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    • 专利摘要:
    MONOBENZOATE USEFUL AS A PLASTIFIER IN PLASTISOL COMPOSITIONS The present invention describes a unique monobenzoate useful as a plasticizer in polymeric dispersions such as plastisols and fused compounds. Monobenzoate comprises 3-phenyl propyl benzoate, a benzoate ester known as a flavoring and fragrance agent, but not previously used as a plasticizer in polymeric applications. Depending on the application, the advantages provided by the use of the monobenzoate of the invention include, among others, excellent solvation properties, low viscosity, viscosity stability and improved rheology, as well as environmental, safety and health advantages over traditional plasticizers.
    公开号:BR112014015883B1
    申请号:R112014015883-5
    申请日:2013-02-14
    公开日:2021-05-11
    发明作者:William D. Arendt；Emily MCBRIDE
    申请人:Emerald Kalama Chemical, Llc；
    IPC主号:
    专利说明:

    field of invention
    [001] This invention is directed to a non-phthalic monobenzoate useful as a plasticizer in a variety of polymeric applications, including, but not limited to, plastisols, adhesives, sealants, architectural coatings, industrial coatings, OEM coatings, paints, paints, varnishes, overlay (“OPV's”), other coatings, polishes and the like. In particular, this invention is directed to the use of a monobenzoate ester, 3-phenyl propyl benzoate to improve the performance of polymeric properties in plastisol applications. The monobenzoate of the invention exhibits rheology, viscosity stability and processability better than or comparable to traditional high solvation or specialized plasticizers used in plastisol applications. The invention is also directed to plastisol compositions comprising the monobenzoate of the invention and mixtures thereof with other plasticizers for use in the compositions. Background of the invention
    [002]Plasticizers, as polymeric additives, have been known for over a century. Larger volume plasticizers have been developed over the past seventy years, initially for use with vinyl and other polymeric substances. Plasticizers are used more often than any other type of polymeric additives, particularly in polyvinyl chloride (PVC) applications. Hundreds of plasticizers have been produced, but only a few remain with acceptable development properties when combined with vinyl or other polymeric materials.
    [003] General purpose phthalates are the best-selling plasticizers each year and are generally selected for flexible vinyl composition.
    [004] A common plasticizer is defined as an organic liquid that softens a polymer and makes it more viable, as the polymer and plasticizer are at least partially compatible. The role of a plasticizer in any polymeric system requires compatibility. Plasticizers are used to adjust the hardness (or softness) of a polymer, provide stain resistance, change tensile properties (such as strength, elongation or flexibility) and facilitate processability, when necessary, in various applications, including without limitation, flexible vinyl ones.
    [005] Plasticizers are also used as a vehicle for the dispersion of resin particles (polymers) such as PVC. Dispersion is initially a heterogeneous two-phase system. Plasticizers promote the formation of homogeneous systems, and polymeric fusion occurs after heating. The higher the solvation energy, the lower the temperature at which the homogeneous system is melted, which in turn reduces the dwell time and increases the speed at which polymer compositions can be processed into a final product, resulting in a longer process. fast, efficient and economical.
    Plasticizers are available in a wide variety of alternative chemicals and include: 1) general purpose ones, 2) specialized types and 3) secondary types and diluents, described in more detail in the present invention. Plasticizers are also distinguished based on their ability to solvate dispersed solid polymers and/or their melting and gelling temperatures in plastisols. Gelation and melting temperatures set the speed of production and are influenced by the solvation energy of the plasticizer. As an example only, the gelling and melting temperatures of a plastisol containing a dibenzoate plasticizer will be lower than those of a plastisol containing a general purpose phthalate, allowing for the speed of processing in this particular application.
    [007] General purpose plasticizers offer an excellent compromise between performance and economy characteristics for most applications. Some examples include: bis (2-ethylhexyl phthalate) (DEHP or DOP), diisononyl phthalate (DINP), dioctyl phthalate (DnOP), diisodecyl phthalate (DIDP), dipropylethyl phthalate (DPHP), di-2-ethylhexyl terephthalate (DOTP or DEHT) and diisononyl-1, 2-cyclohexane dicarboxylate (DIDC, HexamollTM from BASF or DINCH®).
    [008] An environmental study led to the development of “a new generation” of general purpose non-phthalic plasticizers such as DOTP and DIDC. Although DOTP is chemically a phthalate, it is not an orthophthalate, which is used to increase regulatory pressure. This “new generation” of alternative phthalates are viable, however, they do not always provide the desired performance in vinyl compositions, particularly in plastisols (ie, exhibiting lower compatibility, slower speed, higher gel temperatures, lower gel strength) . Mixtures of plasticizers can be used to adjust performance, although there may be some limits to this attempt.
    [009]Some applications, however, require performance that cannot be achieved by using a general purpose plasticizer alone. As an example, we have applications that require better resistance to oils and solvents. General purpose phthalates are easily extracted by non-polar solvents such as hexanes, so the use of alternative plasticizers may be a much better choice. There is also a need for plasticizers with stronger solvators for PVC and other polymeric applications. These solvators also have a favorable rheological profile.
    [0010] Specialized plasticizers have been developed, in part, to fill the need for stronger solvators, with the most popular being low molecular weight phthalates. An example of such a plasticizer is butyl benzyl phthalate (BBP), which is generally employed as a high solvation plasticizer. Di-n-butyl phthalate (DBP) and diisobutyl phthalate (DIBB) are also useful as specialized plasticizers with high solvation. Examples of highly solvated, non-phthalic plasticizers include dibenzoate esters, some citric acid esters, sulfonic acid alkyl esters and certain phosphates. Dibutyl terephthalate (DBTP) and N-alkyl pyrrolidones have also been proposed as a special type of high solvation plasticizers. Some high solvation plasticizers are limited in their use due to high viscosity or poor rheological characteristics. An ideal plasticizer has a good balance between solvation and rheology characteristics.
