catalyst / binder system for the ATRP reaction can be found in US Patent 5,763,548 for Matyjaszewski et al. and US Patent 6,538,091 to Matyjaszewski et al., which are incorporated herein by reference in their totality.
[00082] Some of the modalities of the present invention refer to the methods for preparing a copolymer in thermoplastic clusters containing a radically polymerizable monomer polymer block and a radically polymerized plant oil polymer block that contains one or more polyglycerides, according to the above steps. The radically polymerizable monomers used in the present method include, among others, a vinyl, acrylic, diolefin, nitrile, dinitrile, acrylonitrile monomer, and mixtures thereof. Radically polymerizable monomers used in this method are styrene, α-methylstyrene, t-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, divinylbenzeni, methyl acrylate, C1-C6 (methyl) acrylate (ie, methyl, methylate) butyl acrylate, (meth) heptyl acrylate, or (meth) hexyl acrylate), acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, or mixtures thereof. In a modality, the polymerised vinyl monomer is a vinyl-aromatic monomer, for example, a polystyrene homopolymer. In a modality, the polymerized plant oil is poly (soy oil). An exemplary scheme illustrating the preparation of biopolymeric elastomer -ostermoplastics from conjugated soybean oil and styrene via ATRP is shown in Figure 1.
[00083] Thus, in one modality, the present invention relates to the methods for preparing a thermoplastic and elastomeric copolymer with a copolymer architecture of soybean (styrene-oil) (PS-PSBO) or a polymer architecture of soybean-styrene-PS-styrene-oil-styrene-soy-oil-styrene-soy-oil-styrene-soy-oil-styrene-soya-styrene -PS), through the ATRP reaction. The method comprises the following steps: a) Styrene homopolymer (PS) ATRP, to achieve a molecular weight of 1 to 300 kDa, or 10 to 30 kDa, optionally followed by purification; b) SBO or CSBO ATRP using PS as a macroinitiator, in a solvent suitable for the mutual dissolution of PS and polySBOoupoliCSBO, to generate the PS-PSBO or PS-PCSBO di-block copolymer having a molecular weight of 5 to 500 kDa, 15 at 300 kDa, 40 to 100 kDa, or from 80 to 100 kDa; and c) optionally ATRP of styrene-using PS-PSBO or PS-PCSBO as the macroinitiator, to originate polymer block PS-PSBO-PS or PS-PCSBO-PS having a molecular weight of 7 to 1000 KDa, 7 to 500 kDa, 15 to 350 kDa, 80 to 120 kDa or 100 to 120 kDa.
[00084] Alternatively, the present invention method can comprise the following steps: a) SBO or CSBO ATRP to achieve a molecular weight of 1 to 300 kDa, or 10 to 30 kDa, optionally followed by purification; b) ATRP of the styrene homopolymer (PS), using PSBO or PCSBO as a macroinitiator, in a solvent suitable for the mutual dissolution of PS and PSBO or PCSBO, to generate the PS-PSBO or PS-PCSBO di-block copolymer having a weight molecular from 5 to 500 kDa, 15 to 300 kDa, 40 to 100 kDa, or from 80 to 100 kDa; and c) optionally styrene ATRP to the end of PSBO or PCSBO using PS-PSBO or PS-PCSBO as the initiator, to originate PS-PSBO-PS or PS-PCSBO-PS polymer block having a molecular weight of 7 to 1000 KDa, 7 to 500 kDa , 15 to 350 kDa, 80 to 120 kDaor 100 to 120 kDa.
[00085] A typical plant oil used together according to the method of the present invention is acrylated epoxidated plant oil, such as acrylated epoxidated soybean oil, which contains an acrylated epoxidated and polyglyceride.
[00086] In ATRP of styrene and soybean oil to prepare the thermoplastic elastomer, polymerization can be carried out at a temperature of 120 ° C or less. The ideal temperature is the minimum that the polymerization can occur in reasonable time scales, for example, 6-48 hours. In SBO or CSBO ATRP to prepare PSO- or PCSBO-based thermoplastic elastomer, 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 block polystyrene. Thus, elevated reaction temperatures with conventional radical polymerizations are undesirable in the SBO or CSBO ATRP. Typical reaction temperature for styrene and soybean oil ATRP is 100 ° C or lower, for example, from 60 ° C to 100 ° C, or from 65 ° C to 85 ° C.
[00087] Benzyl bromide or benzyl chloride can be used as a styrene ATRP and soybean oil initiator. CuX (X = Br or Cl) can be used as the catalyst system and PMDETA can be used as the binder. Typically, a 1: 1 molar ratio of CuIX: PX is sufficient to establish the balance between the active and inactive states of the resulting polymers. CuX2 can be used as a counter-catalyst to reduce the concentration of polymer free radical. Typically, a 0.1: 1 molar ratio of counter-catalyst; and a catalyst molar ratio of 1: 1 of binder: (catalyst + counter-catalyst) are desirable to ensure solvation of the catalyst. The molecular weight of the resulting polymer is governed, in part, through the monomer: initiator molar ratio, which can vary between 5: 1 and 1000: 1.
[00088] Solvent is selected based on the requirements for solubilization of polypropylene / polystyrene and a normal boiling point compatible with the polymerization temperature. The solvent used in the ATRP of styrene and soybean oil can be toluene, THF, chloroform, cyclohexane, or a mixture thereof. Solvent type used for ATRP of styrene and soybean oil is toluene. Concentrations of monomers in reactions depend partly on the solubility of the monomer and the polymer products, as well as the evaporation temperature of the solvent. The concentration of the monomers dissolved in the solvent in the ATRP reactions can vary from 5% to 100% of monomer in weight percentage. Typically, a monomer concentration of less than 50%, in mass, is appropriate to ensure the solubility of the resulting polymers and, in addition, to prevent premature gelation.
[00089] In a modality, the method is carried out in the presence of a solvent, without a counter-catalyst. Polymerization can be carried out at a temperature ranging from 65 to 100 ° C. The concentration of the solvent can vary from 10% to 40% by weight ratio between the solvent to monomer B. For example, the concentration of the solvent can vary from 10% to 25% by weight ratio of the solvent to monomer B when polymerization is carried out at 100 ° C. ° C; the concentration of the solvent can vary from 15% to 35% when the polymerization is carried out at 85 ° C; and the solvent concentration can vary from 25% to 40% when the polymerization is carried out at 65 ° C.
[00090] In a modality, the method is carried out in the presence of a counter-catalyst and a solvent. Polymerization can be carried out at a temperature ranging from 65 to 100 ° C, for example, at a temperature ranging from 65 to 85 ° C. The solvent concentration can vary from 15% to 60% by mass ratio between the solvent and monomer B. The solvent concentration can range from 15% to 60% by mass ratio of the solvent to the monomer B. For example, the concentration of solvent can vary from 15% to 25%, when the polymerization is carried out at 100 ° C; the solvent concentration can vary from 20% to 40% when the polymerization is carried out at 85 ° C; and the solvent concentration can vary from 35% to 60% when the polymerization is carried out at 65 ° C.
[00091] After radical polymerization, the copolymer e, based on soaped-oil oil, can still be catalytically hydrogenated to partially or fully saturate the plant oil block. This process removes the reactive unsaturation of the elastic component, providing a greater resistance to oxidation degradation, reduced crosslinkability and increased resistance to the chemical attack. In addition, hydrogenation prevents gelling and subsequent blocking conditions.
[00092] Other aspects of the present invention refer to the use of block copolymers based on polymerized plant oil in a variety of applications. The advantage of using the polymeric materials of the present invention is multifaceted. The block polymers of the present invention are based on plant oils, such as soybean oil. Polymerized soybean oil is intrinsically biodegradable and the raw material is produced through a carbon-negative process (ie, growing soybeans). Thus, these polymeric materials are attractive from an environmental / biorenewable perspective. In addition, the elastomeric properties of the soybean oil polymer 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 raw materials derived from petrochemicals). In addition, with the appropriate modification of soy oil (such as the conjugation of triglycerides, or the development of types of soy oil, which are particularly suitable for polymerization), the thermal chemical properties, microstructure and morphology and mechanical / rheological behavior of polymers based on oil soybeans can be improved and refined to generate highly useful polymers in the plastics industry.
[00093] Examples of applications for the block copolymers of the present invention include their use: as rubbers or elastomers; with hardened modified thermoplastics; asphalt modifiers; with resin modifiers; as modified resins; with leather and cement modifiers; shoes, such as rubber shoe heels, rubber shoe soles; automobiles, such as tires, hoses, feed belts, conveyor belts, printing rollers, rubber squeezers, car mats, truck fenders, ball mill linings, and weather strips; as adhesives, as pressure-sensitive adhesives; in aerospace equipment; withimprovements of the viscosity index; commodity detergents; as diagnostic and support agents, therefore; as dispersing agents; as emulsifying agents; comolubrificantes and / oragentestensivos; as paper additives and coating agents; and in packaging, such as food and beverage packaging materials.
[00094] In some modalities, the polymers in oil-based polymerized plants of the present invention can be used as a main component of a thermoplastic elastomer composition, to improve the thermoplastic and elastic properties of the composition. To form an elastomeric composition, the embedded copolymer can still be vulcanized, cross-linked, compatibilized, and / or combined with one or more other materials, such as other elastomers, additives, modifiers and / or filler. The resulting elastomer can be used as a rubber composition in various industries, such as shoes, automobiles, packaging, etc.
[00095] In a modality, the polymer polymers based on the polymerized plant oil of the present invention can be used in an automobile, such as vehicle tires, hoses, power belts, conveyor belts, printing rollers, rubber squeezers, automotive carpet, truck covers, ball mill coverings. , and time strips. Embedded polymers can serve as a major component in a thermoplastic elastomer composition to improve the thermoplastic and elastic properties of compositions (eg automobiles, vehicle tires). The resulting compositions can be further vulcanized, cross-linked, compatibilized, and / or combined with one or more other materials, such as other elastomers, additives, modifiers and / or filler.
