WO2012177225A1 - Résine de styrène-acrylonitrile dotée de propriétés de transparence améliorées et son procédé de fabrication - Google Patents

Résine de styrène-acrylonitrile dotée de propriétés de transparence améliorées et son procédé de fabrication Download PDF

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Publication number
WO2012177225A1
WO2012177225A1 PCT/TH2011/000024 TH2011000024W WO2012177225A1 WO 2012177225 A1 WO2012177225 A1 WO 2012177225A1 TH 2011000024 W TH2011000024 W TH 2011000024W WO 2012177225 A1 WO2012177225 A1 WO 2012177225A1
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Prior art keywords
approximately
butylperoxy
tert
monomers
cyclohexane
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PCT/TH2011/000024
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English (en)
Inventor
Somchai PATTAMAMONGKOLCHAI
Ronnapa PHONGTHONG
Suthep KWAMPIAN
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Thai Abs Company Limited
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Priority to JP2014516955A priority Critical patent/JP5807113B2/ja
Priority to PCT/TH2011/000024 priority patent/WO2012177225A1/fr
Publication of WO2012177225A1 publication Critical patent/WO2012177225A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/28—Oxygen or compounds releasing free oxygen
    • C08F4/32—Organic compounds
    • C08F4/36—Per-compounds with more than one peroxy radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C08F212/10—Styrene with nitriles

Definitions

  • the present disclosure relates generally to a method for producing, manufacturing, or preparing a styrene acrylonitrile resin. More particularly, the present disclosure relates to a method for producing, manufacturing, or preparing a styrene acrylonitrile resin that has excellent transparency properties, enhanced clarity, reduced hue, very low haze, and/or better physical appearance as a result of a polymerization reaction that occurs in the presence of an appropriate quantity of 1,1- Di(tert-butylperoxy)cyclohexane.
  • Styrene acrylonitrile resin commonly known as SAN resin or SAN
  • SAN resin is a transparent copolymer thermoplastic.
  • SAN is widely used in the applications of food containers, kitchenware, computer products, packaging materials such as cosmetic containers, battery cases, plastic optical fibers, and electronics appliances.
  • SAN is often used in replace of polystyrene due to its greater thermal resistance.
  • SAN resin can be further used to produce or manufacture acrylonitrile butadiene styrene (ABS), which possesses high chemical resistance, strength, toughness, and rigidity.
  • ABS acrylonitrile butadiene styrene
  • SAN is produced, manufactured, or prepared by co-polymerizing styrene and acrylonitrile monomers.
  • the continuous bulk polymerization methods or processes are often used due to advantages in view of minimum or less impurities obtained and less energy consumption or cost.
  • monomers are heated to reach a certain high or relatively high temperature in order to generate free radicals, thereby thermally initiating polymerization reaction. The reaction temperature must be maintained sufficiently high in order not to compromise overall production process of polymerization.
  • a process for producing a styrene acrylonitrile (SAN) resin having enhanced transparency includes exposing an amount (e.g., mass or weight) of styrene monomers and acrylonitrile monomers under consideration to l,l-Di(tert- butylperoxy)cyclohexane, the l,l-Di(tert-butylperoxy)cyclohexane having a concentration between approximately 5 - 500 parts per million (ppm) relative to the amount of the styrene monomers and acrylonitrile monomers under consideration; initiating polymerization reactions involving the styrene monomers and the acrylonitrile monomers exposed to the l,l-Di(tert- butylperoxy)cyclohexane; continuing, maintaining, or sustaining the polymerization reactions for a polymerization time period; stopping the polymerization reactions; and obtaining a SAN resin having a haze
  • the process can additionally include exposing the styrene monomers and the acrylonitrile monomers to a solvent; exposing the styrene monomers and the acrylonitrile monomers to a chain transfer agent; and uniformly blending the styrene monomers and the acrylonitrile monomers with each of the solvent, the chain transfer agent, and the l,l-Di(tert-butylperoxy)cyclohexane.
  • Initiating the polymerization reactions can include exposing the styrene monomers and the acrylonitrile monomers to a temperature between approximately 85 - 130 °C (e.g., approximately 90, 100, 1 10, 1 15, 120, or 125 °C) to facilitate or enable the initiation or polymerization in the presence of l,l-Di(tert-butylperoxy)cyclohexane.