    [0011] Benzoate plasticizers include dibenzoates and monobenzoates, such as diethylene glycol dibenzoate (DEGDB) and dipropylene glycol dibenzoate (DPGDB) esters, which have been used in a wide variety of polymer applications, including in industry of vinyl. DEGDB is an excellent plasticizer, but due to its high freezing point, blends with DPGDB were also developed to take advantage of the utility and low cost of DEGDB. Many years ago a blend of DEGDB, DPGDB and triethylene glycol dibenzoates (TEGDB) was introduced as a highly solvated dibenzoate blend. More recently, a new triple blend of dibenzoate has been introduced as a plasticizer with low volatile compounds (VOC)/coalescents for use in plastisols, adhesives, paints and architectural coatings and polishes, among other applications. This triple blend, comprising DEGDB, DPGDB and 1,2 propylene glycol dibenzoate (PGDB) in various proportions and sold as K-FLEX® 975P, was found to be very versatile for a variety of applications based on its wide range of compatibilities with polymers used in the coatings industry (eg vinyl acrylic, acrylic and styrene acrylic) and has good solvation properties and low volatility. Its performance properties are compared to high solvation phthalate plasticizers as well as traditional benzoate ester plasticizers.
    Monobenzoate esters known to be useful as plasticizers include: isodecyl benzoate, isononyl benzoate, and 2-ethylhexyl benzoate. For example, isodecyl benzoate for use in preparing plastisols in U.S. Patent No. 5,236,987 to Arendt. The use of isodecyl benzoate has also been described in U.S. Patent No. 7,629,413 to Godwin et al. as a useful secondary plasticizer combined with phthalate plasticizers to provide lower viscosity and volatility in PVC plastisols. The use of 2-ethylhexyl benzoate in a mixture with DEGDB and diethylene glycol monobenzoate is described in U.S. Patent No. 6,689,830 to Arendt et al. The use of isononyl benzoic acid esters as film-forming agents in compositions such as plastic paint, mortar, plaster, adhesives and varnishes is described in U.S. Patent No. 7,638,568 to Grass et al.
    [0013] “Half ester” monobenzoates include dipropylene glycol monobenzoate and diethylene glycol, which are by-products of the production of dibenzoates, but which, most of the time, are not objects of production. Half-ester products are not known to have high solvation, although they can be used together. Half-ester products are not known as dibenzoate plasticizers because they are less compatible than the corresponding dibenzoates with PVC. However, half-ester products are compatible with emulsion polymers such as vinyl and/or acrylic ester polymers.
    [0014] Examples of secondary and diluent type plasticizers, used primarily to reduce the viscosity of plastisol, include those based on castor oil and soybean oil. Isodecyl benzoate, a monobenzoate, is also a useful plasticizer of the diluent type.
    [0015] All high solvation plasticizers (regardless of type) add value to vinyl compositions whereas traditional general purpose plasticizers do not. Traditional general purpose plasticizers have good rheological profiles and are compatible with many polymers, but have a low solvating capacity. In addition, most highly solvated plasticizers are phthalates, where safer alternatives are being sought.
    [0016] Therefore, there remains a need for non-phthalic plasticizers, with low volatile compounds (VOC) content for use in polymeric applications, such as plastisols, as an alternative to traditional diluent plasticizers. These alternatives must be compatible with a wide variety of polymers and have a low VOC content and better or comparable performance properties when used in polymeric applications such as traditional vinyl plasticizers. Non-phthalic plasticizers with a low VOC content are particularly desirable in the environmental, health and safety aspects associated with traditional plasticizers of the diluent type.
    [0017] It has been found that an entirely different monobenzoate, 3-phenyl propyl benzoate (3-PPB), is an effective plasticizer alternative for use in polymeric applications, including but not limited to plastisols, paints and other coatings, adhesives, OPV's and paints. In addition to its low VOC content, the advantages of this monobenzoate, compared to traditional plasticizers with high VOC content, such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, are its environmental, safety and health, and its handling properties, which are better than most previously used dibenzoates and monobenzoates. This new monobenzoate is not classified as dangerous, and no marking element is required.
    [0018] The monobenzoate, 3-PPB, was used in the past as a fragrance and flavoring, but not in polymeric applications as discussed in the present invention. It continues to be used in fragrances and flavorings. It has also been used as a solubilizer for certain organic active or functional compounds in personal care products, such as topical sunscreens, as described in U.S. Patent Publication 2005/0152858.
    [0019] While this invention is focused on the use of the plasticizer of the invention in plastisol compositions, other applications for the monobenzoate of the present invention include a variety of coatings, including, but not limited to, overlay varnishes, polishes, paints, paints, adhesives and sealants, which are the subject of copending applications.
    [0020] It is the object of the present invention to offer a plasticizer that has excellent compatibility with a wide variety of polymers and lower VOC content than traditional diluent-type plasticizers used to control plastisol viscosities, to be used alone or with other plastics. - cans, in plastisols and in other polymeric applications where plasticizers are needed.
    [0021] It is also the object of the present invention to offer an alternative non-phthalic plasticizer for use with a primary or secondary plasticizer in PVC applications.
    [0022] It is another object of the invention to offer a non-phthalic plasticizer that has high solvation properties and a good rheological profile, which is useful for improving the compatibility and processability of low solvation plasticizers, while minimizing the disadvantages of high viscosity and low rheology associated with the use of traditional low solvation plasticizers.
    [0023] It is also an object of the present invention to offer mixtures of plasticizers comprising the monobenzoate of the invention.
    [0024] It is also an object of the present invention to provide a plastisol formulation using a non-phthalic plasticizer, 3-PPB, which allows faster and more economical processing, and offers a tensile strength comparable to or better than traditional plasticizers of the diluent type .
    [0025]Other objects of the invention will become clear from the description below. Summary of the invention
    [0026] This invention is directed to the use of non-phthalic monobenzoate ester useful as a plasticizer in polymer dispersions such as plastisols. The monobenzoate of the invention comprises 3-phenyl propyl benzoate (3-PPB), a component not previously known or used as a plasticizer for plastisol compositions.
    [0027] In one embodiment, the invention is a plasticizer comprising 3-PPB useful to provide an improved solvation and rheology in polymeric applications, such as plastisols, cast compositions, injection molding, extrusion and calendering, among others.
    [0028] In a second embodiment, the invention is a plastisol composition comprising the monobenzoate plasticizer of the invention, including but not limited to PVC and acrylics.
    [0029] In a third embodiment, the invention is a mixture of 3-PPB with traditional plasticizers.
    [0030] In a fourth embodiment, the invention is a mixture of 3-PPB with solid plasticizers.