[00096] In a modality, the polymer polymers based on the polymerized plant oil 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 low and varied range of copolymer in bulk. For example, the asphalt composition comprises 1 to 5% by weight of the embedding copolymer.
[00097] In a modality, the polymer polymers based on polymerized plant oil can be used in an adhesive composition. The adhesive composition may also comprise an adhesion agent and / or a plasticizer.
[00098] In a modality, oscopolymers based on polymerized plant oil can be used in a thermoplastic composition. The engineering thermoplastic composition with typical toughness comprises predominantly a vitreous or semi-crystalline component with a minority of rubber or elastomer component to increase the toughness (reduce brittleness) of the material, for example, high impact polystyrene analog (HIPS). To form a tenaciously engineered thermoplastic composition, the copolymer in the present invention can be formulated in such a way that the plant oil block is a major component and serves to absorb the energy that could otherwise lead to fracture of the solid matrix. The copolymer embedded in a tough engineering thermoplastic composition can be combined with other materials, such as other modified thermoplastics, additives, modifiers, or fillers.
[00099] Another aspect of the present invention relates to a thermoplastic polymer comprising one or more units of a radically polymerizable monomer of plant oil containing one or more polyglycerides. All of the above-described modalities for the PB block, such as physical and chemical compositions, structures and properties (eg molecular weight, transition temperature, etc.) are suitable for polymerizable plant-based polymer polymers.
[000100] Another aspect of the present invention relates to a method for preparing a block of polymer or thermoplastic polymer. The method comprises providing a radically polymerizable monomer of plant oil that contains an origlyceride. This plant oil monomer is then polymerized, in the presence of an initiator and a transition metal catalyst system to form the thermoplastic polymer or polymer assembly. This proper thermoplastic polymer can be used as a thermoplastic elastomer. Alternatively, this thermoplastic polymer can be used as a polymer block, and can be further polymerized with other monomers to form a thermoplastic copolymer based on polymerized plant oil. All of the modalities described above for the PB block preparation methods, including the reaction steps and reaction conditions (for example, reaction reagents, the catalyst system, the initiators, the temperature, the solvent, the initiation, reaction determination, etc.), are suitable. for the production of polymer polymer-based polymeric plant-based polymers.
[000101] All of the above described for the applications of polymerised plant-based copolymer based on polymerized plant oil are also suitable for the application of polymer oils based on plant oils.
[000102] Examples of processes for the synthesis of poly (conjugated soy oil) (PCSBO) by means of ATRP and mixing polymers in clusters with asphalts are discussed in the following paragraphs.
[000103] In a modality, PCSBO is synthesized through ATRP.
[000104] Conjugated soybean oil (CSBO) is polymerized in a reproducible way through the ATRP mechanism. A typical CSOY mass polymerization procedure is described as follows. The CSBO is degassed and placed under a pressure gauge. Benzyl bromide or benzyl chloride, due to its structural similarity to the polystyrene repeat unit, is used as the initiator. A copperCuX catalyst and CuX2 counter-catalyst system is used with PMDETA (pentamethyldiethylenetriamine) as a bonding agent. Detailed procedures for preparing conjugated soy oil can be found in the literature (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 Polylactide with Polymerized Soybean Oil, "Macromolecules 43: 1807-1814 (2010); 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 are incorporated by reference in its totality).
[000105] ATRP experiments can be performed by varying the following parameters. Temperature
[000106] Conventional free radical polymerization (CFRP) of CSBO has been evaluated at temperatures ranging from 60-150 ° C. In CFRP, the dependence of the temperature kinetics of polymerization is dominated by the reaction of decomposition of the initiator. The disadvantage of high temperature is a higher polymerization rate with a lower molecular weight and increased chain transfer reactions. Increasing chain transfer reactions is desirable in the production of thermosetting, where polySBOeventually gelates and solidifies as the chains begin to crosslink (Valverde et al., "Conjugated Low-Saturation Soybean Oil Thermosets: Free-Radical Copolymerization with Dicyclopentadiene and Divinylbiedene, Journal" Polymer Science 107: 423-430 (2008); Robertson et al., "Toughening of Polylactide with Polymerized Soybean Oil," Macromolecules 43: 1807-1814 (2010), which are here incorporated by reference in their totality).
[000107] For the method for preparing CSBO-based plastics, the ideal temperature is the minimum at which polymerization can occur over a reasonable time scale, for example, 648 hours. In contrast to conventional free radical polymerization, the main function of the ATRP reaction temperature is to shift the balance towards a greater concentration of free radicals and to increase the rate of propagation. These are desirable for a certain extension; however, as the concentration of free radicals increases, so does the speed of termination and transfer reactions. In CSBO ATRP to prepare PCSBO-based plastics, it is desirable to produce PCSBO with a high molecular weight and low glass transition temperature (Tg), and with the retention of the terminal halogen, which allows the later addition of a polystyrene block. Thus, increasing the rate of termination and transfer of reactions (ie, the high reaction temperature) is undesirable in CSBO ATRP. Halogen
[000108] Halogen atoms are reversibly transferred between the transition metal catalyst system and the ATRP initiator. Both Br and Cl are used for the halogen system. Br systems tend to shift the balance of the ATRP reaction to the left (ladolatent) side of the equation (see, for example, equations (1) and (2) in paragraph [0073]) in comparison to Cl systems. This variable allows flexibility and independently adjusts the speed of propagation (for example, by adjusting the reaction temperature) and the concentration of free radicals. Catalyst Composition and Concentration
[000109] In ATRP, the introduction of CuIXa reaction medium is required to establish the balance between the active and inactive states. Typically, a 1: 1 molar ratio of CuIX: PX is sufficient to establish this balance (Matyjaszewski et al., "Atom Transfer Radical Polymerization," Chemical Reviews 101: 2921-2990 (2001),). In some systems, equilibrium is very far to the right and polymerization is not controlled unless the counter-catalyst, CuIIX2, is introduced to control equilibrium, which is independent of the reaction temperature (Behling et al., "Influence of Graft Density on Kinetics of Surface-Initiated ATRP of Polystyrene from Montmorillonite, "Macromolecules 42: 1867-1872 (2009); Behling et al.," Heirarchically Ordered Montorillonite Block Copolymer Brushes, "Macromolecules, 43 (5): 2111-2114 (2010), which are incorporated here by reference to its totality). Solvent
[000110] Bulk polymerization is the starting point as we directly resolve and place limits at the polymerization temperature and also influence the ATRP balance. The synthesis of polySBO from a polystyrene macroinitiator requires a solvent. Solvent is selected based on the requirements for solubilization of polypropylene / polystyrene and a normal boiling point compatible with the polymerization temperature.
[000111] Reactions are left for 12 hours, and gel permeation chromatography is used to assess the degree of polymerization. The polymerization kinetics is subsequently evaluated and the parameters are improved in such a way that the polySpost posts can be produced in a reproducible way with minimal polydispersity and of target molecular weight. Differential scanning calorimetry is used to evaluate the Tg of polySBO materials, which is 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 Polylactide with Polymerized Soybean Oil," Macromolecules 43: 1807-1814 (2010), which are here incorporated by reference in their totality).
[000112] In a modality, the poly (styrene-block-SBO-block-styrene) (PS-PSBO-PS) is synthesized by means of ATRP.
[000113] Extensive experimentation with the synthesis of copolymers embedded in styrene via ATRP can be useful for the synthesis of PS-PSBO-PS (Behling et al., "Influence of Graft Density on Kinetics of Surface-Initiated ATRP of Polystyrene from Montmorillonite," Macromolecules 42 : 1867-1872 (2009); Behling et al., "Heirarchically Ordered Montorillonite Block Copolymer Brushes," Macromolecules, 43 (5): 2111-2114 (2010), which are here incorporated by reference in their totality).
[000114] The production of three-block copolymers corresponds to a three-step process: 1) ATRP of the styrene homopolymer (PS), to reach a molecular weight of 10 to 30 kDa, followed by purification; 2) ATRP of SBO or CSBO using PS as a macroinitiator, in a solvent suitable for the mutual dissolution of PS and polySBOoupoliCSBOor the reaction temperature determined in the above mode, to generate PS-PSBO or PS-PCSBO; and 3) ATRP of styreneusing PS-PSBO or PS-PCSBO as a macroinitiator, to generate PS-PSBO-PS or PS-PCSBO-PS.
[000115] The resulting PS-PSBO-PS or PS-PCSBO-PS polymer can contain ~ 25% by weight of polystyrene and is in the order of 100 kDa.
[000116] In one modality, the PS-PSBO-PS polymers of the above quality are mixed with asphalt binders.
[000117] As the structure-property relationships for the PS-PSBO-PS system are constructed, compositions and molecular weight ranges that should be more suitable with bitumen modifiers can be identified from the above modality.
[000118] For the three PS-PSBO-PS polymer compositions, they are scaled up to a range of 200 g for further testing with bitumen modifiers.
[000119] The developed biopolymers are mixed with two asphalt for further testing. The phthalitic binders used are derived from raw sources in Canada and Texas as are commonly used in the United States. The phtaltic binders have a performance grade of PG58-28 or PG64-22 as these are the most common steps used for subsequent polymer modification. Osbiopolymers are mixed at 1%, 2% and 4% by weight of the combined phallic ligand. A styrene-butadiene-type polymer is used as a reference point polymer for subsequent technical-economic analysis. The mixture and subsequent rheological test are described in Figure 2 and follow the American Association of State Highway and Transportation Officials (AASHTO) test M 320 to determine the degree of a spherical ligand (AASHTO M 320: Standard Specification for Performance-graded Asphalt Binder. and Transportation Officials, Washington, DC (2002), which is incorporated by reference into its totality)
[000120] Frequency scans are performed on a dynamic shear rheometer (DSR) and rotational viscometer (VR) at various temperatures. Bending beam rheometer tests are performed at various temperatures. A thin film laminating oven (RTFO) and pressure aging vessel (PAV) are used to perform the simulated aging of binder mixtures that represent the aging of binders that occurred during the production of asphalt mixtures and aging in situ, respectively.