  • a temperature between approximately 85 - 130 °C (e.g., approximately 90, 100, 1 10, 1 15, 120, or 125 °C) to facilitate or enable the initiation or polymerization in the presence of l,l-Di(tert-butylperoxy)cyclohexane.
  • maintaining, or sustaining the polymerization reactions can include exposing the styrene monomers and the acrylonitrile monomers to a temperature between approximately 85 - 130 °C for a polymerization time interval of approximately 0.5 - 3.5 hours (e.g., a time interval of approximately 1.0 - 3.0 hours) to facilitate or enable polymerization to continue in the presence of l,l-Di(tert- butylperoxy)cyclohexane.
  • exposing the styrene monomers and the acrylonitrile monomers to 1,1- Di(tert-butylperoxy)cyclohexane occurs in the absence of exposure of the styrene monomers and the acrylonitrile monomers to a polymerization initiator that is other than l,l-Di(tert- butylperoxy)cyclohexane.
  • Other embodiments include exposing the styrene monomers and the acrylonitrile monomers to a polymerization initiator that is other than l,l-Di(tert- butylperoxy)cyclohexane, wherein the concentration of l,l-Di(tert-butylperoxy)cyclohexane is at least approximately 80% greater (e.g., approximately 90%, 95%, or 98% greater) than the concentration of the polymerization initiator that is other than l,l-Di(tert- butylperoxy)cyclohexane.
  • an enhanced transparency SAN resin produced in accordance with an embodiment of the present disclosure can be substantially identical to corresponding properties of SAN resin produced in the absence of l, l-Di(tert- butylperoxy)cyclohexane.
  • an enhanced transparency SAN resin produced in accordance with an embodiment of the disclosure can have a melt flow index (MFI) and an internal viscosity (IV) which are substantially identical to an MFI and an IV for a low transparency SAN resin produced in the absence of l,l-Di(tert-butylperoxy)cyclohexane.
  • a computer based process that is executed on a computer and which is directed to producing or manufacturing a styrene acrylonitrile (SAN) resin having enhanced transparency from styrene monomers and acrylonitrile monomers includes determining a set of process parameters for producing the SAN resin by way of receiving a target haze value in response to user input directed to the computer system; determining an amount of styrene monomers and acrylonitrile monomers under consideration; and automatically determining a l,l-Di(tert-butylperoxy)cyclohexane concentration appropriate for producing a SAN resin having the target haze value with respect to the amount of styrene monomers and acrylonitrile monomers under consideration.
  • SAN styrene acrylonitrile
  • Determining the set of process parameters can further include receiving at least one of a target polymerization reaction temperature and a target polymerization time period in response to user input directed to the computer system; and/or determining an actual or required polymerization time period that is expected to correspond to a target minimum polymer conversion percentage.
  • the process further includes producing a SAN resin having the target haze value, where such production of the SAN resin includes combining the amount of styrene monomers and acrylonitrile monomers under consideration with the determined concentration of a l,l-Di(tert- butylperoxy)cyclohexane.
  • the determined l,l-Di(tert-butylperoxy) cyclohexane concentration can be between approximately 5 - 500 ppm, and the target haze value is significantly less then approximately 0.5 (e.g., the target haze value can be less than or equal to approximately 0.45, 0.40, 0.35, 0.30, 0.25, 0.20, 0.15, or 0.10).
  • FIG. 1 is a flowchart of a process for preparing, manufacturing, or producing an enhanced or high transparency / reduced or low haze styrene acrylonitrile (SAN) resin using l,l-Di(tert- butylperoxy)cyclohexane as a sacrificial agent according to an embodiment of the disclosure.
  • SAN haze styrene acrylonitrile
  • FIG. 2A is a representative graph that illustrates a relationship between percentage conversion realized for a 2 hour polymerization time period versus ppm of l,l-Di(tert- butylperoxy)cyclohexane relative to a total weight of styrene monomers and acrylonitrile monomers mixed or blended with or exposed to l,l-Di(tert-butylperoxy)cyclohexane.
  • FIG. 2B is another representative graph that illustrates a relationship between percentage conversion realized for a 3 hour polymierization time period versus ppm of l,l-Di(tert- butylperoxy)cyclohexane relative to a total weight of styrene monomers and acrylonitrile monomers mixed or blended with or exposed to l,l-Di(tert-butylperoxy)cyclohexane.
  • FIG. 3 is a representative graph corresponding that illustrates a relationship between between measured SAN resin haze values versus ppm of Di(tert-butylperoxy)cyclohexane relative to a total weight of styrene monomers and acrylonitrile monomers that were mixed or blended with or exposed to l,l-Di(tert-butylperoxy)cyclohexane.
