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    • 专利摘要:
    PROCESS TO PRODUCE A DRY POLY (VINYL CHLORIDE) MIXTURE COMPOSITION AND WIRE OR CABLE SHIRT OR SHIRT. Processes are provided to produce a poly (vinyl chloride) deca (PVC) composition with a plasticizer based on a biological source free of phthalates and fillers, having an apparent density greater than 0.67 g / cm3 and an extrusion rate greater than 65 g / min for a 19 mm barrel diameter single-screw extruder with a 25: 1 L / D general purpose polyethylene screw at 75 rpm, and compositions prepared by the processes.
    公开号:BR112014007396B1
    申请号:R112014007396-1
    申请日:2012-09-14
    公开日:2021-01-12
    发明作者:Manish K. Mundra；Neil W. Dunchus；Anthony C. Neubauer；Caroline H. Laufer；Michael B. Biscoglio；Robert F. Eaton；Abhijit Ghosh-Dastidar
    申请人:Dow Global Technologies Llc；
    IPC主号:
    专利说明:

    [0001] [001] This invention relates to mixtures of poly (vinyl chloride) (PVC) and a plasticizer derived from a biological source, and to processes for preparing mixtures of PVC and plasticizer based on a biological source. History of the invention
    [0002] [002] PVC compositions are well known in the art (see, for example, USP 6,063,846, USP 6,608,142 and U.S. patent publication 2005/0203230). PVC compositions that do not contain a plasticizer tend to be rigid and are suitable for the manufacture of rigid products such as pipes and plumbing. PVC compositions that include a plasticizer tend to be flexible and are suitable for use in applications such as coating and insulation of wires and cables, and medical device components. Examples of PVC compositions containing a plasticizer include FLEXALLOY® products obtainable from Teknor Apex.
    [0003] [003] Plasticizers are compounds or mixtures of compounds that are added in polymeric resins to provide ductility and flexibility. Phthalic acid diesters (also known as "phthalate") are well-known petroleum-based plasticizers that are widely used in many flexible polymer products, such as polymer products formed from PVC and other polar polymers. Known petroleum derived plasticizers also include adipic trimellites and polyesters, both typically used in high temperature applications. Mixtures of plasticizer are often used to obtain optimal properties.
    [0004] [004] However, petroleum-based plasticizers, particularly phthalate plasticizers, are under intense scrutiny by public interest groups that are concerned with their negative environmental impact and potential adverse health effects on human beings (especially children). As such, plasticizers derived from other sources become of great interest, particularly those derived from biological sources such as seeds and nuts. Exemplary biological sources include, but are not limited to, oils derived from soybeans, flaxseed, tung seed, coconut, palm, olive, cotton seed, seed of castor and castor. Plasticizers derived from biological sources are generally phthalate free. Plasticizers based on biological sources are advantageous because they help to reduce greenhouse gas emissions, and allow the user to obtain carbon and / or LEED credits (Leadership in Energy and Environmental Design). However, if conventional processes for producing a dry PVC mixture use a plasticizer based on biological sources, it will result in a very dry powder mixture having a low bulk density, for example, less than 0.60 g / cm3, with production feed rates very unsatisfactory for a subsequent extruder or other processing apparatus, for example, a production rate in the range of 10-50 g / min for a 19 mm barrel single spindle extruder with L spindle for general purpose polyethylene / D 25: 1 at a spindle speed of 75 rpm. If a conventional process for producing a dry PVC mixture uses a conventional phthalate plasticizer, it will result in a dry powder mixture having a high bulk density, for example, greater than 0.7 g / cm3, with very good production feed rates for a subsequent extruder or other processing apparatus, for example, a production rate in the range of 65-75 g / min for a 19 mm barrel single-spindle extruder with spindle for general purpose polyethylene with L / D 25: 1 at a spindle speed of 75 rpm. Consequently, there is a need for a process to produce dry mixtures of PVC and phthalate-free plasticizers based on biological sources having the same, or substantially the same, chemical and / or physical properties as dry mixes prepared from PVC and plasticizers from phthalates. Summary of the invention
    [0005] [005] In embodiments of the invention, a process is provided to produce a dry PVC blend composition having an apparent density greater than 0.67 g / cm3, which comprises PVC, a plasticizer based on a phthalate-free biological source and a load. In an embodiment, the process comprises mixing the PVC, plasticizer based on biological source and filler at a temperature ranging from 25 ° C to 70 ° C for a period of time effective to form the dry PVC mix composition. In another embodiment, the process comprises mixing PVC with the biological source plasticizer at 25 ° C to 70 ° C for an adjusted retention time before combining the load to produce the dry PVC mix composition. In incorporations of the process, mixing of PVC, plasticizer based on biological source and filler is carried out until the apparent density is reached at a drop temperature of 55 ° C to 65 ° C. In some embodiments, the dry PVC mix composition has an extrusion rate greater than 65 g / min. In embodiments, the dry PVC mix composition has a density in the range of 0.67-0.76 g / cm3 and a production rate in the range of 68-7 6 g / min for a single screw extruder with a diameter of 19 mm barrel with a 25: 1 L / D general purpose polyethylene spindle at a speed of 75 rpm.