    [0031] Still in other embodiments, the invention is related to the use of the plasticizer of the invention in compositions used in applications such as resistant floors, toys, gloves, wall coverings, leather, fabrics and the like.
    [0032] The use of 3-PPB in amounts similar to traditional plasticizers results in a lower VOC content compared to other diluted plasticizers such as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate or isodecyl benzoate and better or comparable performance and handling properties than those obtained with traditional plasticizers. The monobenzoate of the invention has low toxicity and lacks the health and safety aspects associated with many traditional plasticizers. Brief description of the figures
    [0033] Figure 1 depicts initial viscosity data obtained for the mono-benzoate of the invention when compared to a triple mixture of dibenzoate and a general purpose phthalate plasticizer, DINP.
    [0034] Figure 2 shows melting/gel curves for the monobenzoate of the invention, a triple mixture of dibenzoate and a general purpose phthalate plasticizer, DINP.
    [0035] Figure 3 presents thermogravimetric data for pure plasticizers, including the monobenzoate of the invention, DINP, IDB and TXIBTM from Eastman.
    [0036] Figure 4 shows volatility data from the ASTM D-1203 extended test at 70°C for the monobenzoate of the invention, DINP and IDB.
    [0037] Figure 5 shows the initial viscosities obtained on day 1 and day 7 using Brookfield RVT viscosity, 20 rpm, 23°C for the monobenzoate of the invention, DINP and IDB.
    [0038] Figure 6 (a) presents rheology data: 1-day scan obtained for a basic plastisol composition comprising the monobenzoate of the invention when compared to a triple mixture of dibenzoate (X20, K-FLEX® 975P), BBP, DOTP, DINO and IDB.
    [0039] Figure 6 (b) shows gel melting curves for a basic plastisol composition comprising the monobenzoate of the invention when compared to a triple mixture of dibenzoate (X20, K-FLEX® 975P), BBP, DOTP, DINP and IDB.
    [0040] Figures 7 (a), (b) and (c) show values of tensile strength, modulus and elongation, respectively, for a plastisol comprising the monobenzoate of the invention compared to DINP and IDB.
    [0041] Figure 8 shows the Brookfiled viscosities obtained for various plastisol formulations at onset, day 1, day 3 and day 7 compared to the control formulation comprising DINP 50 phr.
    [0042] Figure 9 shows melting/gel curves for various plastisol formulations when compared to a control formulation comprising DINP 50 phr.
    [0043] Figure 10 presents initial shear data for various plastisol formulations compared to a control formulation comprising DINP 50 phr.
    [0044] Figure 11 presents data from the Brabender heat enhancement experiment for the monobenzoate of the invention.
    [0045] Figure 12 presents data from the heat rise experiment comparing the monobenzoate of the invention with DINP. Detailed description of the invention
    The present invention is directed to a monobenzoate plasticizer useful for a variety of applications as a primary or secondary plasticizer, including but not limited to plastisols. The benzoate plasticizer comprises a single monobenzoate, 3-phenyl propyl benzoate (3-PPB), not previously known or used as a plasticizer in polymeric applications. The preferred embodiment of the invention features 3-PPB combined with a polymer dispersion. The present invention is not limited to any particular polymer, although the invention can be described in terms of vinyl polymers.
    [0047] The monobenzoate plasticizer of the present invention can be commonly used as a primary or secondary plasticizer in blends with other plasticizers with numerous polymeric dispersions, generally as a substitute or alternative product for conventional diluent plasticizers, which have a high content of VOC or plasticizers that do not offer advantageous solvation and rheology. Any known polymers produced in the form of a plastisol by compound melting, injection molding, extrusion or calendering can be used in combination with the novel monobenzoate to prepare a low VOC composition in accordance with the present invention.
    In particular, the plasticizer of the present invention can generally be used with numerous thermoplastic, thermoset or elastomeric polymers, generally as an alternative to conventional plasticizers. By way of example, the monobenzoate of the invention can be used to prepare a low viscosity PVC, PVC copolymer or acrylic-based plastisol according to the present invention.
    Acrylic polymer compositions for various applications can also be used with the monobenzoate of the invention and include various polyalkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate or allyl methacrylate; or various aromatic methacrylates such as benzyl methacrylate; or various alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; or various acrylic acids, such as methacrylic acid and styrene acrylics.
    [0050] In addition to PVC and acrylic plastisols, the monobenzoate of the invention may be useful in other polymeric compositions, including, but not limited to various vinyl polymers, comprising polyvinyl chloride and its copolymers, vinyl acetate, vinylidene chloride, diethyl fumarate , diethyl maleate, or polyvinyl butyral; various polyurethanes and their copolymers; various polysulfides; cellulose nitrate; polyvinyl acetate and its copolymers; and various polyacrylates and their copolymers.
    [0051] Other polymers, for the monobenzoate of the invention, which can be used as a plasticizer, include epoxy resin, phenol-formaldehyde type; melanins and the like. Other polymers will become apparent to those skilled in the art.
    [0052] For the purposes of the invention, the term "plastisol" means a liquid polymeric composition comprising a particulate form of at least one uncrosslinked organic polymer, dispersed in a liquid phase that comprises a plasticizer for the polymer. As used in the invention, "plastisol" also means and includes an "organosol", which is a plastisol where solvents such as liquid hydrocarbons, ketones or other organic liquids are used in amounts greater than about 5% by weight to control the viscosity and other properties of a plastisol.
    [0053] As used in the present invention, "strong solvator" or "high solvation" is a term that describes the efficiency of the plasticizer in penetrating, thickening and gelling the plastisol solid before the full development of physical properties. All plasticizer is absorbed into the PVC of a plastisol at lower temperatures than general purpose plasticizers, facilitating faster formation of a homogeneous phase.
    [0054] The use of the monobenzoate of the invention is not limited to any particular polymer. Other polymer-based compositions that require plasticizers are well known to those skilled in the art.
    [0055] The novel monobenzoate of the present invention can be used as a low VOC substitute for other diluent plasticizers, such as isodecyl benzoate, or as an alternative plasticizer for various traditional polymer dispersions, including without limitation vinyl applications.