  • FIG. 4 is a flow diagram of a process for producing an enhanced or high transparency / reduced or low haze SAN resin or composition using l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent according to another embodiment of the disclosure.
  • Embodiments of the present disclosure are directed to aspects of processes for producing styrene acrylonitrile (SAN) resin having excellent, high, very high, or essentially maximal transparency, or equivalently, reduced, low, very low, or essentially minimal haze values.
  • Processes in accordance with the present disclosure involve exposing styrene and acrylonitrile monomers to an appropriate assistive or sacrificial agent or quasi-catalyst that significantly reduces the temperature at which polymerization occurs, significantly increases a polymerization reaction rate, and significantly increases the extent of monomer to polymer conversion.
  • Embodiments of the present disclosure are additionally directed to SAN resin produced by such processes, where the SAN resin is characterized by low or very low haze values, for instance, haze values less than or significantly less than approximately 0.50, for instance, haze values less than approximately 0.50 and greater than or equal to approximately 0.10 (e.g., haze values between approximately 0.18 - 0.48, or a haze value less than or equal to approximately 0.45, 0.40, 0.35, 0.30, 0.25, 0.20, 0.15, or 0.10).
  • haze values less than or significantly less than approximately 0.50
  • haze values less than approximately 0.50 and greater than or equal to approximately 0.10
  • haze values between approximately 0.18 - 0.48, or a haze value less than or equal to approximately 0.45, 0.40, 0.35, 0.30, 0.25, 0.20, 0.15, or 0.10 e.g., haze values between approximately 0.18 - 0.48, or a haze value less than or equal to approximately 0.45
  • an assistive or sacrificial agent or quasi-catalyst includes or is a particular organic peroxide, namely, l,l-Di(tert-butylperoxy)cyclohexane, which for purpose of brevity and clarity is referred to hereafter as a sacrificial agent.
  • concentration of l,l-Di(tert- butylperoxy)cyclohexane can be established, varied, adjusted, or tailored to produce SAN resins having target or intended haze values, as further described in detail below.
  • While other organic peroxides such as Benzoyl peroxide [C6H 5 C(0)] 2 0 2 , Di-tert-butyl perioxide (CH 3 ) 3 COOC(CH 3 ) 3 , and Tert-butylperoxy isopropyl carbonate C 8 Hi 6 0 4 are known to increase polymerization reaction rate, such other organic peroxides fail to facilitate or effectuate the production of SAN resins having significantly enhanced, high, very high, or maximal transparency (or significantly reduced, low, very low, or minimal haze values). Such other organic peroxides can additionally fail to facilitate or effectuate the production of SAN resins having other desirable properties, such as a high intrinsic viscosity.
  • set set is defined as a non-empty finite organization of elements that mathematically exhibits a cardinality of at least 1 (i.e., a set as defined herein can correspond to a singlet or single element set, or a multiple element set), in accordance with known mathematical definitions (for instance, in a manner corresponding to that described in An Introduction to Mathematical Reasoning: Numbers, Sets, and Functions, "Chapter 1 1 : Properties of Finite Sets” (e.g., as indicated on p. 140), by Peter J. Eccles, Cambridge University Press (1998)).
  • FIG. 1 is a flow diagram of a process 100 for producing a high transparency / low haze SAN resin or composition using l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent according to an embodiment of the disclosure.
  • the process 100 includes a first process portion 110 involving combining (e.g., blending or mixing) given (e.g., predetermined) quantities of styrene monomer, acrylonitrile monomer, and an appropriate solvent in a polymerization reaction vessel or chamber having a volume suitable for carrying a given (e.g., predetermined) mass of chemical constituents under consideration.
  • the vessel can be a stainless steel reactor having an internal volume of, for instance, approximately 5 or more (e.g., approximately 10, 20, 50, 100, 1000, or 2000) liters.
  • the vessel can be maintained under an inert (e.g., Nitrogen) atmosphere at a desired pressure (e.g., approximately 1 bar) during one or more portions of the process 100, in a manner understood by one of ordinary skill in the art.
  • the solvent can include one or more of an alcohol, a ketone, an aromatic hydrocarbon, or other solvent.
  • the solvent can include methanol, ethanol, methyl ethyl ketone (MEK), methyl isobutyl ketone, toluene, xylene, tetrahydrofuran, dimethylformamide (DMF), and/or another substance in which styrene monomer and acrylonitrile monomer are soluble.