    [0006] [006] In an embodiment, the invention is a process for producing a dry blend composition of poly (vinyl chloride) (PVC), the process comprising mixing PVC, a plasticizer based on a phthalate-free biological source, and a filler in a temperature between 25 ° C and 70 ° C and in an effective time to form a dry mixture comprising aggregated PVC particles and an apparent density greater than 0.67 g / cm3. In an embodiment, the invention is a composition prepared by the process. In another embodiment, the invention is an article prepared with the composition.
    [0007] [007] In incorporations, the composition comprises a dry mixture of aggregated PVC particles, which have an average particle size of 0.1 to 10 mm. In some embodiments, the cargo particles agglomerate on the surface of the aggregated PVC particles.
    [0008] [008] In incorporations, the dry mix composition comprises: (A) from 20 to 80% by weight of PVC; (B) 10 to 40% by weight of plasticizer based on biological source; and (C) from 5 to 40% by weight of cargo.
    [0009] [009] The PVC dry mix composition may also include one or more conventional additives such as thermal stabilizers, flame retardant fillers, UV stabilizers, sliding agents, process aids, etc. When used, the sum of all conventional additives can be in an amount greater than 0% by weight up to 40% by weight, based on the total weight of the dry PVC mix composition.
    [0010] [010] In preferred embodiments, the biological-based plasticizer comprises a mixture of an epoxidized oil (i.e., epoxidized liquid triglyceride) and an epoxidized fatty acid C1-C14 ester, preferably an epoxidized C1-C10 fatty acid , more preferably a C1-C8 epoxidated fatty acid, most preferably a C1 epoxidated fatty acid. In an additional preferred embodiment, the biological source plasticizer comprises a mixture of epoxidized soy oil (ESO) and soy oil epoxidated methyl ester (soy-eFAME). In another preferred embodiment the plasticizer based on biological source comprises a mixture of 65:35 to 50:50 (weight / weight) of ESO and soy-eFAME.
    [0011] [011] The invention further provides articles such as a sheath or jacket made of wire or cable made with the dry PVC mixture composition.
    [0012] [012] The use of biological-based plasticizers is advantageous because, in relation to conventional petroleum-based plasticizers, such as phthalates or trimellites, biological-based plasticizers are environmentally convenient and derived from renewable sources. The present process overcomes several problems that prevented several plasticizers based on biological sources from being used in compositions based on PVC resin. Compositions of dry PVC mixtures prepared according to the process of the invention provide improved production feed rates when compared to production feed rates of a dry PVC mix prepared by the conventional phthalate process (using a drop temperature greater than 65 ° C, or more preferably greater than 75 ° C and most preferably greater than 85 ° C), which is due, at least in part, to the level of apparent density and the morphology of the PVC particles in the composition resulting from the process of invention Brief description of the figures
    [0013] [013] Figures 1A-1B are scanning electron microscope (SEM) micrographic images (200 micron scale) of dry mix PVC particles from Comparative Examples using conventional phthalate plasticizer (DIDP) and Inventive Examples using plasticizer a biological source base (LPLS), respectively, from Example 1; and
    [0014] [014] Figure 2 is a graph of the data from Example 5, showing% cumulative and% by volume against microns (μm) of the aggregated PVC particles measured by Malvern sieve analysis. Detailed description of the preferred embodiment Definitions
    [0015] [015] Unless stated to the contrary, implicit in context, or customary in the technique, all parts and percentages are based on weight.
    [0016] [016] In this disclosure, the numerical ranges are approximate, and therefore may include values outside the range unless otherwise indicated. The numeric ranges include all values of and including the lower value and the upper value, in increments of one unit, as long as there is a separation of at least two units between any lower value and any upper value. As an example, if a composition, physical or other property, such as, for example, molecular weight etc., is 100 to 1,000, then all individual values, such as 100, 101, 102, etc., and sub-bands, such as from 100 to 144, from 155 to 170, from 197 to 200, etc., will be expressly listed. For ranges containing values less than one or containing fractional numbers greater than one (for example, 1.1, 1.5, etc.), a unit is considered to be 0.0001, 0.001, 0.01 or 0.1 , when appropriate. For ranges containing single-digit numbers less than ten (for example, 1 to 5), a unit would be condense as typically 0.1. These are just examples of what is specifically intended, and all possible combinations of numerical values between the minimum value and the maximum value listed, will be considered to be expressly stated in this disclosure. Within this disclosure, numerical ranges are provided for, among other things, the relative amounts of plasticizer based on biological sources and PVC in dry mixtures.
    [0017] [017] "Composition" and similar terms mean a mixture or composition of two or more components.
