WO2020091143A1 - Polyol composition, propylene glycol composition and preparation method thereof - Google Patents

Polyol composition, propylene glycol composition and preparation method thereof Download PDF

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Publication number
WO2020091143A1
WO2020091143A1 PCT/KR2018/016754 KR2018016754W WO2020091143A1 WO 2020091143 A1 WO2020091143 A1 WO 2020091143A1 KR 2018016754 W KR2018016754 W KR 2018016754W WO 2020091143 A1 WO2020091143 A1 WO 2020091143A1
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composition
propylene glycol
alkylene oxide
ppm
polyol
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PCT/KR2018/016754
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French (fr)
Korean (ko)
Inventor
하태찬
김성호
박수현
김한나
이상현
최현석
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에스케이피아이씨글로벌 주식회사
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Priority claimed from KR1020180131831A external-priority patent/KR102114896B1/en
Priority claimed from KR1020180131796A external-priority patent/KR102119729B1/en
Application filed by 에스케이피아이씨글로벌 주식회사 filed Critical 에스케이피아이씨글로벌 주식회사
Publication of WO2020091143A1 publication Critical patent/WO2020091143A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B63/00—Purification; Separation; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/32—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions without formation of -OH groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines

Definitions

  • Embodiments relate to polyol compositions, propylene glycol compositions, and methods of making the ionic components selectively removed.
  • Polyol compositions are used in various industrial fields, and are mainly used as raw materials for polyurethane resins such as polyurethane compositions and polyurethane elastomers.
  • the propylene glycol composition is a raw material that has a wide range of application fields, such as raw materials for pharmaceuticals such as unsaturated polyester resins, cosmetics, ointments, antifreezes, surfactants, and high-grade polar solvents.
  • the polyol composition may be prepared by addition polymerization of an alkylene oxide to an active hydrogen compound such as polyhydric alcohol. Since a relatively large amount of alkylene oxide is additionally polymerized with respect to the amount of the active hydrogen compound, the resulting polyol composition may contain impurities that may be introduced from the alkylene oxide and affect subsequent processes.
  • the propylene glycol composition is also generally prepared by reacting propylene oxide with water in a molar ratio of 1: 1, the resulting propylene glycol composition contains impurities that may flow into propylene oxide and affect subsequent processes, etc. Can be included.
  • the embodiment is intended to provide a polyol composition suitable for application in a subsequent process and a method for manufacturing the same, by selectively removing ionic or nonionic impurities to have a low CPR (Controlled Polymerization Rate).
  • Another embodiment is to provide a high quality propylene glycol composition suitable for application in a subsequent process and a method for manufacturing the same, by selectively removing ionic or nonionic impurities to have a low nitrogen (Nitrogen) content.
  • the CPR of the polyol composition according to one embodiment is less than 2.4.
  • a method for preparing a polyol composition includes (1) purifying an alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with a polyhydric alcohol; And (3) obtaining a polyol composition.
  • the CPR of the polyol composition is less than 2.4.
  • the nitrogen content of the propylene glycol composition according to one embodiment is less than 0.4 ppm.
  • Method for producing a propylene glycol composition comprises the steps of (1) purifying the alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with water; And (3) obtaining a propylene glycol composition.
  • the nitrogen content of the propylene glycol composition is less than 0.4 ppm.
  • the polyol composition according to the embodiment has a low CPR, thereby improving the quality of the polyurethane composition produced in a subsequent process.
  • the propylene glycol composition according to the embodiment has a low nitrogen content, thereby improving the quality and is suitable for application in a subsequent process.
  • the embodiment provides a polyol composition having a low Controlled Polymerization Rate (CPR) by selectively removing ionic or nonionic components.
  • CPR Controlled Polymerization Rate
  • the CPR is an index indicating the amount of the basic substance in the composition.
  • 30 g of the composition is mixed with 100 ml of methanol, and the amount of neutralized titrated hydrochloric acid (concentration: 0.001 N) is quantified. Is the result.