  • a second process portion 120 involves introducing a given (e.g., predetermined) amount of a chain transfer and/or molecular size controlling agent such as a mercaptan into the vessel, and blending or mixing vessel contents.
  • the chain transfer / molecular size controlling agent can include or be tertiary dodecyl mercaptan (TDM).
  • TDM tertiary dodecyl mercaptan
  • the second process portion 120 can involve another chain transfer / molecular size controlling agent (e.g., a different mercaptan) depending upon embodiment details.
  • a third process portion 130 involves introducing a given (e.g., predetermined) quantity of 1,1- Di(tert-butylperoxy)cyclohexane as a sacrificial agent into the vessel, and further blending or mixing vessel contents.
  • a given (e.g., predetermined) quantity of 1,1- Di(tert-butylperoxy)cyclohexane as a sacrificial agent into the vessel, and further blending or mixing vessel contents.
  • the amount of l,l-Di(tert- butylperoxy)cyclohexane introduced into the vessel can be between approximately 5 - 500 parts per million (ppm) with respect to a total mass or weight of styrene and acrylonitrile monomers within the vessel.
  • the amount of l,l-Di(tert- butylperoxy)cyclohexane introduced into the vessel can be between approximately 10 - 400 ppm (e.g., approximately 50 - 300 ppm, or approximately 100 - 200 ppm).
  • the quantity of l,l-Di(tert-butylperoxy)cyclohexane under consideration can be selected or determined based upon the total mass or weight of styrene and acrylonotrile monomers under consideration, in view of one or more of a desired, intended, or target (a) polymerization time; (b) polymerization temperature or temperature range; (c) polymerization conversion degree, level, measure, ratio or efficiency; and (d) SAN resin haze value, as further described in detail below.
  • a process 100 in accordance with the present disclosure involves using l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent in the absence or to the exclusion of another chemical substance, composition, or compound that can act as a polymerization initiator, catalyst, or sacrificial agent.
  • l,l-Di(tert- butylperoxy)cyclohexane can be used a sacrificial agent for producing SAN resins having reduced, low, or very low haze values in accordance with the present disclosure, and one or more other chemical substances capable of acting as a polymerization initiator, catalyst, or sacrificial agent (e.g., in a manner that reduces polymerization temperature and/or enhances polymerization conversion) can be introduced into the reaction vessel (e.g., before, during, or after the third process portion 130).
  • the reaction vessel includes l,l-Di(tert- butylperoxy)cyclohexane as well as one or more other chemical substances capable of acting as a polymerization initiator, catalyst, or sacrificial agent
  • the quantity or concentration (e.g., weight percentage) of l,l-Di(tert-butylperoxy)cyclohexane should dominate or overwhelmingly dominate the quantity or concentration of such other chemical substance(s) in order to produce a SAN resin having a significantly reduced, low, very low, or essentially minimal haze value.
  • the quantity or concentration of l,l-Di(tert-butylperoxy)cyclohexane should be greater than or equal to approximately 80%, 90%, 95%, or 98% of the quantity or concentration of such other chemical substance(s).
  • a fourth process portion 140 involves heating the vessel contents to a temperature sufficient to initiate polymerization reactions.
  • the fourth process portion 140 involves heating the vessel contents to a temperature between approximately 85 - 135 °C (e.g., approximately 90 - 130 °C, or approximately 90 - 120 °C, 100 - 1 15 °C, or approximately 1 10 °C).
  • a fifth process portion 150 involves maintaining the vessel contents at a temperature or within a temperature range sufficient to sustain polymerization reactions, such as a set of temperatures within one or more of the aforementioned temperature ranges, for a given (e.g., predetermined) time interval that can be defined as a polymerization time period.
  • the polymerization time period can be approximately 1.0 to approximately 4.0 hours, for instance, approximately 1.5 - 3.5 hours (e.g., approximately 2.0, 2.5, or 3.0 hours).
  • a sixth process portion 160 involves reducing the internal temperature of the vessel to stop further polymerization reactions. In various embodiments, the internal vessel temperature can be cooled to below approximately 80 °C, for instance, to below approximately 50 °C.
  • a seventh process portion 170 involves collecting or recovering enhanced, high, or very high transparency SAN resin from the vessel.
  • SAN resins Preparation of SAN resins and analysis of styrene acrylonitrile (co)polvmer conversion
  • a SAN resin according to an embodiment of the present disclosure was prepared and analyzed using the following process portions or process steps.