    [0056] The total amount of the monobenzoate of the invention used in any particular polymer dispersion may vary depending on the polymer, its characteristics and other components, the process, application or use and the desired results. The total amount of the monobenzoate of the invention may vary depending on the application, generally from about 1 to about 300, desirably from about 10 to about 100, and preferably from about 20 to about 80 parts by weight per each 100 parts total by weight of one or more thermoplastic, thermoset, or elastomeric polymers, including without limitation those identified above. For 3-PPB, a particularly preferred embodiment for a plastisol of about 5 to about 20 parts by weight for every 100 parts by weight of plasticizer total resulted in a total content ranging from 30 to 120 phr.
    [0057] Useful amounts of 3-PPB are set out in the examples. It is expected that one of skill in the art will be able to obtain optional acceptable amounts based upon the intended use and desired performance of the particular polymeric application.
    [0058] The monobenzoate of the invention can be, but need not be, blended with various other conventional plasticizers to improve or enhance the properties of polymeric compositions, including but not limited to compatibility and processability into a plastisol, and improved solvating power. Conventional plasticizers have been described in the present invention and include, but are not limited to, various phthalate esters, phosphate esters, adipate compounds, azelate, oleate, succinate and sebacate, citrates, trimellitates, terephthalate esters, such as DOTP, esters of 1,2-cyclohexane dicarboxylate, epoxy plasticizers, fatty acid esters, glycol derivatives, sulfonamides, sulfonic acid esters, benzoates, bioplasticizers such as PG disoiate and PG monosoiate, chloroparaffin, polyesters and various other hydrocarbons and its derivatives which are generally used as secondary plasticizers, such as epoxidized soybean oil, and the like.
    [0059] Monobenzoates, such as isononyl benzoate, isodecyl benzoate and 2-ethylhexyl benzoate, as well as 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIBTM, an Eastman brand) can also be blended with the monobenzoate from invention, or 3-PPB can replace any of these with the advantage of obtaining solvation and keeping the processable viscosity and rheology at a lower amount.
    [0060] The monobenzoate of the invention can also be mixed with solid plasticizers, such as benzoate with sucrose, dicyclohexyl phthalate, triphenyl phosphate, glycerol tribenzoate, 1,4-cyclohexane dimethanol dibenzoate (CHDM), pentaerythritol tetrabenzoate and esters of alkyl glycol.
    [0061] Other suitable plasticizers are known to those skilled in the art.
    [0062] The monobenzoate of the invention can also be combined with or include various amounts of conventional additives, such as oils, thinners, antioxidants, surfactants, heat stabilizers, flame retardants, resin blends, paraffins, solvents and the like, depending on the particular application or polymer dispersion. Amounts of additives can vary widely, but remain in the range of about 0.1 to about 75 parts by weight for every 100 parts by weight of the plastisol composition.
    [0063]For vinyl applications, there are two different casting methods: plastisols and cast compounds. A plastisol is a liquid dispersion of PVC (or other polymer) in the plasticizer, which can be heated as a diffusion coating, fused in slush molding, dip molded, or rotational molding. The plastisols of the invention can be composed by simple mixing, followed by deaeration in most cases. Casting is a process that uses heat and pressure with agitation to cast vinyl (or other polymer). The objective is to combine the polymer and the plasticizer to form a homogeneous material through a calender, extruder or injection molding.
    [0064] Formulations for simple, basic plastisols and fused compounds are described in the examples; however, the invention is not limited to these formulations.
    [0065] The monobenzoate of the invention has a lower VOC content compared to diluent and secondary plasticizers, and depending on the application, offers comparable or better compatibility, viscosity, stability and rheology, among other advantages. In many examples, the monobenzoate of the invention outperforms industry standard plasticizers, including new or traditional dibenzoate blends. Many traditional plasticizers have properties of high solvation or low viscosity, but not both. Surprisingly, the monobenzoate of the invention offers a balance between high solvation energy, better rheology and lower viscosity, even when used alone.
    [0066] There are a wide variety of uses for the plastisols and cast compounds of the invention, including, but not limited to, heavy duty floors, wall cladding, wear layer, toys, gloves, leather and textile applications. Other uses are known to those skilled in the field.
    [0067] The invention will be described through the following examples. Examples Experimental methodology Preparation of plastisol and vinyl
    [0068]Plastisols were prepared in a Hobart Model N-50 mixer. A 10 minute agitation with speed one (1) was used. A high speed disperser was also used to prepare other plastisols, with stirring for 10 minutes at 1000 rpm. All plastisols were degassed at 1 mmHg to remove as much air as possible.
    [0069] The vinyl for the basic fabric was cast in a closed mold having a thickness of 1.2 mm at a temperature of 177°C for 15 minutes in a Blue M oven. The vinyl for the stain resistance test was cast in a Mathis oven with a thickness of 0.5 mm, at a temperature of 204°C for 2.5 minutes. Airflow has been set to 1500 RPM. Tests/Assessments
    [0070] The objective was to determine the basic performance parameters of the plasticizer of the invention in relation to currently available plasticizers known or standards. Tests that demonstrated efficiency (shore A and stress properties), permanence (extraction and volatility) and processability (viscosity, viscosity stability, rheology and gel/melting) were used. Unless otherwise indicated in the examples, the general tests and/or methodologies described below were used. The tests and methods are known to those skilled in the field.
    [0071] Viscosity and Rheology: Low Shear - Viscosity measurements were made using a Brookfield RVT at 20 RPM for 10 revolutions at a temperature of 23 ± 2°C. ASTM D1823. High shear - TA AR2000ex used. Parallel plates were configured with appropriate spaces (350 microns). Shear at 1000 sec-1. Viscosity evaluation: viscosities were measured at the beginning and 24 hours later.
    [0072] Fusion/gel: TA AR200ex in oscillatory mode. Parallel plates were configured with appropriate spaces (600 microns). The test temperature was started at 40°C and heated at a rate of 5°C/minute until reaching 220°C.
    [0073] Efficiency - Shore A - ASTM D2240; Tension - ASTM D638, Type IV die, 50.8 cm/minute pull rate.