    [0018] [018] "Plasticizer" and similar terms mean a substance that decreases at least one of modulus and tensile strength, and increases at least one of flexibility, elongation, impact resistance, and tear strength of a PVC resin to which it is added. A plasticizer can also decrease the melting point of a PVC resin, decrease the glass transition temperature (Tg) and / or improve the processability of the PVC resin to which it is added.
    [0019] [019] "Plasticizer based on biological source" and similar terms mean a biochemical plasticizer derived from a biological source, such as plants, animals, bacteria, yeasts, algae, etc. A plasticizer based on a biological source may comprise a single biochemical plasticizer or a mixture of two or more biochemical plasticizers. U.S. 2010/0010127 describes biochemical plasticizers and methods for their production.
    [0020] [020] "Bulk density" is defined as the weight per unit volume of material and is used mainly for powders or pellets. Bulk density is measured in the unit g / cm3 according to ASTM D1895 B.
    [0021] [021] When used herein, the term "epoxidized fatty acid ester" is a compound with at least one fatty acid moiety that contains at least one epoxide group.
    [0022] [022] An "epoxide group" is a three-membered cyclic ether (also called oxirane or an alkylene oxide) in which an oxygen atom is attached to two carbon atoms that are already attached to each other.
    [0023] [023] When used herein, the term "production feed rate" is the feed rate in g / min of a 19 mm barrel diameter single spindle extruder with a L / D general purpose polyethylene spindle 25: 1 at a spindle speed of 75 rpm, which is measured by collecting and weighing extruder production for a specific increment of time (3 minutes) and reported as g / min. Biologically based plasticizers
    [0024] [024] The biological-based plasticizer comprises one or more epoxidized biochemical plasticizers. For the purposes of this disclosure, a plasticizer is epoxidized if it contains at least one epoxide group. Non-limiting examples of suitable epoxidized biochemical plasticizers include naturally occurring epoxidized oils such as Vernonia oil, etc .; esters of epoxidized fatty acids from plant and animal oils such as epoxidized soybean oil (ESO), epoxidized corn oil, epoxidized sunflower seed oil, epoxidized palm oil, epoxidized linseed oil, epoxidized canola oil, epoxidized canola oil epoxidized rapeseed, epoxidized safflower oil, epoxidized tung oil, epoxidized tallow oil, epoxidized castor oil, epoxidized fish oil, epoxidized bovine fat oil, epoxidized algae oil, etc .; esters of C1-C14 fatty acids epoxidized from plant, algae and animal oils including methyl, ethyl, propyl, butyl and 2-ethylhexyl esters, such as soybean oil methyl ester (soy-eFAME), etc .; derivatives of epoxidated fatty acids such as epoxidized propylene glycol dioleate, epoxidated methyl stearate, epoxidated butyl stearate, epoxidated 2-ethylhexyl stearate, epoxidized stearyl stearate, epoxidized carboxylate epoxidized soy oil cyclohexyl-methyl-3,4-epoxy-cyclohexane, diepoxy poly (ethylene glycol) soya, etc .; and any combination of the above. Preferred biochemical plasticizers include ESO and soy-eFAME.
    [0025] [025] In a preferred embodiment, the biochemical plasticizer comprises a mixture of one or more epoxidized fatty acid esters (eg, ESO) and one or more epoxidated C1-C14 fatty acid esters (eg, soy-eFAME). A preferred blend of biochemical plasticizers comprises soy-eFAME and ESO in a weight ratio of 75:25 to 25:75, preferably from 35:65 to 50:50. In general, soy-eFAME is composed of 10-15% by weight of saturated fatty acids (palmitic acid and stearic acid) and 85-90% by weight of unsaturated fatty acids (oleic acid, linoleic acid, linolenic acid). A non-limiting example of an appropriate blend of plasticizers is the biochemical plasticizer ECOLIBRIUM LPLAS (The Dow Chemical Company), which is composed of a mixture of soy-eFAME and ESO. Poly (vinyl chloride) resins
    [0026] [026] The poly (vinyl chloride) resin (also referred to as a vinyl chloride polymer) component of the dry mix PVC composition is a high molecular weight solid polymer that can be a poly (vinyl chloride homopolymer) ) or a vinyl chloride copolymer having copolymerized units of one or more additional comonomers. Grafting vinyl chloride copolymers are also suitable for use in dry mix PVC compositions. For example, ethylene copolymers, such as ethylene / vinyl acetate copolymer, and ethylene copolymer elastomers, such as EPDM (copolymers comprising copolymerized units of ethylene, propylene and dienes) and EPR (copolymers comprising copolymerized units of ethylene and propylene ) that are grafted with vinyl chloride can be used as the component vinyl chloride polymer in the dry mix PVC composition. Charge
    [0027] [027] The dry mix PVC composition includes one or more fillers. Examples of suitable fillers include silica, clay, titanium dioxide, talc, calcium carbonate, calcined kaolin (clay), and other mineral fillers. The loads can be coated or uncoated. Optionally, the load can be subjected to a drying process to reduce the water content. The filler should be included in the composition in an amount within the range of greater than 0 to 40, preferably from 5 to 40% by weight, preferably from 5 to 30% by weight based on the weight of the dry mix composition. Additions
    [0028] [028] The PVC dry mix composition may optionally contain additives such as antioxidants (for example, hindered phenolics (such as IRGANOX® 1010 or IRGANOX® 1076), free radical purgers, phosphites (for example, IRGAFOS® 168 , all trade names of Ciba Geigy), pigments (TiO2 particles), thermal stabilizers, light stabilizers, blowing agents, lubricants, dyes, processing aids, crosslinking agents, flame retardants, anti-condensation agents, curing agents, reinforcers of retardants, coupling agents, antistatic agents, nucleating agents, sliding agents, viscosity controlling agents, tackiness agents, non-stick agents, surfactants, diluent oils, acid purgers, metal deactivators, and the like. that the compositions are made-to-measure for use in various applications. If additives are present, they represent a amount less than or equal to 15% by weight based on the total weight of the dry mix composition.