[000121] These tests allow the understanding of the effects of the polymer content, effects of the oil source, and the behavior of the mixtures developed. Prior to testing, separation tests are carried out to assess the ability of polymers without meeting the standards of the American Society for Testing and Materials (ASTM) standards for maintaining homogeneity, ASTM D7173 using a rotational viscosimeter (ASTM Standard C33: Standard Practice for Determining the Separation Tendency of Polymer from Polymer Modified Asphalt, ASTM International, West Conshohocken, PA (2003),). Each test is performed in triplicate in the same mixes, which allows analysis of variance (ANOVA) and subsequent regression analysis.
[000122] Statistical analysis of the data is performed using the physical data of the biopolymers and the rheological and chemical properties. The analysis also includes ANOVA to identify the independent variables that are significant, for example, which variables effect the shear modulus of the ligands derived from DSR tests. Once the significant variables are identified, the regression analysis can be performed using the significant variables to identify the interactions between the variables and understand their magnitude / effects relationship on the dependent variable. Additional data analysis includes the development of master ligand curves to compare the rheological properties of the ligands over a range of temperatures. EXAMPLES
[000123] 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 (Epoxidized Soybean OilAcrylated-block-styrene) (PAESO-PS) via Radical Transfer Polymerization Atom
[000124] Benzyl chloride (BCl), copper (II) chloride (CuIICl2), and N, N, N ', N' ', N' '- pentamethyldiethylene triamine (PMDETA) were purchased from Aldrich Chemical and used without additional purification. Copper (I) chloride (CuICl) was purchased from Aldrich Chemical and purified with acetic acid. Epoxidatedacrylated soybean oil (AESO) was purchased from Fisher Scientific, dissolved in high-efficiency liquid chromatography (HPLC) grade tetrahydrofuran (THF) and purified on basic alumina and inhibitor removers (Aldrich product No. 311332). Before being used, THF in AESO was removed by means of rotary evaporation and the AESO gasified monomer used by using three freeze-pump-thaw cycles. HPLC grade toluene was purchased from Fisher Scientific, purified on basic alumina, and degassed before use. The styrene was purchased from Fisher Scientific and purified by three freeze-pump-thaw cycles followed by shaking overredibutylmagnesium and subsequent vacuum distillation. Radical Atom Transfer Polymerization (ATRP) of acrylated and epoxidized soybean oil
[000125] ATRP synthesis was carried out in a similar way to the processes described in Mathjaszewski et al., "Controlled /" Living "Radical Polymerization. Kinetics of the Homogeneous Atom Transfer Radical Polymerization of Styrene," Journal of the American Chemical Society 119 (4): 674-680 ( 1997),. The AESO monomer, the initiator (BCI), the catalyst (CuCl), the binder (PMDETA), and the solvent were mixed under an argon atmosphere, in a round-bottom flask, with the following proportions of the various components: several monomer mass proportions: solvents; 100: 1 molar ratio of monomer: initiator; a 1: 1 molar ratio of initiator (BCI) to catalyst (CuCl), a 1: 1 molar ratio of binder (PMDETA) to catalyst, and a 0.1: 1 molar ratio of counter-catalyst (CuCl2) to catalyst. Reaction kinetics
[000126] Experiments were carried out to find a better solvent system for the polymerization reaction, evaluated by factors such as ease of purification, ease of removal of the solvent from the final polymer, solubility of the final polymer of the solvent, and the influence of the solvent on the kinetics of the solvent. reaction. Chloroform, THF, and toluene have been studied as solvents. Toluene proved to be a better solvent candidate than other solvents for its higher evaporation temperature and better polymer solubility with the product.
[000127] Experiments were also carried out to investigate the kinetics of the reaction (ie, the conversion of monomer into polymer as a function of time), with all reaction conditions fixed except for the temperature and the monomer ratio for the solvent. Kinetics studies evaluated all combinations of three temperatures (65 ° C, 85 ° C and 100 ° C) and six monomer concentrations ranging from 50 to 100 weight percent monomer. The molecular weight distribution of each polymer product, poly (epoxidatedacrylated soybean oil) (PAESO), was determined by size exclusion chromatography (seeFigure 3). The reactions that did not reach the gel point were closed by deactivating the reaction system until the ambient temperature, after 72 hours. PAESO was dissolved in THF, passed through basic alumina, and then precipitated in 1:10 volumetric ratio of water to methanol. The precipitate was dried in a vacuum oven at room temperature to obtain a constant mass. To further characterize the degree of polymerization of AESO, nuclear magnetic resonance (NMR) was carried out with the dry samples (see Figure 4). Synthesis of P (AESO-B-Styrene)
[000128] In a 100 ml round-bottom flask, 10 g of styrene was mixed with 20 g of PAESO which was dissolved in 20 g of THF and 2.5 g of toluene. THF was removed by evaporation at the beginning of the polymerization reaction. CuCl, PMDETA, and BCI were all added, with the same proportion of reagent-monomer according to the same procedure as in the AESO polymerization discussed above. The reaction proceeded for 72 hours at 100 ° C, with moderate agitation. After the reaction is finished, the polymer product is filtered through an alumina column to remove the catalyst. The solution was not used several times in 1:10 proportion from water to methanol. . The polymer is collected and dried at room temperature under vacuum. 1H NMR was performed to prove the presence of polystyrene in the product (see Figure 5). Differential scanning calorimetry (DSC) of PAESO and PAESO-PS
[000129] DSC was performed to measure the glass transition temperatures (Tg) of the polymers. PAESO and PAESO-PS were each characterized by DSC to find Tg. Figure 6 shows the DSC graph for the PAESO sample at 240 minutes, where two different glass transitions are visible. Figure 7 shows the DSC graph for the PAESO-PS di-block after 72 hours, the glass transition to the PAESO block is visible, but no definite glass transition was observed during the polystyrene block.
[000130] The PASEO-PS complex-dynamic module was designed using an advanced rheometric expansion system (ARES), re-controlled by deformation in the parallel silver configuration. The results are shown in Figure 8. Isothermal frequency sweeps with a frequency range were performed within the linear viscoelastic regime, using a 2.5% formation. The initial temperature was adjusted to 150 ° C and the final temperature was adjusted to 25 ° C. The temperature changed in a decrease of 10 ° C allowing 1 minute as the equilibration time. The elastic modulus G ', is almost variable at the frequency and temperature above 80 ° C, a characteristic of elastic solids. Example 2 - General synthesis procedures for preparing poly (acrylated epoxidized soybean oil) (PAESO) through radical polymerization by atom transfer
[000131] 10 g of AESO (CAS # 91722-14-4) and 20 g of HPLC-grade THF were mixed and passed through a chromatography column filled with basic alumina and inhibitor removers (Sigma Aldrich product No. 311332). THF was moved using rotary evaporation. AESO was subjected to three "freeze-pump-thaw" cycles. In each cycle, the AESO was frozen under vacuum or nitrogen liquid in a vacuum flask and allowed to thaw. This process removes any dissolved gases. 10 g of toluenograu HPLC was gasified in the same way. 10 g of AESO and 10 g of toluene in addition are added to a 50 ml bottle of rounded bottom in a glove box filled with argon. When mixing 16.9 mg of BCl (50: 1 molar ratio of monomer to AESO initiator), 13.2 mg CuICl (1: 1 molar ratio of initiator to catalyst), 23 mg of PMDETA (1: 1 molar ratio of binder for catalyst), and 1.8 mg CuIICl2 (10: 1 molar ratio of catalyst to counter-catalyst) were added before the bottle was sealed. The mixture was immersed in a silicone oil bath with temperature control at 100 ° C for 12 hours, and then stopped at room temperature. The resulting PAESO was recovered from the solution by precipitation in 200 ml of 10 ° C methanol. Additional dissolution-precipitation cycles were conducted to further purify the product to remove residual AESO and catalyst.
[000132] The final product had a yield of 1.6 g PAESO. Size exclusion chromatography (SEC) indicated a bimodal distribution with Mn, 1 = 21.8 kDa, PDI1 = 1.047, and Mn, 2 = 91.6 kDa, PDI2 = 1.11. See SEC results in Figure 9.Example 3 - General synthesis procedures for preparing poly (styrene-block-soybean oil epoxidated-acrylate-block-styrene) (PS-PAESO-PS) via radical polymerization by atom transfer
[000133] 10 g of styrene (Sigma-Aldrich) was subjected to three "freeze-pump-thaw" cycles, followed by stirring for 10 mmol of dibutylmagnesium and subsequent by vacuum distillation. The styrofoam is then polymerized using ATRP using the benzyl chloride / CuCl / PMDETA system following the procedures described in the literature (Matyjaszewski et al., "Controlled /" Living "Radical Polymerization. Society 119 (4): 674-680 (1997),). The product showed a yield of 8.3g PS-Cl, and was characterized by SEC having Mn, S = 24.7 kDa and PDIs = 1.057. See Figure 10.