  • Preparation was performed in a nitrogen atmosphere. Approximately 1 125 grams of styrene monomer, approximately 375 grams of acrylonitrile monomer, and approximately 150 grams of Ethyl benzene were introduced into a 5-liter reactor or reaction chamber. The pressure within the reactor was maintained at approximately 1 bar under nitrogen atmosphere. Ethyl benzene was used as a solvent and viscosity reducing medium for the reaction system. Styrene monomer, acrylonitrile monomer, and ethyl benzene were mixed for approximately 15 minutes to ensure uniformity. Following mixing, approximately 1.5 gram of tertiary dodecyl mercaptan (TDM) was added as a molecular size controlling agent or chain transfer agent. In addition, l,l-Di(tert- butylperoxy)cyclohexane was added as a sacrificial agent in varying amounts or concentrations, as detailed hereafter.
  • TDM tertiary dodecyl mercapt
  • approximately 0.015 gram (equal to 10 ppm based on total weight of styrene and acrylonitrile monomers), approximately 0.030 gram (equal to 20 ppm), approximately 0.075 gram (equal to 50 ppm), and approximately 0.150 gram (equal to 100 ppm), or 0.210 gram (equal to 140 ppm) of l,l-Di(tert-butylperoxy)cyclohexane were added into the reactor, after which reactor contents were further mixed or agitated for approximately 15 minutes.
  • the resulting mixture present in the reactor was heated using a heating rate of approximately 2 °C per minute up to a final temperature of approximately 140 °C for the experiment in the absence of l,l-Di(tert-butylperoxy)cyclohexane, or a final temperature of approximately 110 °C for the experiments in the presence of l,l-Di(tert- butylperoxy)cyclohexane.
  • the temperature was accordingly maintained at approximately 140 °C or approximately 110 °C as a reaction temperature for a duration or polymerization time period of approximately 1, 2, 3 or 4 hours to allow the polymerization reaction to occur.
  • the polymerization reaction was interrupted or stopped by subjecting or exposing the reactor vessel to liquid nitrogen for approximately 3 minutes.
  • Five grams of SAN samples obtained from the styrene and acrylonitrile polymerization reaction were collected and completely dissolved in approximately 100 milliliters of Methyl Ethyl Ketone (MEK). Subsequent complete dissolution, SAN samples were precipitated by introducing and stirring approximately 50 milliliters of methanol (MeOH) until SAN contents were entirely precipitated. Following the precipitation, SAN contents were filtered and dried at a temperature of approximately 80 °C for approximately 5 hours. SAN contents obtained were weighed, and percentage conversion was calculated.
  • Methyl Ethyl Ketone Methyl Ethyl Ketone
  • Table 1 shows a percentage conversion of styrene and acrylonitrile monomers to form styrene acrylonitrile resin (SAN) (co)polymer in the absence and presence of l,l-Di(tert- butylperoxy)cyclohexane as a sacrificial agent at different concentrations. As shown in Table 1, considering or comparing results corresponding to any individual reaction time (i.e.
  • a percentage conversion to SAN polymer increased from approximately 35.1, 41.9, 46.8, 62.8, 66.8, to 71.3 when an amount or concentration of l,l-Di(tert- butylperoxy)cyclohexane increased from approximately 0, 10, 20, 50, 100, to 140 ppm.
  • 1,1- Di(tert-butylperoxy)cyclohexane as a sacrificial agent can facilitate or effectuate a decrease in the reaction time required to obtain target conversion, as compared to a polymerization reaction without l,l-Di(tert-butylperoxy)cyclohexane. For example, a conversion of approximately 50% required approximately 4 hours at a reaction temperature of approximately 140 °C in the absence of l,l-Di(tert-butylperoxy)cyclohexane.
  • FIG. 2A is a representative graph corresponding to the results shown in Table 1, which illustrates a relationship between percentage conversion realized for a 2 hour polymerization time period versus ppm of l,l-Di(tert-butylperoxy)cyclohexane (relative to the total weight of styrene monomers and acrylonitrile monomers that were mixed or blended with or exposed to l,l-Di(tert- butylperoxy)cyclohexane).
  • Table 1 illustrates a relationship between percentage conversion realized for a 2 hour polymerization time period versus ppm of l,l-Di(tert-butylperoxy)cyclohexane (relative to the total weight of styrene monomers and acrylonitrile monomers that were mixed or blended with or exposed to l,l-Di(tert- butylperoxy)cyclohexane).