    [0029] [029] Examples of halogen-free inorganic flame retardant fillers include metal hydrates such as aluminum hydrate and magnesium hydrate, metal hydroxides such as magnesium hydroxide (Mg (OH) 2) and aluminum trihydride (ATH) ( for example, APYRAL 40CD (Nabeltec)), metal oxides such as titanium dioxide, silica, alumina, huntite, antimony trioxide, potassium oxide, zirconium oxide, zinc oxide, carbon black, carbon fibers, expanded graphite , talc, clay, organo-modified clay, calcium carbonate, red phosphorus, wollastonite, mica, ammonium octamolybdate, fries, hollow glass microspheres, glass fibers, and the like. In some embodiments, the dry-mix PVC composition preferably includes a thermal stabilizer. Non-limiting examples of suitable thermal stabilizers include lead-free metal mixture thermal stabilizers, lead stabilizers, organic thermal stabilizers, epoxides, monocarboxylic acid salts, phenolic antioxidants, organic phosphites, hydrotalcites, zeolites, perchlorates and / or beta-diketones . Non-limiting examples of beta-diketones are: dibenzoyl methane, palmitoyl benzoyl methane, stearoyl benzoyl methane and mixtures thereof. A non-limiting example of suitable dibenzoyl methane is RHODIASTAB® 83. A non-limiting example of appropriate mixtures of palmitoyl benzoyl methane and stearoyl benzoyl methane is RHODIASTAB® 50. Examples of lead-free mixed metal thermal stabilizers include MARK® 6797, MARK® 6776 ACM, MARK® 6777 ACM, THERM-CHEK® RC215P, THERM-CHEK® 7208, NAFTOSAFE® EH-314, BAEROPAN® MC 90400 KA, BAEROPAN® MC 90400 KA / 1, BAEROPAN® MC 8553 KA-ST 3-US , BAEROPAN® MC 9238 KA-US, BAEROPAN® MC 90249 KA, and BAEROPAN® MC 9754 KA. Thermal stabilizers can be used in amounts of 0 to 40, preferably 0 to 5, preferably 1 to 3% by weight, based on the weight of the dry mix composition. Relative quantities of PVC, plasticizer and filler
    [0030] [030] PVC is mixed with plasticizer and filler to achieve a desired dry mix consistency. The relative amounts of PVC, plasticizer and filler may vary, but preferably, the amount of the component PVC is 20 to 80% by weight, preferably 25 to 75% by weight, preferably 30 to 60% by weight, of the biochemical plasticizer is from 10 to 40% by weight, preferably from 15 to 35% by weight, preferably from 15 to 30% by weight, and the load is more than 0 to 40% by weight, preferably from 5 to 40% by weight, preferably from 5 to 30% by weight, based on the total weight of the dry mix composition. In some embodiments, the dry blend composition further comprises a thermal stabilizer in an amount of 0 to 5% by weight, preferably 1 to 3% by weight, and / or a flame retardant in an amount of 0 to 20% by weight, preferably from 0 to 10% by weight, based on the total weight of the dry mix composition. Preparation of the dry mix composition
    [0031] [031] In incorporations, the dry PVC mixture is prepared by absorbing the biochemical plasticizer in the PVC powder and the adhesion of the charge particles on the surface of the PVC particles.
    [0032] [032] Dry mix composition can be prepared using high, medium or low intensity solid mixers such as HENSCHEL or PAPENMEYER mixers or similar (high intensity), or LÖDIGE plow blade mixer or similar mixers (medium intensity) , or a BRABENDER® mixer, a tape mixer or similar mixers (low intensity). In a first step, powdered PVC is mixed during heating to a stock temperature that is at or below the melting point of the pure PVC resin, preferably ranging from 25 ° C to 70 ° C. The heating of the powdered PVC can be done through the use of a heated jacket of the mixer and / or by frictional heat that is generated during the mixing process. In preferred embodiments, the PVC powder is combined with a thermal stabilizer, preferably in a weight ratio of 97-99: 3-1.