[000134] A catalyst / binder solution was prepared by adding 1.35 g of CuICl and 1.73 g PMDETA to a 100 ml volumetric flask, followed by adding toluene degassed to an HPLC, producing a concentration of the 0.1 M catalyst / binder solution The final concentration of the 10 M catalyst binder solution was determined by sequential 10-day dilution of the 0.1 M solution with toluene. A similar procedure was used to prepare a 1M CuIICl2 counter-catalyst solution. The PS-CI macroinitiator was purified by means of three precipitation solvation cycles (using a 3: 1 volumetric ratio of methanol for propanol as the precipitating agent), and was dried until constantly at room temperature under vacuum. 0.25 g of purified PS-CI (0.01 mmol), 0.1 ml of catalyst solution, 0.1 ml of counter-catalyst solution, 10 g of AESO (prepared as in Example 2), and 10 g of degassed toluene and HPLC were mixed under an argon atmosphere, in a round-bottomed flask and heated at 100 ° C for 12 hours using a controlled temperature oil bath. The resulting PS-PASEO-CI was recovered by precipitation in a 3: 1 volumetric mixture of methanoleisopropanol, purified by subsequent solvation-precipitation cycles, and dried to constant under vacuum. The product had a yield of 1.79 g of PS-PAESO-CI, and was characterized by SEC to have Mn = 168kDa and PDI = 1:04. See Figure 10.
[000135] The final PS block was added to PS-PAESO as follows. 1.5 g of purified PS-PASEO-CI, 0.1 ml of catalyst solution, 0.1 ml of counter-catalyst solution, 0.25 g of purified styrene, and 3 g of toluene-dramatically added to a round bottom flask, under argon and sealed atmosphere. The flask was heated at 100 ° C for 6 hours and then extinguished at room temperature. PS-PAESO-PS was recovered and purified through three sequential solvation-precipitation cycles. The final product had a yield of 1.68 g of PS-PAESO-PS, and was characterized by SEC to have Mn = 193 kDa, PDI = 1: 063. See Figure 10. The final styrene composition in PS-PAESO-PS was 33.7% by weight per 1H-NMR. Example 4 - Evaluating the Effects of a Bio-elastomerMixed with an asphalt binder
[000136] An experimental plan has been developed for evaluating the effects of a developed bio-elastomer (copolymer based on plant oil) that is mixed with a phthalant ligand and comparing this standard with standard asphalt. The base asphalt had a performance grade (PG) 52-34 as determined by the American Association of State Highway and Transportation Officials (AASHTO) specification M-320 and was supplied by a regional asphalt supplier. The two conventional elastomers selected to mix with the PG52-34 binder were Kraton 1101 and Kraton 1118 since both are used with the asphalt binder provided for the modification. Mixing of elastomers in the PG52-34 phthalic binder was carried out using a Silverson L4RT-A laboratory shear mill in room-sized stainless steel containers for 90-150 minutes at 3000 rpm, using the J-KEM Scientific temperature probe for 170 ° C digital temperature control in a blanket of heating. The elastomers were mixed at 1, 2, 3, 4, and 5% by weight of the total binder mixture, resulting in about 280 g of each mixture samples for the subsequent test.
[000137] The dynamic shear rheometer test of the non-aged thin film laminating furnace (RTFOT), and RTFOT and pressure aging vessel (PAV) were carried out at various temperatures to determine the shear modulus (G *), phase angle (δ), and the combined effects - G * / sinδ) on the non-aged and aged RTFOT G ^ sinδ on the RTFOT and aged PAV - of the various mixtures. Mass loss determination was also performed in samples that were submitted to RTFOT aging. Beam-bending rheometer test at various temperatures was performed on aged RTFOT and PAV mixtures resulting in rigidity (S) and m-value to be determined for the mixtures. The tests were carried out in each mixture in triplicate.
[000138] Statistical assumptions were used to determine if there were statistical differences in the test results for the three different elastomers, as well as the percentage of each elastomer added to the PG52-34 spherical link.
[000139] An example of the hypotheses to be tested among the three different elastomers is as follows: Ho: G *, 1% Kraton 1101 at 64 ° C = G *, 1% Bio-elastomer at 64 ° CHa: G *, 1% Kraton 1101 at 64 ° C # G *, 1% Bio-elastomer at 64 ° C.
[000140] An example of the assumptions that assess the existence of no differences at various levels of elastomer content: Ho: G *, 1% Bio-elastomer at 64 ° C = G *, 2% Bio-elastomer at 64 ° C Ha: G *, 1% bio-elastomer at 64 ° C # G *, 2% bio-elastomer at 64 ° C. Example 5 - Determine the gel point for AESO polymerization
[000141] The AESO monomer synthesized in Examples 2-4 contains 1-3 polymerizable fractions. The polymerization of these fractions to form PAESO can produce polymers with a certain degree of branching. Conventional free radical polymerization does not offer any way by which the degree of branching can be controlled. Thus, thermosetting are the only products that can be anticipated by conventional free radical polymerization. Controlled free radical polymerization chemistry, such as ATRP, however, offers the ability to limit the extent of polymerization in such a way that the branching is attenuated to a level below the gelation point. Thus, the polymers resulting from the polymerization of controlled free radicals (for example, by ATRP) are thermoplastic. It is, therefore, important to control the reaction conditions, such as gel point limiting conditions, for the production of copolymers in thermoplastics. PAESO is produced in this example to show the different reaction conditions in relation to the gelation point.
[000142] Consequently, experiments were carried out to test gelation times for a set of concentrations of initiator and catalyst (ie, benzyl chloride and CuICl), see Table 2. Experiments were carried out to understand the effect of the solvent, counter-catalyst, and temperature of PAESO . 5 g of purified AESO, 6 μgCuiCI, and 7 μg of B were added to each of the 12 vials in an argon glove box. 5 g of toluene 0.8 μg CuiiCl2 were added to 6 vials in a manner that 4 sets, each containing 3 vials had combinations with / without CuiiCI2 and with / semiventible. Within each set, 1 flask was heated to 65 ° C, another to 85 ° C, and another to 100 ° C to start ATRP. Eachphrase was monitored periodically to assess whether PAESO had reached its geI point, as observed by an increase in the response risk, phase separation, or the reaction medium. Results are shown in Table 2. Table 2: gel point conditions in Example 5

"-" = gelation not available within 72 hours
[000143] It has been shown that the addition of solvent (20% by mass of solvent / monomer) and CuIICl2 in a reaction system at 65 ° C delayed polymerization to the maximum, and no gelation occurred under such condition in 72 hours. Reactions with the highest monomer percentage, without CuIICl2 at 100 ° C reached gelification within 10 hours after the reaction starts. Example 6, general synthesis procedures for preparing poly (Styrene-Block-Block AESO-Styrene) via radical polymerization by atom transfer
[000144] The poly (styrene-block-AESO-block-styrene) was synthesized using the procedure analogous to the synthesis of the homopolymers of the copolymers in di-blocsExamples 1 -3.
[000145] Styrene polypolymerized using: BCl, CuCl, PMDETA, and toluene, similarly, as described in Examples 1 and 3. The reaction continued for 48 hours at 100 ° C, the product was then dissolved in THF and passed through alumina, followed by precipitation of a mixture 3: 1 methanol to isopropanol. The resulting producer was collected and dried under vacuum at 70 ° C, and then redissolved in THF.
[000146] The above product was mixed with AESO together with CuCl, PMDETA, and toluene. THF was removed by evaporation at the beginning of the polymerization reaction. The reaction proceeded for 6 hours at 100 ° C, with moderate agitation. The solution was passed through alumina and precipitated several times in 1:10 proportion of water to methanol. The polymer is collected and dried under vacuum at room temperature.
[000147] The di-blocofoiredis dissolved again in THF (THF was removed before the polymerization started), and mixed with styrene, together with CuCl, PMDETA and toluene. The reaction proceeded for 8 hours at 100 ° C and the product did not precipitate several times in relation to 1: 10 of water to methanol, collected and dried under vacuum at room temperature. Example 7 - Molecular characterization of polymers produced in Examples 1-3 and 6
[000148] 1H NMR spectra were determined using a Varian VXR-300 spectrometer in deuterated chloroform (CDCl3) or deuterated tetrahydrofuran (d8-THF) at ambient temperature. Molecular weights and molecular weight distributions were determined using gel permeation chromatography (GPC) with respect to polystyrene patterns (chloroform HPLC as the solvent) in a Waters 717 autosampler and a Waters 515 HPLC System with a Waters refractive index detector 2414. A GPC HPLC-tetrahydrofuran was used for samples that were not soluble in chloroform.Example 8 - Modification of asphalt with thermoplastic elastomers based on PAESO
[000149] The viability of PAESO-based elastomerostermoplastics as a substitute for traditional SBS polymers used in asphaltofoidal modification has been determined. The bitumen is mixed with 1 - 5%, mass, of biopolymer based in PAESO for 3 hours at 180 ° C.
[000150] The results demonstrated that the rheology of these biopolymers, which mixed with bitumen showed a greater increase in storage and loss module G ‘and G" compared to their petroleum-based counterparts. See Figure 11. Discussion of Examples 1-8
[000151] Polymers from vegetable oils have been gaining more and more attention with public policy makers and companies are equally interested in replacing traditional and petrochemical raw materials due to their environmental and economic impact. In recent years, the cost of bio-monomer has become highly competitive (in many cases, more economical than petrochemical raw materials). With the appropriate modification of soy oil (such as the conjugation of triglycerides, or the development of types of soy oil, which are particularly suitable for polymerization), the thermal chemical properties, microstructure and morphology, and mechanical / rheological behavior of polymers based on soy oil can be tuned to make these biopolymers very useful in the plastics industry.