  • 2B is another representative graph corresponding to the results shown in Table 1, which illustrates a relationship between percentage conversion realized for a 3 hour polymierization time period versus ppm of l,l-Di(tert-butylperoxy)cyclohexane (relative to the total weight of styrene monomers and acrylonitrile monomers that were mixed or blended with or exposed to l,l-Di(tert-butylperoxy)cyclohexane). As indicated in Table 1 and each of FIGs.
  • polymer conversion is significantly enhanced even when a small concentration of 1,1- Di(tert-butylperoxy)cyclohexane (e.g., approximately, 5, 10, or 20 ppm) is considered, and very significantly or dramatically enhanced as l,l-Di(tert-butylperoxy)cyclohexane concentration further increases (e.g., to or beyond approximately 30, 40, 50, 80, 100, 120, 140, or more ppm).
  • results obtained from comparative example one suggest that a method, process, or technique for preparing or producing SAN resin according to multiple embodiments of the present disclosure can give rise to a significant or substantial increase in percentage conversion of styrene and acrylonitrile monomers at a significantly reduced reaction temperature to form SAN resin due to an activity, functionality or feature of a sacrificial agent, an assistive agent, and/or a quasi-catalyst provided by the present disclosure.
  • a SAN resin according to an embodiment of the present disclosure was prepared using the following process portions or process steps.
  • Preparation was performed in a nitrogen atmosphere. Approximately 1125 grams of styrene monomer, approximately 375 grams of acrylonitrile monomer, and approximately 150 grams of Ethyl benzene were introduced into a 5-liter reactor or reaction chamber. Ethyl benzene was used as a solvent and viscosity reducing medium for the reaction system. Styrene monomer, acrylonitrile monomer, and ethyl benzene were mixed for approximately 15 minutes to ensure uniformity. Following mixing, approximately 1.5 grams of tertiary dodecyl mercaptan (TDM) as a molecular size controlling agent or chain transfer agent was added, and reactor contents were further agitated for 15 minutes.
  • TDM tertiary dodecyl mercaptan
  • the resulting mixture present in the reactor was heated to approximately 150 °C and maintained at approximately 150 °C as a reaction temperature for a duration of approximately 3 hours. Following polymerization, the temperature was decreased to below approximately 50 °C to stop the polymerization reaction.
  • SAN specimens were tested for melt flow index (MFI), intrinsic viscosity (IV), and HAZE value.
  • Melt Flow Index also known as Melt Flow Rate or Melt Index, is a measure of the ease of flow of the melt polymer, with units of grams of polymer in ten minutes. MFI of SAN resin according to experiments in example one was measured according to ASTM D1238: Standard Test Method for Melt Flow Rates of Thermoplastics by Extrusion Plastometer p. 273- 286.
  • IV Intrinsic viscosity of SAN resin was measured in accordance with an in-house protocol. Intrinsic viscosity is a dimensionless value.
  • HAZE value indicative of the transparency of SAN resin, was determined according to ASTM D1003: Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics p. 205-210. Briefly, HAZE value is calculated as a percentage of a diffuse transmittance relative to a total transmittance obtained from a Hazemeter. A lower HAZE value corresponds to SAN resin having a higher transparency or better appearance.
  • SAN resin was prepared or produced using analogous process portions as in comparative example two as provided above. However, in example one, the resulting mixture present in the reactor was heated to approximately 140 °C and maintained at approximately 140 °C as a reaction temperature in the process portion (ii) Polymerizing styrene and acrylonitrile monomers.
  • SAN resin was prepared or produced using analogous process portions as in comparative example two as provided above. However, in example two, approximately 0.075 grams of l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent, and approximately 1.5 grams of tertiary dodecyl mercaptan (TDM) as a molecular size controlling agent or chain transfer agent were added into the reactor in the process portion (i) Introducing monomers and reagent.
  • TDM tertiary dodecyl mercaptan
  • SAN resin was prepared or produced using analogous process portions as in example two as provided above.
  • example three approximately 0.150 grams of l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent was added into the reactor in process portion (i) Introducing monomers and reagent. In other words, approximately 100 parts per million (ppm based on total weight of styrene and acrylonitrile monomers) of l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent was additionally introduced into the reactor.
  • the characteristics and properties of the SAN resin specimens of example three are shown in Table 2 below.
  • SAN resin was prepared or produced using analogous process portions as in example three as provided above.