    [0033] [033] After reaching the PVC stock temperature, the biochemical plasticizer is added to the component PVC with stirring. In some incorporations, the PVC stock and plasticizer are mixed for a minimum residence time ("retention time") before combining the component load and optional additives with the PVC / plasticizer mixture. In some embodiments, the retention time before adding the load is 0.5 to 5.0 minutes, preferably 1 to 3 minutes, to allow absorption of the plasticizer into the PVC powder such that a consistency of the material is of aggregated particles. Preferably, the aggregated PVC particles have an average particle size ranging from 0.1 to 10 mm, preferably from 0.1 to 5 mm, with the preponderance of the particles having an average particle size from 1 to 5 mm, preferably from 3 to 5 mm. Although not preferred, in some embodiments, the charge can be added together with the plasticizer in the PVC stock.
    [0034] [034] Temperatures and process times of PVC and plasticizer, and the order of charge addition (and of optional thermal stabilizer and or other additives) can be adjusted, for example, according to the diffusion characteristic of the plasticizer in the particles of PVC, coupled with the solubility of the liquid plasticizer at a given temperature, such that there is sufficient surface tension of the partially dried PVC granules to allow the filler and stabilizer to bond to the PVC particles.
    [0035] [035] PVC, plasticizer based on biological source and filler components are then mixed for up to 45 minutes, preferably less than 25 minutes with a minimum of 1 minute, until a drop temperature such that the apparent density of the dry mixture is at least 0.67 g / cm3, preferably at least 0.7 g / cm3. Bulk density can be monitored during the mixing process to avoid under-mixing or over-mixing the dry mix composition and to maximize the dry mix properties (eg extruder feed rate). The "drop temperature" is a higher temperature at which the dry mix composition is discharged or evacuated differently from the mixing equipment to an additional processing apparatus such as an extruder, pelletizer, etc. The drop temperature is adjusted to a temperature based on the desired bulk density of the dry PVC mixture with plasticizer incorporated in the PVC. In embodiments, the drop temperature is in the range between 55 and 65 ° C, preferably 60 ° C.
    [0036] [036] The process of the invention increases the apparent density of dry PVC mixtures compositions prepared with a biochemical plasticizer aggregating the PVC particles and through the adhesion of the charge particles on the surface of the PVC particles during the agglomeration process, which preferably it is uniform adhesion. In some embodiments, the process results in an increase in the apparent density of the dry PVC mix composition by 20 to 40%, for example, from a minimum of 0.60 g / cm3 to a maximum of 0.85 g / cm3.
    [0037] [037] Figure 1A is a SEM image (200 micron scale) of PVC particles from a dry mix composition prepared with DIPD phthalate plasticizer. By comparison, the dry mix composition resulting from the present process has a consistency that dries to the touch under ambient conditions and an appearance illustrated in Figure 1B (200 micron SEM image) showing aggregated PVC particles from a dry mix composition prepared with the biochemical plasticizer LPLAS 1101 with agglomerated particles of the load adhered to the surface of the PVC particles.
    [0038] [038] The surprising properties of dry PVC mix compositions prepared according to the process of the invention allow subsequent processing at an increased production feed rate during the initial part of a melt composition step due, at least in part, to the size and morphology of the PVC particle aggregates / filler and / or the apparent density of the dry mix composition, than to the improved fluidization kinetics and higher process rates (for example, through an extruder or composition extruder). Manufacturing articles
    [0039] [039] The dry PVC mix composition can then be discharged into a holding compartment for later use, or combined (via, for example, melt extrusion) and molded into an article (eg film, pellets, etc.) . For example, the dry PVC mix composition can be further combined with component ingredients using a mixing apparatus such as a FARREL continuous mixer and / or a single or two-screw extruder such as a Werner & Pfleiderer two-screw extruder or a BUSS KHEADER continuous single-screw extruder.
    [0040] [040] In particular embodiments, the dry PVC mix composition can be applied as a cable cover, for example, a cover, sheath or insulating layer, in known quantities and by known methods (for example, with equipment and methods described in USP 5,246,783 and 4,144,202). Typically, the composition is prepared in a reactor / extruder equipped with a cable sheath matrix and after components are formulated, the composition is extruded onto the cable when the cable is stretched through the matrix. The layer (coating) is then typically subjected to a curing period at temperatures from room temperature to, but below, the melting point of the composition until the article has reached the desired degree of crosslinking. Curing can start in the reactor / extruder. Examples
    [0041] [041] The following examples illustrate incorporations of methods for compositions of dry PVC mixtures according to the present invention. Unless otherwise stated, all parts and percentages are by weight. Materials and methods
    [0042] [042] The materials listed in Table 1 are used in the Comparative Examples and in the Inventive Examples.