[000152] Until now, some success has been achieved through the application of traditional cationic and free radical polymerization pathways for vegetable oils to generate thermosetting plastics <b0 />. Pfister & Larock, Bioresource Technology 101: 6200 (2010), which has been incorporated by reference into its totality, researched a variety of polymers ranging from soft to hard rubbers, rigid plastics using the cationic polymerization of vegetable oils, mainly SBO, to produce thermo-curing agents as a thermo-curing agent. Lu et al. synthesized polyurethane films transported in water based on soy oil with different properties, varying from elastomeric polymers to hard plastics, changing the polyol functionality and the hard segment content of the polymers (Lu et al., Polymer 46:71 (2005); Lu et al., Progress in Organic Coatings 71: 336 (2011), which are incorporated by reference into their totality). Wool et al. reported the use of soybean oil for different types of bio-based products such as molding composites on sheets, elastomers, coatings, foams, etc. For example, Bunker et al. were able to synthesize pressure-sensitive adhesives using polymerization in miniemulsion of acrylatedmethyl oleate, a soy oil monoglyceride derivative (Bunker et al, International Journal of Adhesion and Adhesives 23:29 (2003); Bunker & Wool, Journal of Polymer Science Part A: Polymer Chemistry 40 : 451 (2002), which are incorporated by reference into their totality). The polymers produced were comparable with their oil experts. Zhu et al. > were able to generate an elastic network based on acrylated methylesteric ester through mass polymerization using ethylene glycol as the crosslinking agent (Zhu & Wool, Polymer 47: 8106 (2006),). Lu et al. were able to create thermosetting resins synthesized from soybean oil that can be used in applications of blade molding compounds. These resins were synthesized through the introduction of acid functionality and on soy. The acid groups reacted with the different metal oxides or hydroxides that form the slide, while the C = C groups are subject to polymerization by free radicals (Lu et al., Polymer 46:71 (2005),). Bonnaillie et al. oram able to create a thermosetting plastic foam system using a pressurized carbon dioxide foaming process from epoxidated acrylated soy oil (AESO) (Bonnaillie & Wool, Journal of Applied Polymer Science 105: 1042 (2007),). Wool et al. were able to synthesize from liquid molding resins that were able to be cured with high modulus hardenable polymer and composites that we use plant oil-derived triglycerides (US Patent 6,121,398 to Wool et al., which is incorporated by reference in its entirety by reference).
[000153] Controlled chain branching and crosslinking were preventable using the mentioned conventional technical polymerization pathways due to the multifunctional nature of triglycerides, multiple initiation sites throughout the chain structure, and chain transfer / termination reactions. Thus, each polyitriglyceride repeat unit has the potential to form reticulations with, at least, another polyitriglyceride; when about a fraction of 1 / N of such a unit has reticulations (N indicates the number of repetition units in the polymer chain), the polymers are referred to as their "gel point", in which an infinite network of formed polymer and the material is a thermosetting polymer.
[000154] Controlled radical polymerization with ATRP limits the number of initiation sites, dramatically reduces the rate of chain transfer and termination reactions, and also has the ability to produce customized chain architectures, such as cluster polymers (BCPs). An advantage of the application of ATRP for the polymerization of triglycerides is that the initiation of new chain branches from other growing chains is eliminated. However, chain branching, in the last analysis leading to gelation, is still possible, and will proceed quickly, if the polymerization speed or polymer concentration becomes very large. When propagation chain reactions towards all functional sites in both free monomers and repetition units that are already incorporated in an identical chain, the general expectation is that the gel point will be reached in an extremely low conversion, in such a way that, before de-gelation, the poly-glyceride production continues to increase. This general expectation is supported by the last two decades of thermosetting reports from vegetable oils produced by conventional cationic polymerization and free radicals.
[000155] However, in the results of Examples 1-8, for the first time, a controlled radical polymerization technique was applied to synthesize di-block-elastomer and copolymer containing polystyrene (PS) and poly (AESO) (PAESO). Surprisingly, ATRP has proven to successfully control the polymerization of AESO so that the polymerization ends in a desired molecular weight and composition composition. PAESO thermoplastic homopolymers were created from a sticky rubber with a low molecular weight in a highly elastic viscoelastic material at a high molecular weight. Di-block (PS-PAESO, PAESO-PS) and tri-block (PS-PAESO-PS) copolymers were created through a range of block compositions and molecular weights.
[000156] Without appropriate conditions, early gelation may still extend to ATRP polymerization techniques if the reactivity ratios between spreading radicals and all functional sites that did not react on the triglycerides were rigorously identical. However, in Examples 1-8, it has been demonstrated that the preference for a free monomer uptake radical can be exacerbated by the appropriate selection of temperatures, solvent / solvent concentration, and selection of the catalyst / counter-catalyst system. Under such conditions, it was possible to produce polymerized triglycerides for target molecular weights of up to 500 kDa, before the gel point.
[000157] In the examples, plant oils, such as AESO, with an average of 3.4 acrylates (Lu et al., Polymer 46:71 (2005), which is incorporated by reference into their totality), and styrene were used to form polymers in analogous assemblies, for example, PS-polybutadiene-PS (SBS) polymers of the Kraton® family. The addition of styrene helped to improve the processability, helped in the control of the melting state properties of polymers (glass transition temperature (Tg), elastic modules, etc. (RICHARD P. WOOL & XIUZHI SUSAN SUN, BIO-BASED POLYMERS AND COMPOSITES (Academic Press, Burlington, MA 2005), which is incorporated by reference into its totality), and physical cross-linking services below PS Tg (100 ° C). In a typical SBS elastomer, the styrene composition is about 10-30% by weight so to which the spherical or oscillometric domains form in a matrix of butadiene. When the temperature is below the transition temperature of the polystyrene glass (Tg = 100 ° C), the polybutadiene matrix is liquid (Tg <-90 ° C) but is connected between the polystyrene-vitreous spheres , which serves as physical binders. When the temperature is above the glass transition temperature of polystyrene, the entire elastomer system is melted and can be easily processed. a) reticulated from the port of Tgt values so low when -56 ° C (Yang et al., Journal of Polymers and the Environment 19: 189 (2011), which is incorporated by reference in its entirety). Thus, poly (soybean oil) is an excellent candidate to serve as the liquid component in the thermoplastic elastomer based on polystyrene and polystyrene.
[000158] Block oscopolymers (BCPs) containing styrene and butadiene, in particular the Kraton® (SBS) family of polymers (SBS) have been used all over the world in different application ranges: pressure-sensitive waste, tires, packaging materials, footwear, and bitumen / asphalt modifiers. , which is one of its biggest markets. With the forecast for growing asphalt-liquid during the next decade, there is a strong need for a new type of cost-effective, viable, environmentally compatible polymers that can be used as an asphalt modifier instead of standard styrene-butadien modifiers. The soybean oil-based polymers described in the examples provided viable material properties with bitumen modifiers. Example 9 - Soybean oil-based thermoplastic and polymeric block copolymers via ATRP and their characterization
[000159] ATRP synthesis was carried out in a manner analogous to the procedure described by Matyjaszewski et al, Journal of the American Chemical Society 119: 674 (1997),. See the procedures described in Examples 1-3 and 6.
[000160] Using acrylated epoxidated soybean oil (AESO) as the monomer, benzyl chloride (BCl as the initiator, copper (I) chloride (CuICl) and copper (II) chloride (CuIICl) as the catalyst and counter-catalyst, respectively, and N, N, N ', N' ', N' '- pentamethyldiethylenetriamine (PMDETA) as the binder. A 1: 1 ratio of initiator (BCl) to catalyst (CuICl), a 1: 1 ratio of binder ( PMDETA) for monomer and a 0.1: 1 molar ratio of counter-catalyst (CuCl2) for monomers were used.
[000161] Experiments were carried out to obtain a better solvent system for the polymerization reaction, evaluated by factors such as ease of purification, ease of removal of the final polymer, solubility of the final polymer in the solvent, and the influence of the solvent on the reaction kinetics . Chloroform, THF, toluene and were studied as solvents. Toluenes will be a better solvent than the other solvents due to its higher evaporation temperature and better solubility with the polymeric product.
[000162] Experiments were also carried out to investigate the kinetics of the reaction (that is, the conversion of monomer in polymer to a function of time), with all the reaction conditions fixed except for the temperature, the presence of CuIICl2, and the ratio of the monomer to solvent. Kinetics studies evaluated all combinations of three temperatures (65 ° C, 85 ° C and 100 ° C, the addition of the counter-catalyst, and six monomer concentrations ranging from 0.5 to 1.0 weight percent monomers). The reactions were allowed to proceed until the gel point was reached. The reactions that did not reach the gel point were terminated by extinction at room temperature, after 72 hours. The molecular weight distribution of each product, poly (epoxidatedacrylated soybean oil) (PAESO), was determined by size exclusion chromatography, seeFigure 12.
[000163] The results of the above experiments have provided a view on the effect of the solvent, counter-catalyst, and temperature on the gelation of PAESO. It was observed that the addition of solvent (20% solvent / monomer mix) and CuIICl2 in a reaction system at 65 ° C reduced the polymerization to the maximum, and no gelation occurred under that condition in 72 hours. Reactions with a higher percentage of monomer, without CuIICl2 at 100 ° C reachedugelification within 10 hours after the reaction starts.
[000164] The polymerization of styrene containing di-blocks and triblocos was carried out at 100 ° C. No solvent was used for the polymerization of styrene homopolymer, but the solvent was present for solvating polymers in the polymerization of di-blocks and tri-blocks. Table 3 lists some of the polymers used for characterization. Table 3. Compositions of biopolymer used for characterization.
a Total molecular weight of BCP b Polydispersity Percentage of styrene in BCPd Molecular weight of styrene in the first block and Molecular weight of styrene in the second block
[000165] 1H NMR was performed on the sample, which proved the presence of polystyrene in the product. See Figure 4.