    [0074] Permanence - volatility - EPA 24, ASTM D2369, 11°C for 1 hour; and a TGA isothermal scan at a temperature of 110°C for four hours. An isothermal TGA for one hour under an atmosphere of air at a temperature of 110°C was also employed. ASTM D1203 was also used as an extended test for volatile loss. Example 1 - Basic plastisol Evaluations - Processability
    [0075] The following examples demonstrate the effectiveness of the monobenzoate of the invention with an initial basic plastisol formulation described below:

    [0076] The monobenzoate of the invention was compared to X-20 (K-FLEX 975P, a triple mixture of dibenzoate comprising 20% by weight, 1,2-propylene glycol dibenzoate and 80% by weight of a dibenzoate mixture of 80 /20 DEG/DPG) and DINP. Figure 1 presents initial viscosity data obtained for the monobenzoate of the invention compared to a general purpose phthalate, showing better rheology than the triple mixture of dibenzoate.
    [0077] Table 1 below shows the melt/gel values obtained for 3-PPB, X-20 and DINP (a general purpose phthalate plasticizer). Table 1

    [0078] Figure 2 shows the gel/fusion curves for 3-PPB, X20 and DINP.
    [0079] The above results reflect that 3-PPB is a viable alternative for use in plastisol compositions and is an acceptable partial substitute for general purpose phthalates traditionally used in this type of application. Unexpectedly, 3-PPB had lower viscosity, better rheology and better solvation properties when used in plastisol applications than most traditional plasticizers. 3-PPB also achieved a lower melting temperature, as shown in table 1 and figure 2, providing faster processing time and/or lower energy costs in plastisol applications. These results are consistent with the heat increase experiments performed with cast compounds, comparing 3-PPB and DINP, as shown in figure 12. Example 2 - Basic plastisol evaluations - processability, permanence
    [0080] The basic plastisol formulation of example 1 was used in this example.
    The monobenzoate of the invention (X-613) was compared to DINP, IDB (isodecyl benzoate) and 2,2,4-trimethyl 1,3-pentanediol diisobutyrate (TXIB, an Eastman brand).
    [0082]The thermogravimetric data of the pure plasticizers are shown in Figure 3. The results demonstrate that 3-PPB is significantly less volatile than TXIBTM and IDB, presenting longer permanence and lower VOC production than these two plasticizers . An extended test, showing the loss of volatiles for 3 days, at a temperature of 70°C of DINP, IDB and 3-PPB, is shown in Figure 4. The results showed that 3-PPB has a better volatility (permanence) than than the idb during the three-day period.
    [0083] The initial, 1st and 7th day viscosities obtained for 3-PPB, DINP and IDB are shown in Figure 5. These data demonstrate a higher viscosity of 3-PPB than that obtained for IDB, but much smaller than that of DINP phthalate. The data demonstrate that 3-PPB has good solvation properties and lower viscosity compared to traditional phthalate, and is a viable alternative for plastisol applications. IDB has a lower viscosity but is a less efficient solvator than 3-PPB. Example 3 - basic plastisol evaluation - rheology and gel/fusion
    [0084] The basic plastisol formulation of example 1 was used in this example.
    [0085] In this example, 3-PPB (X-613) was compared to DINP, Eastman's TXIBTM, DOTP, X20, IDB and BBP (butyl benzyl phthalate). Rheology data (1-day scan) and gel/fusion curves were obtained for the group as shown in Figures 6(a) and 6(b), respectively.
    [0086] The results demonstrate that as the shear rate is increased, a higher viscosity is expected. The viscosity of DINP, IDP and 3-PPB held, while that of DOTP and BBP slightly increased and leveled off. That of the triple dibenzoate mixture (X20) increased rapidly, followed by a decline. The results showed that 3-PPB is comparable to IDB and DINP, and has superior rheology to X20, BBP and DOTP.
    [0087] The melt/gel data illustrates the relative solvation characteristics of various plasticizers. Figure 6(b) presents the results of the fusion/gel evaluation, revealing better results for 3-PPB compared to X20 and unexpectedly better than the BBP control, which is considered an industry standard. DOTP, DINP and IDB demonstrated worse solvation properties than 3-PPB. 3-PPB is at least twice as efficient as IDB as a solvator while maintaining viscosity and rheology.
    [0088] Overall, the results demonstrate that 3-PPB offers a combination of excellent rheology and better solvation properties than many available plasticizers. Example 4 - Basic plastisol evaluation - efficiency
    [0089] The tensile strength (psi/kPa), modulus (100%) and elongation (%) values were obtained for DINP, IDB and 3-PPB (X-613). The results obtained are shown in figures 7(a), (b) and (c), respectively, and reflect that the 3-PPB is in total a little more efficient than the IDB. Example 5 - Plastisol Wear Layer Assessments
    [0090] The evaluated basic formulations are described below in table 2, including mixtures of DINP and IDB, DINP and 3-PPB, DINP, IDB and 3-PPB (X-613).


    [0091] Figure 8 shows the Brookfield viscosities obtained for the various formulations: 1st day, 3rd day and 7th day compared to the control formulation comprising DINP 50 phr. The results showed that 3-PPB initially had a higher viscosity than IDB, but lower than DINP.
    [0092] Over time, the viscosity of 3-PPB remained stable, while the formulation with IDB 5 phr showed an increased viscosity compared to 3-PPB 5 phr.
    [0093] The fusion/gel data obtained for the various formulations are shown below in table 3 and the respective curves in figure 9. The results demonstrate that at equal levels, 3-PPB is better than the DINP control in terms of relative solvation characteristics, and is comparable or somewhat better than the BDI in terms of its relative solvation characteristics. The 3-PPB data reflect a good balance between gel and fusion allowing rheological behavior to be predicted and adjusted. Table 3

    [0094] The initial shear results are shown in Figure 10. The results showed that all formulations performed performed better than the DINP control. The results for 3-PPB showed that it has a good rheological profile making it a suitable plasticizer for use in plastisol formulations.