    [0043] [043] The following procedure is used to prepare dry PVC mix compositions. Dry mix preparation
    [0044] [044] Initially, PVC (97-99% by weight) and BAEROPAN® MC 9754 KA (1-3% by weight) are mixed together in a 20 L plow mixer (Gebr. Lödige Maschinenbau, Germany ) at 100 rpm and heat up to stock temperature. The plasticizer is preheated to 60 ° C and then pumped into the PVC stock mixture (in a pumping time of 5.5 minutes). The mixing at the stock temperature continues for the projected retention time and then the CaCO3 charge is added. Mix the mixture until the discharge (drop) temperature is reached. Bulk density is measured according to ASTM D-792. Casting composition
    [0045] [045] The dry PVC mix composition is then fed into a 19 mm dry feed extruder (single spindle, Brabender) to characterize the maximum extrusion rate at a fixed rotation per minute without leaking the loading funnel. The dry mix composition is mixed at a melting temperature of 180 ° C (zone 1: 175 ° C, zone 2: 175 ° C, zone 3: 180 ° C, zone 4: 180 ° C). Plate preparation
    [0046] [046] Samples of the PVC dry mix compositions are compression molded using a Greenard Hydrolair steam press (with rapid cooling capability) operating in manual mode. Prepare a 50 milliliter plate of 8 x 8 for each sample. The press is preheated to 180 ° C (± 5 ° C). A total of 50-85 g of material is pre-weighed and placed in the center of a 50 milliliter stainless steel plate between the mold set consisting of treated Mylar for mold release and aluminum foils. The filled mold is then placed in the press and the pressure is increased to 2,200 psi and 180 ° C for 5 minutes. Example 1
    [0047] [047] Tables 2-3 list formulations of Conventional and Comparative Examples, and Table 4 lists Inventive Examples. Conventional Examples 1-2 (Table 2) are formulated with the DIDP phthalate plasticizer and processed according to the processing conditions of PVC / phthalate plasticizer, bulk density and conventional production rates, using conventional industrial parameters of a temperature of PVC stock at 90 ° C at the time of adding the phthalate plasticizer and a discharge temperature of 85 ° C. Comparative Examples 1-9 (Table 3) are formulated with the biochemical plasticizer ECOLIBRIUM LPLAS-1101 using a PVC stock temperature and discharge (drop) temperature ranging from 55 ° C-75 ° C. Inventive Examples 1-2 (Table 4) are formulated with the biochemical plasticizer and processed at a PVC stock temperature and a discharge temperature of 60 ° C.
    [0048] [048] The results of the Conventional, Comparative and Inventive Examples are shown in Tables 2-4.
    [0049] [049] The results demonstrate that the extrusion production rates for Inventive Examples 1-2 (73 and 80.4 g / min) match or exceed the extrusion production rates for Conventional Examples 1-2 (63.3 and 76.2 g / min) prepared with the DIDP plasticizer. The apparent density values of the extrusion rate of Inventive Examples 1-2 similar to those of the dry mixtures of Conventional Examples 1-2 (Table 2) formulated with the DIDP plasticizer.
    [0050] [050] The results shown in Tables 3 and 4 demonstrate that more than a 100% improvement in the extrusion production rate for Inventive Examples 1-2 prepared according to the process of the invention at 73 and 80.4 g / min compared to Comparative Examples 1-9 at 3.5 to 49.1 g / min. Example 2 (Fluidization Test)
    [0051] [051] A fluidization test is performed to determine the fluidity of the powder mixtures for Comparative Examples 1-2 (Table 3 and for Inventive Examples 1-2 (Table 4). The test with gaseous nitrogen ( N2) flowing through a calibrated glass flow meter, through a glass distillation column (> 50 mL) equipped with a glass distributor. Fifteen (15) grams of the PVC dry mix compositions are placed on the column and the N2 gas flows through the glass distillation column The minimum speed at which the particles are fluidized is visually observed The minimum fluidization speed is recorded as the fluidization speed for dry PVC mixtures.
    [0052] [052] The test results show a minimum fluidization speed of 12.7 L / min for Inventive Examples 1-2 (Table 4) and 2.3 L / min for Comparative Examples 1-2 (Table 3) . The results demonstrate that the Inventive Examples are less easily fluidized than the Comparative Examples, which is a significant factor in the extruder feed rate (production). The apparent density of the Comparative Examples at 0.60 g / cm3 versus that of the Inventive Examples at 0.72 g / cm3 correlates with the fluidization results. Example 3 (Retention time)
    [0053] [053] The dry PVC mixtures shown in Table 5 below are prepared using various retention times of the PVC stock mixture with the plasticizer before adding the CaCO3 load.