[000166] To characterize the viscoelastic properties of biopolymers, DSC was used to find the glass transition temperatures (Tg) of the polymers. DSC experiments were carried out in a TA-Instruments Q2000 differential scanning calorimeter equipped with a liquid nitrogen cooling system (LNCS). Three consecutive heating and cooling operations were carried out for each sample (-100 ° C to 150 ° C) using standard aluminum containers and a heating / cooling speed of 10 ° C / min. PAESO showed a glass transition temperature (Tg) of -48 ° C for rubber polymers. See Figure 6.
[000167] Rheology measurements were performed on a TA Instruments AR2000ex voltage controlled rheometer, with a convection oven, used to test polymers under gaseous nitrogen flow to prevent polymer degradation. The samples were tested in a silver plated parallelogram using a temperature ramp test at a heating speed of 5 ° C and a voltage of 2%. The samples were mixed with hydroxytoluenobutylated (BHT), to avoid cross-linking of the polymer. Figure 13 is the rheology curve of the PAESO homopolymer showing a low module and the behavior of the PAESO homopolymer type at high temperatures, typical of a thermoplastic elastomer. Deviation factors used to calculate the TTS graph in Figure 13 were shown in Figure 14.
[000168] The traction test was performed on an Instron 4204 Tension Test Frame and Controller, using a medium speed of 50 mm / min. See Figure 15. The stress vs. stress curves. strain for PS-PAESO-PS # 1 were compared with commercially available petroleum-based copolymer: SBR and Kraton D1118, as shown in Figure 16. The results showed that the elastic characteristics of the biopolymer showed an almost linear increase in strain-related strain. These characteristics are similar to those of SBR polymers, due to the high rubber content of the biopolymer. Stretching to the top of PS-PAESO-PS # 1 was six times higher than that of SBR and twice more than the Kraton D1118. Another characteristic of the biopolymer's elasticity was the lack of yield, which can be seen in the Kraton D1118 triblock.
[000169] To study the deformation of the polymer under loading and unloading, the specimens were subjected to 10 consecutive loading and unloading cycles. The tests were performed using an average speed of 50 mm / min and ranging from 0 to 55% deformation. Figure 17 shows the graph for PS-PAESO-PS # 1 on its first load, followed by the first hysteresis cycle, then by the cycle, and allowed to continue to find the maximum voltage. The graph showed the softening of the biopolymer with each consecutive loading / unloading cycle; while no deformation was observed. This softening appeared to be caused by the alignment of the polymer chains and / or the possibility of breaking the links between secondary chains. Young's modulus was represented graphically in relation to the number of cycles, showing an increase in the elasticity modulus as we increase cycles. See Figure 17. This non-linear behavior indicated the high elasticity of the biopolymer.
[000170] Real-space images of BCPs were collected with a transmission / scanning electron microscopeTecnai G2 F20 in a high-voltage voltage of 200 kV by ultra-thin sectioning (-80 nm) of the BCPs in thermo-genic temperature using a Leica Ultramicrotome EMUCT-125UCT with a. The TEM image of the PS-PAESO-PS triblock stained with osmium tetroxide OsO4 revealed a semi-periodic microstructure of styrene troughs surrounded by AESO regions in a clear pattern. See Figure 18. The capacity of these polymers for separate microwaves demonstrated that there was a strong incompatibility between the two blocks, which indicates the formation of microdomains rich in AESO and styrene.
[000171] Experiment conducted on modified asphalt with different composition of triblock copolymers based on PS and PAESO, and the results were compared with the experimental results obtained with the asphalt modified with two commercially available SBS polymers. Results of laboratory rheological tests of asphalt-biopolymer mixtures demonstrated that the biopolymers improved the shear modulus of the asphalt complex in a similar and even greater extent as commercially available SBS polymers. See Figure 11.Discussion of Example 9
[000172] ATRP polymerization of plant oils produced plastics, as opposed to hardenable polymers produced by free radical polymerization. In ATRP, polymerization began when soybean oil molecules became halogenated and began to form low molecular weight linear chains. This process continued until they reached a certain number of repetition units, where they connected to another chain or attacked another monomer to increase the length of the chain by one. The previous path had a low probability according to the high monomeric concentration and the propagation rate was much higher than the intermolecular chain transfer rate. In this last path, the most likely, polymers would start to grow in a hyper-branched way, where most of the active sites available for cross-linking were contained in the core of a region in the form of a "donut". When the active chain found this molecule, it would have an easy access to the finely thick shell nucleus, but it would significantly reduce access to the nucleus, where most of the functional sites were. This qualitative justification manifested in the polymer chain transfer rate, expressed by equation (3), which was achieved by increasing the scale of the number of active sites in the shell. The transfer rate will be the same as for the free radical modified by a percentage of active sites, which can be estimated by the relationship between the volume of the shell (Vshell) to the volume of the sphere (Vsphere).


[000173] Recent advances in polymerization technology have led to the development of elastomeric block copolymers produced with polystyrene and polymerized soy derived triglycerides, contrasting the last two decades of research that have produced highly linked materials. Using polymerized polyglycerides, copolymers in SBS tri-biotype were produced when block "B" was replaced with polymerized soybean oil. The ATRP polymerization technique was used to synthesize biopolymers without allowing the construction of macromolecules with precisely defined degrees of polymerization and the ability to form complex molecular architectures, such as polypolymers.Example 10 - Modification of asphalt with biopolymers derived from biopolymers derived from soybean oil biopolymers.
[000174] Triglyceride oils are composed of three chains of fatty acids linked by a glycerol center. Triglycerides derived from soybean oil were used for the synthesis of block thermoplastic copolymers (BCPs) using radical polymerization by atom transfer (ATRP). ATRP, a controlled radical polymerization technique, allows the construction of macromolecules with precisely defined degrees of polymerization and the ability to form complex molecular architectures, such as polopolymers in bulk (HIEMENZ R.C. & LODGE T.P., POLYMER CHEMISTRY (FLC), Rat.,.
[000175] For the synthesis of polymers a, soybean oil (Renewable Energy Group, Ames, IA) was purified on basic alumina, followed by epoxidation of double bonds and subsequentaccrylation to obtain the epoxidatedacrylated soybean oil (AESO). AESO and styrene were used as monomers, copper (I) chloride (CuCl) as the catalyst, benzyl chloride as the initiator, copper (II) chloride (CuCl2) as the counter-catalyst, N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA) as the binder, and toluene as a solvent, during all polymerizations. ATRP polymerization resulted in the creation of a thermoplastic terminated in hyper-branched halogenated poly (styrene-block-AESO-block-styrene) decopolymer-block (PS-PAESO-PS). The halogen termination provides functional sites for other chemistry. The detailed procedures for the synthesis of PAESO and PS-PAESO-PS have been described in Examples 1-3 and 6.
[000176] The effect of an asphalt modification polymer is determined by several parameters of polymers, including: chain architecture, composition, and molecular weight distribution. Even if a modified polymer does not disperse finely asphalt and may be more difficult to incorporate into the mixture, it is more effective in improving the elasticity in relation to the linear polymer (Lu & Isacsson, "Compatibility and Storage Stability of Styrene-Butadiene-Styrene Copolymer Modified Bitumens: 1997, 6" and 6 Structures ).
[000177] BCPs styrene butadiene-based copolymers (SBS) must also meet the various requirements to be compatible with asphalt. Oscopolymers SBS must be rich in embutadiene (generally 60-70%) and the molecular weight of the styrene fraction must exceed 10,000 <b0 /> daltons <e1 /> to obtain rich polystyrene (PS) domains (Lewandowski, "Polymer Modification of Paving Asphalt Binders," Rubber Chemistry and Technology 76 (3): 447 (1994),). Osbiopolymers (PS-PAESO-PS) produced for this example contained 72% poly (AESO). Figures 19A-B show the increase in molecular weight (average number) and polydispersity of the homopolymer of styrene (Figure 19A) and poly (styrene-block-AESO) diblock (Figure 19B) as a function of time. After approximately 700 minutes, the molecular weight of polystyrene increases beyond 10,000 daltons and the diblock to 150,000 daltons. Asphalt Modification with Biopolymers PS-PAESO-PS
[000178] To study the effectiveness of the PS-PAESO-PS biopolymer developed as an asphalt modifier, mixtures of asphalt modified with the PS-PAESO-PS biopolymer were compared with asphalt mixtures modified with two commercially available SBS polymers Kraton® D1101 and D1118. Both Kraton® SBS polymers are linear SBS polymer polymers. D1101 has a styrene content of 31% by weight of polymer and D1118 has a styrene content of 33% by weight of polymer.
[000179] A soft asphalt from a local refinery, using a Canadian source, was used as base asphalt. All asphalt-polymer mixtures were prepared in the laboratory, with a silverson L4RT tension mixer at 3000 rpm. The asphalt was heated up to 150 ° C and about 500 grams of asphalt were poured into each of the eight different aluminum cans of 0.95 liters of water to prepare eight liters of 500 grams. The polymers were added to the 3% lots, in total weight of the asphalt-polymer mixture.
[000180] The temperature of mixing the asphalt with the biopolymers was determined. For cadapolímero, twolots were prepared, with a lotemixed for 3 hours at 180 ° C and the other lotemixed for 3 hours at 200 ° C. The rest of the strips of a total of eight batches of asphalt were prepared as control treatments in the added polymer. One batch control treatment was tested immediately after being poured into the aluminum can, while the other batch of control treatment was first placed in the shear mixer for 3 hours at 200 ° C before being tested. No crosslinking agent, as sulfur was used during the mixing process. A mildly based binder containing relatively low asphaltene fractionation can be used to result in improved mixture compatibility and stability in an SBS polymer system (Alonso et al., "Rheology of Asphalt Styrene-butadiene Blends," Journal of Materials Science 45: 2591-2597 ( 2010),).