  • Table 2 Characteristics and properties of the SAN resin specimens of comparative example two and example 1-4
  • Table 2 shows characteristics and properties of the SAN specimens obtained by process steps as described in comparative example two and examples 1-4.
  • melt flow index (MFI) MFI
  • IV intrinsic viscosity
  • HAZE value corresponding to % haze
  • MFI of SAN resins or specimens produced or prepared in the absence of l,l-Di(tert-butylperoxy)cyclohexane (i.e. comparative example two and example one) were approximately or generally similar to MFI values of SAN resins or specimens produced or prepared in the presence of l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent (i.e. examples two to four).
  • the HAZE value of SAN resins or specimens produced in the absence of l,l-Di(tert-butylperoxy)cyclohexane at the reaction temperature of 150 °C was approximately 0.68 (i.e., approximately 68%).
  • the HAZE value of SAN resin decreased from approximately 0.68 to approximately 0.56 when the reaction temperature was decreased from approximately 150 °C (i.e. comparative example two) to approximately 140 °C (i.e, example one). This result indicated that reducing reaction temperature could decrease HAZE value or yield more transparent resins due to a lower or reduced amount of by-products associated with or generated from a polymerization reaction.
  • the HAZE values of SAN resins or specimens produced in the presence of 1 , 1 -Di(tert-butylperoxy)cyclohexane at a concentration of approximately 50 (i.e, example two), approximately 100 (i.e, example three), and approximately 150 ppm (i.e, example four), at a reaction temperature of approximately 130 °C were approximately 0.48, 0.28, and 0.18, respectively.
  • FIG. 3 is a representative graph corresponding to the results shown in Table 2, which illustrates a relationship between between SAN resin HAZE values realized versus ppm of Di(tert- butylperoxy)cyclohexane (relative to the total weight of styrene monomers and acrylonitrile monomers that were mixed or blended with or exposed to l,l-Di(tert-butylperoxy)cyclohexane). As indicated in Table 2 and FIG.
  • HAZE values are significantly reduced (or SAN resin transparency is significantly improved, enhanced, or increased) even when a small concentration of l,l-Di(tert-butylperoxy)cyclohexane (e.g., approximately, 5, 10, or 20 ppm) is considered, and HAZE values are very significantly or dramatically reduced (or SAN resin transparency is very significantly or dramatically improved, enhanced, or increased) as l,l-Di(tert- butylperoxy)cyclohexane concentration further increases (e.g., to or beyond approximately 30, 40, 50, 80, 100, 120, 140, or more ppm).
  • a set of haze values, curves, or functions; and/or (b) a set of polymer conversion percentages or polymer conversion curves or functions relative to Di(tert- butylperoxy)cyclohexane concentration and one or more temperature values or temperature ranges can be generated, stored, retrieved, or accessed to aid the determination or selection of manufacturing process parameters that can result in the production of SAN resins having target, intended, or adjusted / tailored haze values.
  • the production of a SAN resin having a target, intended, or tailored haze value can occur within or approximately within a target or desired (e.g. minimum) polymerization time period.
  • One or more of the aforementioned values, curves, or functions can be generated, stored, retrieved, or accessed on or using an automated system, such as a computer or electronic system that is configured to automatically or semi-automatically manage one or more aspects of an enhanced transparency SAN resin manufacturing process in accordance with an embodiment of the disclosure.
  • an automated system such as a computer or electronic system that is configured to automatically or semi-automatically manage one or more aspects of an enhanced transparency SAN resin manufacturing process in accordance with an embodiment of the disclosure.
  • FIG. 4 is a flow diagram of a process 200 for producing an enhanced or high transparency / reduced or low haze SAN resin or composition using l,l-Di(tert-butylperoxy)cyclohexane as a sacrificial agent according to another embodiment of the disclosure.
  • a first process portion 210 involves retrieving (e.g., from a computer readable medium such as a memory) or receiving (e.g., as a result of user input, which can be received by way of user interaction with an input device such as a touch screen display, a computer mouse, or a keyboard) a target or desired haze or transparency value; and a second process portion 220 involves retrieving or receiving at least one of a target or desired polymerization reaction temperature and a target or desired polymerization time period.
  • a third process portion 230 involves determining a l, l-Di(tert-butylperoxy)cyclohexane concentration (e.g., relative to an amount of styrene monomers and acrylonitrile monomers under consideration, such as a total mass or weight of such monomers) that is expected to result in the production of a SAN resin having the target or desired haze or transparency value.