    [0054] [054] The results in Table 5 show the effect of retention time on the apparent density (g / cm3) in discharge and the extrusion rate (g / min). For Inventive Examples 1-3, the retention time before adding the CaCO3 charge is zero, 1 minute, and 2 minutes, respectively. For the Comparative Example, the retention time is 3 minutes. The Comparative Example has a lower bulk density (0.62 g / cm3) and a lower extrusion rate (63.5 g / min) compared to the Inventive Examples.
    [0055] [055] Table 6 refers to examples listed in Tables 3-4, and lists maximum retention times (in minutes) against PVC stock temperature (° C).
    [0056] [056] By matching the retention time with the PVC stock temperature, one can control the particle agglomeration characteristics and apparent density of the dry PVC mixture. The ranges for stock temperature, holding times and drop temperatures will change depending on the components (for example, type of plasticizer), the component ratio and / or the quantity of plasticizer. As an example, if the average molecular weight of the plasticizer or plasticizer mixture decreases, the retention time, stock temperature and drop temperature can be reduced to achieve, consequently, a well agglomerated, high density dry mixture that will provide a high production feed rate. In another example, with a reduction in the amount of the biochemical plasticizer, there will be less plasticizer available for the agglomeration of the PVC particles, and thus the retention time and drop temperature can be reduced. As another example, when using a low molecular weight biochemical plasticizer (for example, soy-eFAME), a rapid diffusion of PVC particles can occur, thus reducing the retention time at a given temperature. By comparison, if a high molecular weight biochemical plasticizer (eg ESO) is used, a lower diffusion rate of the PVC particles may occur, requiring a longer retention time at the same given temperature. Example 4 (PVC stock temperature)
    [0057] [057] Dry PVC mixtures listed in Table 7 below are prepared. Comparative Example 1 is prepared comprising a phthalate plasticizer (DIDP) using a PVC stock temperature of 90 ° C according to typical industrial process conditions. Comparative Examples 2-3 and Inventive Example 1 (prepared with LPLAS-1101) are prepared using different PVC stock temperatures of 90 ° C, 80 ° C, and 60 ° C, respectively.
    [0058] [058] The results show that Inventive Example 1 has an apparent density at discharge (0.75 g / cm3) and an extrusion rate (75.2 g / min) similar to the apparent density (0.72 g / cm3) and extrusion rate (76.20 g / min) of Comparative Example 1 prepared with DIDP plasticizer using a higher stock temperature (90 ° C versus 60 ° C). Inventive Example 1 also has a higher bulk density and higher extrusion rate than Comparative Examples 2-3 produced using a higher PVC stock temperature (80 ° C, 90 ° C). Example 5 (Size of agglomeration against apparent density)
    [0059] [059] Dry PVC mixtures listed in Table 8 below are prepared and the agglomeration size of the PVC particles is measured.
    [0060] [060] The dry PVC mixture of Inventive Example 1 (Table 4) (dry mixture of PVC / LPLAS 1101) has a similar appearance, particle size distribution, bulk density and fluidization characteristics as in Conventional Example 1 (Table 2 ) (dry mixture of PVC / DIDP). The characteristics of the dry PVC mixture of Comparative Example 1 (Table 3) (dry mixture of PVC / LPLAS 1101) are not similar to those of Conventional Example 1 (Table 2) (dry mixture of PVC / DIDP).
    [0061] [061] The minimum mean particleboard of a single PVC particle for each of the examples is about 200 μm. Other particles or aggregates other than PVC (ie loads) ranging from 1 to 200 μm may also be present in the system.
    [0062] [062] The minimum particle size of PVC particles is measured by scanning electron microscopy (SEM) and confirmed by measurements using a Malvern sieve analysis. Malvern sieving is a conventional technique for particle size analysis, providing mass distributions across a wide range of sizes. In general, the technique separates a sample according to the size of the particles by passing them through a series of fine mesh sieves stacked on top of each other. Then, the particle size distribution is calculated by measuring the mass of the particles retained in each sieve. In doing so, it is assumed that, by shaking the sieve pile, the particles are able to fall through the sieve pile until they are correctly distributed. This requires the battery to be shaken for a significant period of time. This technique represents a useful method for separating particles based on their sizes. In summary, Malvern sieve analysis separates a sample according to the size of the particles by passing them through fine mesh sieves stacked on top of each other. Then, the particle size distribution is calculated by measuring the mass of the particles retained in each sieve. Figure 2 shows the results, which shows cumulative% and volume% versus micron (μm).
    [0063] [063] The average maximum PVC particle size (μm) is reported based on the direct measurement of the larger particles against a ruler. Since the Malvern sieve process tends to break larger particles, PVC agglomerates above 500 μm are not measured in this test. Example 6
    [0064] [064] Dry PVC mixtures listed in Table 9 below are prepared using different PVC stock temperatures (and no retention times before loading).