  • the CPR value may be lowered as ionic or nonionic impurities in the polyol composition are effectively removed.
  • the CPR of the polyol composition according to one embodiment is less than 2.4.
  • the CPR of the polyol composition according to another embodiment is 2.0 or less.
  • the CPR of the polyol composition according to another embodiment is 0.8 or less.
  • the CPR of the polyol composition is 0 or more.
  • the CPR of the polyol composition is 0.1 or more, 0.26 or more, or 0.3 or more.
  • the CPR of the polyol composition is 0 or more and less than 2.4, 0 to 2.3, 0 to 2.2, 0 to 2.1, 0 to 2.0, 0 to 1.9, 0 to 1.8, 0 to 1.7, 0 to 1.6, 0 to 1.5 , 0 to 1.4, 0 to 1.3, 0 to 1.2, 0 to 1.1, 0 to 1.0, 0 to 0.9, 0 to 0.8, 0.2 to 0.8, 0.3 to 0.8, 0.4 to 0.8, but is not limited thereto.
  • the nitrogen content of the polyol composition according to one embodiment is less than 0.43 ppm.
  • the nitrogen content of the polyol composition according to another embodiment is 0.3 ppm or less.
  • the nitrogen content of the polyol composition may be 0.2 to 0.4 ppm, 0.2 to 0.38 pm, 0.2 to 0.36 pm, 0.2 to 0.34 pm, 0.2 to 0.32 pm or 0.2 to 0.3 ppm, but is not limited thereto.
  • the polyol composition may include an ionic component, a nonionic component and a solvent.
  • the polyol composition may include an ionic component, that is, a cationic component and an anionic component.
  • the cationic component may be one or more selected from the group consisting of NH 2 + , NH 4 + and molecular sieves having the functional group.
  • the cationic component may include NH 4 + .
  • the cationic component may include NH 2 + and NH 4 + .
  • the cationic component but be made of a NH 4 +, but is not limited to such.
  • the anionic component is NO 2 - can be at least one member selected from the group consisting of the minute, and with it to the functional group itself -, NO 3.
  • the anionic component is NO 2 - can include.
  • the anionic component is NO 2 - can include - and NO 3.
  • the anionic component may be made of NO 2 ⁇ , but is not limited thereto.
  • the ionic component may include a nitrogen-containing ionic component.
  • the ionic component is NH 2 +, NH 4 +, NO 2 - it can include at least one selected from the group consisting of - and NO 3.
  • the ionic component is NH 2 +, NH 4 +, NO 2 - can be made of at least one selected from the group consisting of - and NO 3.
  • the polyol composition may include a nonionic component in addition to the ionic component.
  • the non-ionic component may include an amine-based component.
  • the amine component is diisopropylamine (diisopropylamine), diethylamine (diethylamine), triethylamine (dimethylamine), diethanolamine (diethanolamine), dimethylethylamine (dimethylethylamine), methyldiethanolamine (methyldiethanolamine ), Trimethylamine (Trimethylamine) and monoisopropylamine (monoisopropylamine) may include one or more selected from the group consisting of.
  • the factor that increases the nitrogen content of the polyol composition is due to the nitrogen-containing ionic component and nitrogen-containing nonionic component in the alkylene oxide.
  • the polyol composition may include a solvent.
  • the solvent may include one or more selected from the group consisting of water, methanol, acetaldehyde, propionaldehyde, methyl formate and dimethoxymethane.
  • a method for preparing a polyol composition includes (1) purifying an alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with a polyhydric alcohol; And (3) obtaining a polyol composition.
  • the CPR of the polyol composition is less than 2.4.
  • step 1 a step of purifying the alkylene oxide crude composition is performed (step 1).
  • the alkylene oxide crude composition is a composition immediately after being prepared by an alkylene oxide production process, and means a composition containing unnecessary ionic components and the like in a subsequent process.