[000181] After the asphalt-polymer mixtures are prepared, the complex module (G *) and the phase angle of the mixtures were measured at high and low temperatures, using the dynamic shear rheometer (DSR) and beam-bending rheometer (BBR).
[000182] The Multiple Stress Creep Recovery (MSCR) test was conducted on materials aged in a laminating film oven (RTFO) following the specification of the American Association of State Highway and Transportation Officials (AASHTO) TP 70-11. The test was conducted at 46 ° C, due to the high temperature level of the virgin asphalt. The original material (semi-aging) of each mixture was also tested in a DSR at various temperatures and frequencies so that master curves can be constructed, which characterize the rheological properties of polymer-asphalt mixes over a wide range of temperatures.
[000183] Asphalt cement is normally modified with poly (styrene-block-butadiene-block-styrene) (SBS), a thermoplastic elastomer (TPE). Modification of polymers is known to substantially improve the physical and mechanical properties of asphalt paving mixtures. Modification of the polymer increases the elasticity of the asphalt at high temperatures, as a result of an increase in the storage module and a reduced phasing angle, which improves the groove resistance. It also increases the complex module, but reduces creep stiffness at low temperatures, thereby improving cracking resistance (Isacsson & Lu, "Characterization of Bitumens Modified With SEBS, EVA and EBA Polymer," Journal of Materials Science 34: 737-3745 (1999),). SBS-type polymers are usually added to phallic floorings when additional performance is desired or when optimizing life cycle costs is guaranteed. SBS allows the production of many special mixes, including cold mixes, emulsion chip seals, and micro-surface mixes.
[000184] SBS TPEs are embedded polymers (BCPs) composed of styrene-butadiene-styrene polymer chains that create a morphological array of polystyrene-emblococilindric glass domains within a polybutadiene rubber matrix (Bulatovic et al. ): 1-6 (2012),). SBS polymers are thermoplastic which means that they can be easily transformed into liquids at higher temperatures than their glass transition temperature, due to the nature of their linear strings. In cooling, polystyrene rigid end blocks glaze and act as anchors for liquid rubber domains, providing a restorative force when handling (FRIED J.R., POLYMER SCIENCE AND TECHNOLOGY (Prentice Hall, Upper Saddle River, NJ, 2nd ed. 2008),).
[000185] SBS is incorporated into asphalt by mixing and shearing at high temperatures to uniformly disperse the polymer. When mixed with the asphaltoligant, the polymerincase of asphaltmaltene to form a continuous three-dimensional polymer network (Lesueur, "The Colloidal Structure of Bitumen: Consequences on the Rheology and on the Mechanisms of Bitumen Modification," Advances in Colloid and Interface Science 145: 42-82 ( 2009),). At high temperatures, the polymer network becomes fluid and still provides a hardening effect that increases the modulus of elasticity of the mixture. At temperatures below, a network of cross-links within the asphalt develops again, evenly affecting performance degradation at the temperature due to the elastic properties of polybutadiene (Airey G. D., "Styrene Butadiene Styrene Polymer Modification of Road Bitumens," Journal of Materials Science 39: 951-959 (2004). The resulting performance properties extend the working temperature range of the binder-polymer system.
[000186] The butadienic monomer used in SBS is normally derived from petrochemical raw materials, a by-product of ethylene production. The price has risen rapidly, not only due to the increase in the price of oil, but also due to changes in the global market of supply and demand. As shale gas becomes more abundant, collapses are more commonly used with light petrochemical supplies, such as ethane to produce ethylene and its co-products. However, using lighter supplies reduces butadiene production, thereby adjusting the supply (Foster, "Lighter Feeds in US Steam Crackers Brings New Attitude Toward On-purpose Butadiene, Propylene Prospects," Platts Special Report: Petrochemicals 1-6 (2011),). Many commercially relevant elastomers require polybutadiene for their rubber and softness properties. As a result, there is a growing interest in sustainable polio polymers synthesized from plant-based raw materials to replace the need for their own chemical chemists, specifically the identification of alternative raw materials that can be made to mimic the properties of polybutadiene.
[000187] Flaxseed, rapeseed, flaxseed, and soy are examples of biodegradable and renewable resources that are available with triglyceride compounds that can be synthesized for the elastic component in BCPs. Soybean oil, for example, is composed of 86% mono and polyunsaturated fatty acid molecules that contain necessary double bonds for standard polymerization chemistry for the production of macromolecules. However, the multifunctional nature of soybean oil allows it to crosslink easily with other polyglycerides which lead to the formation of a thermosetting plastic, in an irreversible way, of highly highly polymerized polymer. Bhuyan et al, "Micro- and Nano-tribological Behavior of Soybean Oil-based Polymers of Different Crosslinking Densities," Tribology International 43: 2231-2239 (2010), demonstrated that a variety of plant oils can be successfully polymerized through cationic polymerization in hardenable polymer, with a wide spectrum of physical properties and aesthetic appearance.
[000188] Example 10, however, showed that I use polymerized triglycerides to produce a polybutadiene substitution and their incorporation with styrene to form thermoplastic thermoplastic polymer blocks that have been used to modify asphalt binders.
[000189] In Example 10, the rigidity of the asphalt-polymer mixture before and after aging in RTFO, under pressures of 1.0 kPa and 2.2 kPa, respectively, is shown in Figure 20. The asphalt has a degree of performance (PG) 46-34 according to AASHTO M320 "Standard Specification for Performance Graded Asphalt Binder," since the original asphalt had an administrative value G * / Sin (δ) of 51.3 ° C. After 3 hours of mixing in the shear mill at 200 ° C, the PG of the virgin asphalt was only slightly increased with a G * / Sin (δ) value of 52.6 ° C. This shows the mixing process used in this study does not significantly affect the age of the asphalt and increases the degree of performance. Any increase in the complex module or reduction of the phase angle was, therefore, in its major cause caused by the polymer that influences the rheological properties of the asphalt.
[000190] Figure 20 <i0 /> also shows that increasing the mixture temperature 180 ° C to 200 ° C increased the PG temperature of the asphalt. The two commercial SBS mixes performed similarly with the D1118 mixture with a slightly higher G * / Sin (δ) value of 62.0 ° C when mixed with asphalt at 200 ° C. Increasing the mixing temperature had a greater effect on the biopolymer mixture. At 180 ° C, the original G * / Sin (δ) value for the biopolymer mixture was 55.7 ° C, while at 200 ° C, the original G * / Sin (δ) value for the biopolymer mixture was 62, 3 ° C. A comparison of all original values G * / Sin (δ) shows the biopolymer mixed at 200 ° C has the highest PG temperature.
[000191] Figure 21 shows the low critical temperatures, with a limitable deformation stiffness (300MPa) and a limiting value (0.3) determined in a load time of 60 seconds in the BBR. The low temperature of virgin asphalt was -36.3 ° C and an increase of -35.3 ° C after mixing for 3 hours in the shear mixer. The lower cryptic temperature also increases for each polymer mixture by increasing the temperature of the mixture from 180 ° C to 200 ° C, indicating that the increased performance benefits on the high temperature side have been compromised on the low temperature side.
[000192] With the exception of mixtures of biopolymers, each asphalt-polymer mixture passed the -34 ° C criteria to be classified as a 46-34 asphalt. However, the range of continuous grades shown in Table 4 shows the range of performance level of asphalt-polymer-mixed at 200 ° C was only 0.3 ° C less than asphalt mixed SBS D1101 and 1.4 ° C less than asphalt mixed SBS D1118. The continuous PG range indicates the temperature susceptibility of biopolymers and their physical performance over a working temperature range were very close to the commercially available SBS polymers. These results were obtained before any study carried out to optimize the formulation of the PS-PAESO-PS biopolymer as an asphalt modifier. Table 4. Continuous PG banding of asphalt-polymer mixtures

[000193] Although many state transport agencies in the United States use a form of AASTHO M-320 as an acceptance specification for asphalt binders, the temperature test parameter G * / Sin (δ) has been shown to apply a voltage level not high enough to adequately test the polymer-modified binders for its resistance to permanent deformation. Recently, the Multiple Stress Creep Recovery (MSCR) test was developed in the United States using DSR to apply higher stress levels to capture the polymer's hardening and elastic response effects on a polymer-modified asphalt (D'Angelo et al., "Revision of the Superpave High Temperature Binder Specification : The Multiple Stress Creep Recovery Test, "Journal of the Association of Asphalt Paving Technologists 76: 123-162 (2007), which is incorporated by reference in its totality).
[000194] Non-recoverable creep compliance (Jnr) calculated from the MSCR test is shown in Figure 22. Lower Jnr values indicate good resistance to deformation. The commercial mixtures of polymer-SBS asphalt at 200 ° C and the mixture of biopolymer at 200 ° C, presented the lowest Jnr values. Biopolymer mixtures together with commercial mixtures at 200 ° C will achieve the highest Extremely Heavy Traffic level criteria since their Jnr values fall below 0.5 kPa.
[000195] In addition to the Jnr values, the MSCR test also measures the "recovery" value, which indicates the percentage of voltage recovered during the test. Higher percentages of deformation recovery indicate the presence of an elastomeric polymer and the quality of the asphalt-polymer mixture. In Figure 23, the higher mixing temperature appears to improve the polymer network established in the binder. Similar results were found by D'Angelo & Dogre, "Practical Use of Multiple Stress Creep and Recovery Test," Transportation Research Record 2126, Transportation Research Board, National Research Council, Washington, DC, 73-82 (2009),, in a SBS mix study using the MSCR test. The results of this test also showed the contrast and elastic recovery between the commercial mixtures of polymer SBS (47.8% for D1101 and 48.6% for D1118) and the mixture of biopolymers (21.1%) at the upper mixing temperature.