    [0065] [065] Comparative Examples 1-2 are prepared using typical industrial process conditions, ie, PVC stock temperatures of 90 ° C and 80 ° C in a given plasticizer load, 5-10 minutes of addition time. plasticizer, and a loading load of 30% by weight. Comparative Example 3 has the same composition, but the consistency of wet cement when prepared by the process of the invention using a PVC stock temperature of 60 ° C, which demonstrates that a dry PVC / DIDP mixture cannot be produced by the process of the invention using the lowest stock temperature.
    [0066] [066] Similarly, Comparative Examples 4-5 prepared using typical industrial process conditions (PVC stock temperatures of 80 ° C and 90 ° C) produced mixtures having lower apparent density and extrusion rate compared to Inventive Example 1 having the same PVC / LPLAS formulation, but prepared according to the process of the invention (PVC stock temperature 60 ° C).
    [0067] [067] Inventive Example 1 (mixture of PVC / LPLAS) prepared according to the process of the invention (using a PVC stock temperature of 60 ° C) has an apparent dry mix density (0.75 g / cm3) and extrusion rate (75.2 g / min) comparable to Comparative Example 1 (dry PVC / DIDP mixture prepared using typical industrial process conditions (PVC stock temperature 90 ° C)). Example 7 (Changes to process conditions)
    [0068] [068] Table 10 below provides process conditions for a range of stock temperatures, holding times and drop temperatures to produce a dry blend of PVC with ECOLIBRIUM LPLAS-1101, a biochemical plasticizer composed of a 50:50 mixture (weight / weight) of ESO and soy-eFAME in a loading of 24% by weight according to the process of the invention.
    权利要求:
    Claims (9)
    [0001]
    Process for producing a dry poly (vinyl chloride) (PVC) mixture composition, characterized by the fact that it comprises: (A) mixing PVC powder, while heating to a stock temperature of or below the melting point of pure PVC resin; (B) after the stock temperature is reached, add a plasticizer based on biological source to the PVC component with agitation; (C) mix the PVC powder and the plasticizer for a retention time before adding a charge; the retention time being 0.5 to 5.0 minutes; and (D) mixing the PVC powder, the plasticizer based on biological source and the filler for 1 to 45 minutes at a drop temperature to form a dry mix composition comprising aggregated PVC particles with an apparent density greater than 0.67 g / cm3, the drop temperature being 55 ° C to 65 ° C.
    [0002]
    Process according to claim 1, characterized in that the biological-based plasticizer comprises an ester mixture of an epoxidated fatty acid ester and C1-C14 ester of epoxidized fatty acid.
    [0003]
    Process according to claim 2, characterized in that the biological source plasticizer comprises a mixture of epoxidized soy oil (ESO) and epoxidized methyl ester of soy oil (soy-eFAME).
    [0004]
    Process, according to claim 3, characterized by the fact that the biological-based plasticizer comprises a mixture of 75:25 to 25:75 (weight / weight) of ESO and soy-eFAME.
    [0005]
    Process according to claim 1, characterized in that the dry PVC mixture composition comprises: (A) from 20 to 80% by weight of PVC; (B) 10 to 40% by weight of plasticizer based on biological source; and (C) from 5 to 40% by weight of cargo.
    [0006]
    Process according to claim 1, characterized in that the dry PVC mix composition has an extrusion rate greater than 65 gm / minute for a single-screw extruder with a 19 mm (0.75 inch) barrel diameter with a general purpose polyethylene spindle with 25: 1 L / D at a spindle speed of 75 rpm.
    [0007]
    Process according to claim 1, characterized in that the aggregated PVC particles have an average particle size of 0.1 to 10 mm.
    [0008]
    Process according to claim 1, characterized in that the filler particles are agglomerated over the agglomerated PVC particles.
    [0009]
    Wire or cable jacket or jacket, characterized by the fact that it is made from a composition prepared by the process defined in claim 1.
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    同族专利:
    公开号 | 公开日
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    TWI565733B|2017-01-11|
    JP6101270B2|2017-03-22|
    KR20140070566A|2014-06-10|
    US9056965B2|2015-06-16|
    EP2751199B1|2017-01-04|
    CA2850326A1|2013-04-04|
    BR112014007396A2|2017-04-04|
    CN103842428B|2016-06-08|
    CA2850326C|2019-11-12|
    MX341216B|2016-08-11|
    EP2751199A1|2014-07-09|
    US20140235769A1|2014-08-21|
    KR101963926B1|2019-03-29|
    JP2014534287A|2014-12-18|
    WO2013048775A1|2013-04-04|
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2020-06-16| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application according art. 36 industrial patent law|
    2020-10-27| B09A| Decision: intention to grant|
    2021-01-12| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 14/09/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161541223P| true| 2011-09-30|2011-09-30|
    US61/541,223|2011-09-30|
    PCT/US2012/055324|WO2013048775A1|2011-09-30|2012-09-14|Process for mixing polyvinyl chloride with a bio-based plasticizer|
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