  • a l, l-Di(tert-butylperoxy)cyclohexane concentration e.g., relative to an amount of styrene monomers and acrylonitrile monomers under consideration, such as a total mass or weight of such monomers
  • the third process portion 230 can involve accessing stored data and/or functions that estimate or establish one or more relationships between haze or transparency values and l, l-Di(tert-butylperoxy)cyclohexane concentration with respect to polymerization reaction temperature, and the selection of a l,l-Di(tert- butylperoxy)cyclohexane concentration, possibly in view of a target or desired polymerization reaction temperature.
  • a fourth process portion 240 can involve determining a polymerization time period that matches or is close (e.g., as close as possible) to a target or desired polymerization time period.
  • the fourth process portion 240 can involve the identification or selection of a polymerization time period that corresponds or is expected to correspond to a target or minimum desired polymer conversion percentage, possibly with respect to a target or desired polymerization reaction temperature under consideration.
  • the first through fourth process portions 240 can result in the determination of a set of process parameters (e.g., l,l-Di(tert-butylperoxy)cyclohexane concentration, and one or more of polymerization reaction temperature, polymerization time period, or other parameters) for SAN resin manufacture or production.
  • a fifth process portion 250 involves producing an enhanced or high transparency / reduced or low haze SAN resin having the target haze or transparency value using the process parameters determined in association with the first through fourth process portions 240.
  • the fifth process portion 250 can involve one or more portions of a process in accordance with an embodiment of the present disclosure, such as the process 100 described above with respect to FIG. 1.
  • One or more aspects of the second process 200 described with respect to FIG. 4 can be automated or computer based, and correspondingly implemented using a computer system, control system, or state machine that is specifically programmed or designed to perform particular operations described above, for instance, by way of execution of stored program instructions.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne un procédé de production d'une résine de styrène-acrylonitrile (SAN) présentant une transparence améliorée ou un voile réduit incluant : l'exposition de monomères de styrène et de monomères d'acrylonitrile à du 1,1-di(tert-butylperoxy)cyclohexane, le 1,1-di(tert-butylperoxy)cyclohexane présentant une concentration entre approximativement 5 et 500 parties par million (ppm) par rapport au poids total des monomères de styrène et des monomères d'acrylonitrile ; l'initiation des réactions de polymérisation impliquant les monomères de styrène et les monomères d'acrylonitrile exposés au 1,1-di(tert-butylperoxy)cyclohexane ; la continuation des réactions de polymérisation pendant un laps de temps de polymérisation ; l'arrêt des réactions de polymérisation ; et l'obtention d'une résine de SAN présentant une valeur de voile significativement inférieure à approximativement 0,50 (par exemple inférieure ou égale à approximativement 0,45, 0,40, 0,35, 0,30, 0,25, 0,20, 0,15 ou 0,10).
PCT/TH2011/000024 2011-06-20 2011-06-20 Résine de styrène-acrylonitrile dotée de propriétés de transparence améliorées et son procédé de fabrication WO2012177225A1 (fr)

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JP2014516955A JP5807113B2 (ja) 2011-06-20 2011-06-20 向上した透明性を有するスチレン−アクリロニトリル樹脂およびその製造方法
PCT/TH2011/000024 WO2012177225A1 (fr) 2011-06-20 2011-06-20 Résine de styrène-acrylonitrile dotée de propriétés de transparence améliorées et son procédé de fabrication

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US20180072881A1 (en) * 2015-12-24 2018-03-15 Lg Chem, Ltd. Composition for preparing san copolymer, san copolymer, preparation method therefor, heat-resistant abs resin blend comprising same, and heat-resistant abs pellets

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WO2022071115A1 (fr) * 2020-09-30 2022-04-07 東洋エンジニアリング株式会社 Procédé de production d'un copolymère à base de styrène-acrylonitrile

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JPS54107994A (en) * 1978-02-14 1979-08-24 Denki Kagaku Kogyo Kk Preparation of styrene resin
JPS6187713A (ja) * 1984-10-08 1986-05-06 Nippon Oil & Fats Co Ltd スチレン系重合体の製造方法
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US10717859B2 (en) * 2015-12-24 2020-07-21 Lg Chem, Ltd. Composition for preparing SAN copolymer, SAN copolymer, preparation method therefore, heat-resistant ABS resin blend comprising same, and heat-resistant ABS pellets

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