    [0095] The above results establish that 3-PPB is a high solvator presenting a good solvation and lower viscosity than some traditional plasticizers, which makes its use alone suitable or combined in plastisol applications. Some traditional plasticizers are also highly volatile, making them unsuitable for use with plastisols according to regulatory standards. Traditional plasticizers generally offer excellent solvation or excellent rheological characteristics, but not both. Using mixtures of DINP (and other plasticizers) with IDB, in particular, is an attempt to obtain good solvation and good rheological characteristics. The product of the present invention alone offers good solvation and good rheological characteristics. The product is also useful with blends. Example 6 - Cast Composite Evaluations
    [0096]Torque rheometry is a method for measuring the actual processing conditions of a compound. Heat enhancement experiments illustrate the differences when fusion occurs with different plasticizers. The measured temperature and torque curves together with the physical changes of the compound can be studied. Another point of interest is the relative melting temperature, which occurs when the storage temperature is increased rapidly. This temperature indicates the point where solvation occurs, resulting in a considerable increase in torque leading to the formation of compound fusion. The relative melting temperature helps to determine the solvation characteristics of plasticizers used in PVC. From this point onwards, an analysis of how different plasticizers affect the processing ability of a cast PVC compound or plastisol can be carried out, demonstrating how the processing factors of one plasticizer may be more favorable than others.
    [0097]Increase in Brabender heat. The general heat enhancement formula shown in table 4 below was weighed and mixed using a metal spatula, forming a white cake-like powder. The A.C.W. Brabender Intellitorque® was used in the study. The Brabender was equilibrated with an initial temperature of 40°C, and after being loaded with 50cm3 of the sample, the temperature was increased at a rate of 3°C/per minute until it reached 200°C. Six cylinders mixed the compound at a speed of 63 rpm with an interval of 1 second. After loading, the conductor was closed using a press and a weight of 5 kg. Each sample was then processed until degradation began. The plasticizers evaluated contained PGDB (1,2-propylene glycol dibenzoate), K-FLEX® 975P (X-20, a triple mixture of dibenzoate), PG, K-FLEX® 850P (a dual mixture of dibenzoate), X-613 (3-PPB), BBP, DINP, DIDC and DOTP.
    [0098] The results of the experiments are shown in tables 5 and 6.


    [0099] Table 5 above illustrates the torque, time and temperature for each sample and indicates when the melt flow of the compound has been reached. In general, benzoates had faster melt times than general purpose plasticizers. Shorter melt times indicate superior plasticizer solvation properties.
    [00100]The heat increase results in table 6 indicate the time, torque and temperature where degradation starts for each sample. The time, torque and temperature where relative melting takes place are also represented. DINP, DOTP and DICC have the highest temperatures for relative melting, indicating a lower solvation capacity.
    [00101] Figure 11 presents Brabender heat rise data for 3-PPB, and Figure 12 presents Brabender data for 3-PPB compared to DINP. Figure 12 is a good demonstration of the high solvation properties of 3-PPB compared to general purpose plasticizers. Both compounds were processed using the same starting temperatures and the same rate of temperature change. The difference in their torque values was caused by changes in the melt characteristics that each sample produced. Figure 12 demonstrates that 3-PPB melts faster than DINP melted compound. The 3-PPB compound starts to melt within the first 5 minutes of starting the process. DINP compound requires a higher temperature and more energy to start casting.
    [00102] Brabender isothermal evaluations - the same plasticizers tested in the heat rise experiments were evaluated for isothermal tests. The formula used was slightly modified to include epoxidized soybean oil (ESO) as well as higher levels of stearic acid and plasticizer. The formula is described below in table 7.
    [00103]Using the formula in table 7, the materials were weighed and mixed like a metal spatula. In this test, the ACW Brabender Intellitorque® mixer was programmed to maintain a constant temperature of 150°C. The 50 cm3 sample volume was loaded in the same way as in the heat rise test. The experiments were completed at the beginning of the rapid increase in torque.

    [00104]Isothermal testing is important because different plasticizers can be analyzed with respect to the effect of the solvator class. This experiment simulates actual processing conditions and can be used to rate the ability of plasticizers to facilitate vinyl processing. The data in Table 8 below demonstrates little difference between the plasticizers that exhibit high solvation and the general purpose ones that were tested, as the compounds melt very quickly because they are subjected to high temperature throughout the test. None of the samples were subjected to degradation during the test time.
    [00105] The results of the evaluations of the cast compounds have demonstrated that 3-PB is compatible in PVC melt compounding applications and exhibits excellent solvation properties compared to general purpose blends of dibenzoate and plasticizers.


    [00106] According to the patent rules, the best way to describe the invention and the preferred modalities were presented; the scope of the invention is not limited to this, but to the appended claims.
    权利要求:
    Claims (5)
    [0001]
    1. Use of an alternative non-phthalic monobenzoate as a plasticizer to disperse a polymer to form a plastisol, CHARACTERIZED by the fact that the plasticizer consists of 3-phenyl propyl benzoate.
    [0002]
    2. Plastisol composition CHARACTERIZED by the fact that it comprises: a polymer dispersed in a plasticizer used as defined in claim 1, wherein the polymer is a homopolymer or copolymer of polyvinyl chloride, an acrylic based polymer, vinyl acetate , vinylidene chloride, diethyl fumarate, diethyl maleate, polyvinyl butyral, a polyurethane and copolymers thereof, a polysulfide, a polyvinyl acetate and copolymers thereof, a polyacrylate and copolymers thereof, an epoxy, a melanin or a phenol-formaldehyde polymer, and wherein the alternative non-phthalic monobenzoate plasticizer as defined in claim 1 is used alone as a primary plasticizer or a secondary plasticizer in combination with other plasticizers to disperse the polymer to form a plastisol.
    [0003]
    3. Plastisol, as defined in claim 2, CHARACTERIZED by the fact that 3-phenyl propyl benzoate is combined with another plasticizer which is a phthalate ester, a phosphate ester, an adipate, an azelate, an oleate, a succinate, a sebacate, a citrate, a trimellitate, a terephthalate ester, 1,2-cyclohexane dicarboxylate esters, epoxy plasticizers, fatty acid esters, glycol derivatives, sulfonamides, sulfonic acid esters, benzoates, bioplasticizers, chloro- paraffin, polyesters, hydrocarbons, hydrocarbon derivatives, or mixtures thereof.
    [0004]
    4. Plastisol, as defined in claim 2, CHARACTERIZED by the fact that 3-phenyl propyl benzoate is combined with any one of isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate, 2,2,4-trimethyl-diisobutyrate 1,3-pentanediol, epoxidized soybean oil, PG disoiate, PG monoisolate or mixtures thereof.