[000196] Figure 24 plots the MSCR recovery as a function of Jnr. The curve in the graph represents the recovery values in the minimum recommended percentage of an asphalt modified by polymer that should have sufficiently delayed elastic response. Values above the line indicate the presence of an elastomeric polymer and a quality mixture. The percentage of biopolymer recovery does not plot above the curve which means that the biopolymer mixing and / or formulation process can be further improved to increase the quality of asphalt mixtures. Commercial polymers are linear polymers and therefore should be more compatible with a radial polymer phalant when a crosslinking agent is not used. In contrast, the biopolymer has a branched network due to polydiglycerides. A cross-linking agent can improve the capacity of the biopolymer to form a uniformly dispersed and slightly etched network on the asphalt.
[000197] The master curves used to analyze the rheological properties of asphalt-polymer mixtures were built from data using the DSR. Frequency sweeps were carried out in samples of 25 mm placanagama of linear viscoelastic materials from 0.1 Hz to 50 Hz, at intervals of 6 ° C from 16 ° C to 70 ° C. main curve for shear complex module (G *) data was constructed using Excel Solver. G * isochrones were moved to adjust the Williams-Landel-Ferry (WLF) model with 40 ° C as the reference temperature. The shift displacement factors used to transfer phase angle data to construct the main phase angle curve. Equation 5 presents the WLF equation.
ondeaT = displacement factor, C1 and C2 = constants, Tr = reference temperature, and T = material temperature.
[000198] The master shear modulus curves in Figure 25 show that the biopolymer has increased the stiffness of the asphalt through a wide frequency range. In Figure 26, the biopolymer also reduced the phase angle of the asphalt, but not for lower levels like the two SBS polymers. In Figure 26, the asphalt modified with the two SBS polymers had a drop in the phase angle, which shows the evidence of the polymer rubber plateau. Similar rubber landing does not appear to show on the modified biopolymer asphalt. These data suggest the mixing and / or formulation process of biopolymer can be further improved to provide the asphalt with a sufficient elastic response. The phased angle can be the result of the hardening effect from the polystyrene-vitreous phase.
[000199] In Example 10, using polymerized triglycerides, copolymers in SBS triblocotype were produced when block "B" was replaced with polymerized soybean oil. The ATRP polymerization technique was used to synthesize the biopolymers that allow the construction of macromolecules with precisely defined degrees of polymerization and the ability to form complex molecular architectures, such as polymers in bulk.
[000200] The effectiveness of the PS-PAESO-PS biopolymer as an asphalt modifier was evaluated and compared with the asphalt modified with two linear SBS polymers Kraton®. All asphalt-polymer mixtures were prepared with a modified asphalt based on 3% polymer. The results of the rheology tests showed the biopolymer's ability to increase the range of asphalt grade in an almost identical way as commercially available SBS polymers, although the biopolymer's critical low temperature was 1.4 ° C higher than the SBS polymer D1118. The results of the MSCR tests also showed that the biopolymer reduced the Jnr value as low as that of the two commercially available SBS polymers.
[000201] The biopolymer and SBS polymers showed differences in performance that were measured by their elastic response in the MSCR test and their phase angle at different temperatures. The current should still be the optimized formulation of the biopolymer which does not appear to indicate a level of rubber in the main angular phase curve of the asphalt-polymer mixture and provided a 21.1% MSCR recovery compared to the 48.6% elastic recovery provided by the SBS polymer D1118. However, this can be overcome by optimizing the asphalt and biopolymer mixture formulation and mixing procedures.
[000202] Although the preferred modalities have been represented and described in details, it will be evident to specialists in the relevant technical that various modifications, additions, substitutions and the like can be made to depart from the spirit of the present invention and are therefore considered to be within the scope of the present invention with the following definitions.

权利要求:
Claims (22)
[0001]
1. Thermoplastic block copolymer, characterized by the fact that it comprises at least one block of PA and at least one block of PB, where PA represents a polymer block comprising one or more units of monomer A and PB represents a polymer block comprising one or more units of monomer B, with monomer A being a vinyl, acrylic, diolefin, nitrile, dinitrile or acrylonitrile monomer and monomer B being a radically polymerizable plant oil monomer containing one or more triglycerides.
[0002]
2. Thermoplastic block copolymer, according to claim 1, characterized by the fact that the block copolymer has: a PA-PB-PA or PBPA-PB triblock polymer architecture, or PA- PB-PA-PBPA or PB-PA-PB-PA-PB, or an architecture (PA-PB) n, where n is an integer ranging from 2 to 10, or an architecture (PA-PB) n-PA, where n is an integer ranging from 2 to 10, or a PB- (PA-PB) n architecture, where n is an integer ranging from 2 to 10.
[0003]
3. Thermoplastic block copolymer according to claim 1, characterized by the fact that the PA block comprises repeating units of monomer A and the PB block comprises repeating units of monomer B.
[0004]
4. 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, vinylxylene, vinylnaphthalene, vinylpyridine, divinylbenzene, acrylate methyl, (meth) methyl acrylate, (meth) ethyl acrylate, (meth) propyl acrylate, (meth) butyl acrylate, (meth) heptyl acrylate, (meth) hexyl acrylate, acrylonitrile, adiponitrile, methacrylonitrile, butadiene, isoprene, and mixtures thereof, preferably where omomer A is styrene.
[0005]
5. Thermoplastic copolymer, according to claim 1, characterized by the fact that the PB block comprises a straight chain or polymerized chained plant oil, ouradicals.
[0006]
6. Thermoplastic copolymer, according to claim 1, characterized by the fact that the PB block is polymerized plant oil which is subsequently partially partially saturated via catalytic hydrogenation after polymerization.
[0007]
7. Thermoplastic copolymer according to claim 1, characterized by the fact that the plant oil is soybean oil, linseed oil, flax seed oil, or rapeseed oil.
[0008]
8. Thermoplastic copolymer, according to claim 1, characterized by the fact that the polymer consists of a PA-PB-PA polymer triblock architecture, with the PA block being a gold-plated polystyrene of the same type, and the PB block being a polymerized soybean oil. linear chain or branched chain or radicals thereof.
[0009]
9. Elastomeric composition, characterized by the form comprising the thermoplastic copolymer as defined in claim 1, wherein the thermoplastic polymer is vulcanized, cross-linked, compatibilized and / or composed with one or another other elastomer, additive, modifier and / or filler.
[0010]
10. Engineering thermoplastic composition with toughness, characterized by the fact that it comprises the thermoplastic copolymer as defined in claim 1.
[0011]
11. Asphaltic composition, characterized by the role of which comprises the thermoplastic copolymer as defined in claim 1 as an additive, modifier and / or asphalt filler.
[0012]
12. Adhesive composition, characterized by the form of which comprises: the thermoplastic polyopolymer as defined in claim 1 and a tackifier and / or a plasticizer.
[0013]
13. Vehicle tire, characterized by the skin comprising the thermoplastic copolymer as defined in claim 1, wherein the tire is vulcanized, cross-linked, compatibilized and / or composed with one or more other material.
[0014]
14. Method for preparing a thermoplastic copolymer, the dithomethod characterized by the phosphate comprising: providing a radically polymerizable monomer represented by A or a PA polymer block comprising one or more A monomer units; epolymerize the monomer The radical pathway modified the polymer block PA with monomer B in the presence of an initiator and a transition metal catalyst system to form the thermoplastic copolymer.
[0015]
15. Method according to claim 14, characterized by the fact that said radical polymerization comprises: a) radical polymerization of monomer A in a suitable solvent to dissolve PA; and b) radical polymerization of monomer B in a suitable solvent to dissolve PA and PB, with PA from step a) being the initiator, to form a PA-PB block copolymer.
[0016]
16. Method for preparing a thermoplastic copolymer, the dithomethod characterized by the phosphate comprising: supplying a radically polymerizable plant oil monomer containing one or more polyglycerides, represented by B or a PB polymer block comprising one or more B monomer units; radical epolymerization of monomer B or polymer block PB with monomer A in the presence of an initiator and a transition metal catalyst system to form the thermoplastic copolymer.
[0017]
17. Method according to claim 16, characterized by the fact that said radical polymerization comprises: a) radical polymerization of monomer B in a suitable solvent to dissolve PB; and b) radical polymerization of monomer A in a suitable solvent to dissolve PA and PB, with PB from step a) being the initiator, to form a PB-PA block copolymer.
[0018]
18. Method according to claim 15 or 17, characterized by the fact that it further comprises: c) the radical polymerization of monomer A or monomer B with the copolymer embedded in the step b) as the initiator, thereby adding a block of additional polymer to the embedded polymer).
[0019]
19. Method according to claim 14 or 16, characterized by the fact that said radical polymerization is carried out by atom transfer radical polymerization.
[0020]
20. Thermoplastic polymer, characterized by the fact that it comprises one or more units of a radically polymerizable plant oil monomer containing one or more polyglycerides.
[0021]
21. Method for preparing a thermoplastic polymer or embedding polymer, the dithomethod characterized by the phosphate comprising: providing a radically polymerizable plant oil monomer containing one or more polyglycerides; the radical epolymerization of the plant oil dithomonomer in the presence of an initiator and a transition metal catalyst system to form the thermoplastic polymer or polymer block.
[0022]
22. Method according to claim 14 or 16, characterized by the fact that the method is carried out in the presence of a counter-catalyst and a solvent at a temperature ranging from 65 to 85 ° C.

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-10-06| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-02-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-03-30| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 18/01/2013, 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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US201261587816P| true| 2012-01-18|2012-01-18|

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US61/587,816|2012-01-18|

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PCT/US2013/022131|WO2013109878A1|2012-01-18|2013-01-18|Thermoplastic elastomers via atom transfer radical polymerization of plant oil|

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