    [0005]
    5. Plastisol, as defined in claim 2, CHARACTERIZED by the fact that 3-phenyl propyl benzoate is combined with a solid plasticizer which is benzoate with sucrose, dicyclohexyl phthalate, triphenyl phosphate, glycerol tribenzoate, 1-dibenzoate, 4-cyclohexane dimethanol (CHDM), pentaerythritol tetrabenzoate, alkyl glycol esters or mixtures thereof.
    类似技术:
    公开号 | 公开日 | 专利标题
    BR112014015883B1|2021-05-11|use of an alternative non-phthalic monobenzoate as a plasticizer to disperse a polymer to form a plastisol, as well as the plastisol and its composition
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    同族专利:
    公开号 | 公开日
    EP2814878A1|2014-12-24|
    IN2014DN06861A|2015-05-22|
    WO2013123188A3|2015-03-12|
    MX2014009820A|2014-09-25|
    AU2013221560A1|2014-06-26|
    JP2016188372A|2016-11-04|
    AU2013221533B2|2015-11-26|
    RU2584011C2|2016-05-20|
    JP2015518057A|2015-06-25|
    MX2014009821A|2015-03-03|
    AU2013221582A1|2014-08-28|
    WO2013123188A2|2013-08-22|
    JP2015518058A|2015-06-25|
    BR112014015883A2|2017-06-13|
    IN2014DN06860A|2015-05-22|
    CA2864240A1|2013-08-22|
    RU2014136797A|2016-04-10|
    CA2864252A1|2013-08-22|
    US20140275376A1|2014-09-18|
    CA2863431A1|2013-08-22|
    EP2814894A4|2016-03-09|
    KR101626123B1|2016-05-31|
    AU2013221533A1|2014-08-28|
    WO2013123149A2|2013-08-22|
    AU2013221560B2|2015-11-05|
    AU2013221582B2|2016-01-21|
    WO2013123127A1|2013-08-22|
    MX2014008582A|2014-08-22|
    EP2814878A4|2015-07-29|
    KR20140126374A|2014-10-30|
    CN104704077A|2015-06-10|
    BR112014015883A8|2017-07-04|
    RU2601458C2|2016-11-10|
    CN104080850A|2014-10-01|
    KR20140131538A|2014-11-13|
    SG11201404896SA|2014-12-30|
    US20150038625A1|2015-02-05|
    EP2841512A4|2016-03-09|
    WO2013123149A3|2015-03-12|
    JP5985660B2|2016-09-06|
    US9725573B2|2017-08-08|
    JP2015506409A|2015-03-02|
    US20150025187A1|2015-01-22|
    EP2814894A2|2014-12-24|
    CA2864252C|2016-08-09|
    SG11201403068VA|2014-09-26|
    RU2014136798A|2016-04-10|
    KR20140131537A|2014-11-13|
    EP2814878B1|2018-05-23|
    RU2014136796A|2016-04-10|
    EP2841512A2|2015-03-04|
    SG11201404897TA|2014-10-30|
    CN104619430A|2015-05-13|
    CA2863431C|2017-03-21|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US1899214A|1932-02-10|1933-02-28|Eastman Kodak Co|Cellulose organic ester composition containing phenylethyl benzoate|
    GB546716A|1941-01-25|1942-07-28|John Heron Mcgill|Production of improved coatings on fabric supports|
    GB1155572A|1965-08-28|1969-06-18|Bridgestone Tire Co Ltd|Adhesives for Tyre Cords|
    GB1103681A|1966-01-28|1968-02-21|Geigy Uk Ltd|Chemical compositions|
    GB1321383A|1970-11-12|1973-06-27|Sheller Globe Corp|Vinyl chloride resin moulding compositions|
    US3987001A|1975-02-03|1976-10-19|Chevron Research Company|Ultraviolet protectorant composition|
    JPS6357550A|1986-08-28|1988-03-12|Chisso Corp|Production of stabilized ester based plasticizer|
    US5236987A|1987-07-02|1993-08-17|Velsicol Chemical Corporation|Isodecyl benzoate coalescing agents in latex compositions|
    US5102654A|1990-04-18|1992-04-07|Revlon, Inc.|Nail enamel emulsion lacquer comprising a water phase and a lacquer phase|
    US5747573A|1994-02-07|1998-05-05|H. B. Fuller Licensing & Financing, Inc.|High heat resistant hot melt adhesive|
    US5728760A|1995-04-11|1998-03-17|Great Lakes Chemical Corporation|Use of ring-brominated benzoate compounds as flame retardants and/or plasticizers|
    JPH0948745A|1995-08-04|1997-02-18|Kuraray Co Ltd|Production of carboxylic acid ester|
    US6300400B1|1997-04-18|2001-10-09|Illinois Tool Works Inc.|Wallboard adhesive|
    FR2766834B1|1997-07-29|1999-10-08|Eurocopter France|ADHESIVE COMPOSITION FOR HOT GLUING AND GLUING PROCESS FOR IMPLEMENTING IT|
    US5990214A|1997-07-31|1999-11-23|Velsicol Chemical Corporation|Liquid glycol benzoate compositions|
    US5965111A|1998-05-01|1999-10-12|The Procter & Gamble Company|Fast drying water-borne nail polish|
    US6221571B1|1998-12-10|2001-04-24|Eastman Kodak Company|Silver halide light-sensitive element|
    US6130031A|1998-12-11|2000-10-10|Eastman Kodak Company|Photographic element containing a benzolylacetanilide DIR coupler|
    US6689830B1|1999-10-15|2004-02-10|Velsicol Chemical Corporation|Film forming compositions containing benzoic acid esters of 8-carbon alcohols as additives|
    JP2002194159A|2000-12-25|2002-07-10|Kanegafuchi Chem Ind Co Ltd|Vinyl chloride-based paste resin composition and disposable glove|
    US6537530B2|2001-01-26|2003-03-25|Tevco, Inc.|Phthalate free nail polish enamel composition employing novel plasticizers|
    CN101676341B|2001-02-22|2013-01-09|威士伯采购公司|Coating compositions containing low voc compounds|
    US6939551B2|2001-05-21|2005-09-06|Coty Inc.|Cosmetic films|
    US7056966B2|2001-08-30|2006-06-06|Velsicol Chemical Corporation|Liquid benzoate ester compositions and aqueous polymer compositions containing same as plasticizers|
    JP2003334441A|2002-03-13|2003-11-25|Kyoeisha Chem Co Ltd|Solid acid catalyst for esterifying carboxylic acid|
    US20030185774A1|2002-04-02|2003-10-02|Dobbs Suzanne Winegar|Cosmetic coating composition comprising carboxyalkyl cellulose ester|
    US7071252B2|2002-09-12|2006-07-04|Velsicol Chemical Corporation|Plasticizer compositions for non-aqueous plastisols|
    DE10249912A1|2002-10-26|2004-05-06|Oxeno Olefinchemie Gmbh|Benzoic acid isodecyclester mixtures, preparation and their use|
    US7285587B2|2002-12-20|2007-10-23|Eastman Chemical Company|Flame retardant polyester compositions for calendering|
    US20050152858A1|2003-07-11|2005-07-14|Isp Investments Inc.|Solubilizing agents for active or functional organic compounds|
    US7166275B2|2003-07-11|2007-01-23|Isp Investments Inc.|Compositions containing phenethyl aryl esters as solubilizing agents for active organic compounds|
    DE10336150A1|2003-08-07|2005-03-10|Oxeno Olefinchemie Gmbh|Foamable compositions containing isononyl benzoate|
    DE10341428A1|2003-09-09|2005-03-31|Oxeno Olefinchemie Gmbh|Use of isononyl benzoates as film-forming aids|
    WO2005069822A2|2004-01-14|2005-08-04|Finetex, Inc.|Phenylethyl benzoate for use in cosmetics, toiletries and personal care products|
    WO2006077131A1|2005-01-18|2006-07-27|Exxonmobil Chemical Patents Inc.|Improvements in or relating to plasticiser compositions|
    US20060241197A1|2005-04-25|2006-10-26|Velsicol Chemical Corporation|Plasticizer compositions for flexible closed cell foams|
    US8034860B2|2006-07-21|2011-10-11|Eastman Specialties Holdings Corporation|Organosol plastisol compositions|
    WO2008014505A2|2006-07-28|2008-01-31|Isp Investments Inc.|Blends for improved solubilization of active and functional organic compounds|
    DE102006038715A1|2006-08-18|2008-02-21|Evonik Röhm Gmbh|Plastisols based on a methyl methacrylate copolymer|
    US7812080B2|2006-12-06|2010-10-12|Genovique Specialties Holdings Corporation|Low-color foam compositions|
    JP2008231370A|2007-03-23|2008-10-02|Mitsubishi Rayon Co Ltd|Polymer particles, method of manufacturing the same, plastisol composition, and article|
    JP5015648B2|2007-04-11|2012-08-29|サイデン化学株式会社|Optical pressure-sensitive adhesive composition and optical functional film|
    US20090292058A1|2008-05-23|2009-11-26|Velsicol Chemical Corporation|Aqueous Polymer Compositions Exhibiting Increased Open Time With Reduced Levels Of Volatile Organic Compounds|
    US20110028624A1|2009-07-30|2011-02-03|Genovique Specialties Holdings Corporation|Polymer Compositions That Include High Solvating Plasticizer And Surfactant|
    US20110118362A1|2009-11-13|2011-05-19|Randal Dull|Polymers for cardiopulmonary therapies|
    JP5705998B2|2010-12-30|2015-04-22|エメラルド・カラマ・ケミカル・エルエルシーＥｍｅｒａｌｄ Ｋａｌａｍａ Ｃｈｅｍｉｃａｌ，ＬＬＣ|Novel dibenzoate plasticizer / fusion aid blends for low VOC coatings|
    IN2014DN06860A|2012-02-14|2015-05-22|Emerald Kalama Chemical Llc|EP3351101A1|2011-09-19|2018-07-25|Fenwal, Inc.|Container for storing red blood cells|
    IN2014DN06860A|2012-02-14|2015-05-22|Emerald Kalama Chemical Llc|
    WO2015124236A1|2014-02-20|2015-08-27|Fresenius Hemocare Netherlands B.V.|Medical containers and system components with non-dehp plasticizers for storing red blood cell products, plasma and platelets|
    US10995198B2|2014-09-26|2021-05-04|Emerald Kalama Chemical, Llc|Monobenzoate analogs useful as plasticizers in plastisol compositions|
    CN106715557B|2014-09-26|2019-04-12|艾默罗德卡拉玛化学品公司|It can be used as the mono benzoate analog of plasticiser in plastisol composition|
    DE102015200498A1|2015-01-14|2016-07-14|Wacker Chemie Ag|Aqueous polymer dispersions for adhesives|
    CN105086236B|2015-08-14|2017-07-11|联塑科技发展有限公司|A kind of RPVC（U‑PVC）Plastics and its pipe fitting and preparation method|
    CN105733491A|2016-04-18|2016-07-06|广东普赛达密封粘胶有限公司|Low-TVOC polyurethane weather-proof sealant and preparation method thereof|
    KR20190033486A|2016-06-01|2019-03-29|학 에스. 강|Ultra low heat fusion PVC alternative Plastisol coating and printing ink|
    US11193035B2|2016-06-01|2021-12-07|Hack S. Kang|Ultra low thermo fusion PVC plastisol coating and textile printing ink|
    EP3438179B1|2016-12-12|2022-02-02|LG Chem, Ltd.|Plasticizer composition and resin composition including same|
    KR102236923B1|2017-12-04|2021-04-07|주식회사 엘지화학|Plasticizer composition and resin composition comprising the same|
    EP3802693A1|2018-06-07|2021-04-14|Eastman Chemical Company|Highly filled plastisols|
    US10793807B2|2018-07-19|2020-10-06|International Flavors & Fragrances Inc|Organoleptic compounds|
    KR102211886B1|2019-04-03|2021-02-03|성원판지 주식회사|Self-adhesive and sealed eco-friendly paper packaging materials|
    CA3135399A1|2019-04-05|2020-10-08|Emerald Kalama Chemical, Llc|Low voc multifunctional additives to improve waterborne polymer film properties|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-15| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-24| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-03-16| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-05-11| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/02/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261598372P| true| 2012-02-14|2012-02-14|
    US61/598,372|2012-02-14|
    PCT/US2013/026049|WO2013123127A1|2012-02-14|2013-02-14|Monobenzoate useful as a plasticizer in plastisol compositions|
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