  • the alkylene oxide crude composition may include an alkylene oxide, an ionic component, a nonionic component and a solvent.
  • the alkylene oxide crude composition may include an ionic component.
  • the ionic component may be a cationic component or an anionic component.
  • the ionic component includes NH 4 + , and the content of NH 4 + included in the alkylene oxide crude composition is 0.1 to 5 ppm.
  • the ionic component contains NH 4 + , and the content of NH 4 + contained in the alkylene oxide crude composition is 0.1 to 3 ppm, 0.1 to 2.5 ppm, 0.3 to 2 ppm, or 0.5 to 1.5 ppm.
  • it is not limited thereto.
  • the ionic component is NO 2 - content of 0.1 to 5 ppm - NO 2 contained in the crude alkylene oxide composition, comprising: a.
  • the ionic component is NO 2 - and wherein the alkylene oxides with NO 2 contained in the crude composition to - may be a range of 0.1 to 3 ppm content of 0.1 to 1 ppm or from 0.25 to 0.75 ppm, this limited It does not work.
  • the ionic component may include a nitrogen-containing ionic component.
  • the ionic component is NH 2 +, NH 4 +, NO 2 - it can include at least one selected from the group consisting of - and NO 3.
  • the ionic component is NH 2 +, NH 4 +, NO 2 - can be made of at least one selected from the group consisting of - and NO 3.
  • the ionic component contains 30 to 90% by weight of the cationic component based on the total weight of the ionic component.
  • the ionic component may include 40 to 90% by weight, 50 to 90% by weight, or 50 to 80% by weight based on the total weight of the ionic component. More specifically, the ionic component may include 60 to 80% by weight of the cationic component based on the total weight of the ionic component, but is not limited thereto.
  • the alkylene oxide crude composition may include a nonionic component in addition to the ionic component.
  • the contents of the nonionic component are the same as those stated in the polyol composition.
  • the alkylene oxide crude composition may include a solvent.
  • the solvent may include one or more selected from the group consisting of water, methanol, acetaldehyde, propionaldehyde, methyl formate and dimethoxymethane.
  • the alkylene oxide crude composition includes dimethoxymethane (DMM) and methyl formate (MF), and the content of the dimethoxymethane (DMM) and methyl formate (MF) is 10 to 3,000 ppm, It may be 10 to 1,000 ppm, 10 to 500 ppm or 20 to 100 ppm, but is not limited thereto.
  • the CPR (Controlled Polymerization Rate) of the alkylene oxide crude composition is 0.2 to 20.
  • the CPR of the alkylene oxide crude composition may be 0.2 to 10, 0.2 to 5, 0.2 to 2, 0.5 to 3, 0.5 to 2 or 0.8 to 1.5, but is not limited thereto.
  • the CPR of the alkylene oxide crude composition does not satisfy the appropriate range, it is difficult to control the reactivity in the process of manufacturing the subsequent product using the raw material, and the CPR value of the latter product using the raw material exceeds the product CPR standard. . Therefore, when the CPR value of the alkylene oxide crude composition satisfies an appropriate range, product quality may be improved. Specifically, it is more advantageous to maintain the CPR value of the alkylene oxide crude composition at a maximum of 2.0 or less.
  • the remaining cationic impurities are factors that increase the CPR value of the alkylene oxide crude composition even after the impurities are neutralized.
  • Nitrogen content of the alkylene oxide crude composition is 0.2 to 10 ppm. Specifically, the nitrogen content of the alkylene oxide crude composition is 0.2 to 7 ppm, 0.2 to 5 ppm, 0.2 to 3 ppm or 0.2 to 2 ppm. More specifically, the nitrogen content of the alkylene oxide crude composition may be 0.5 to 1.8 ppm, 1.0 to 1.8 ppm or 1.2 to 1.8 ppm, but is not limited thereto.
  • the factors that increase the nitrogen content of the alkylene oxide crude composition are due to the aforementioned nitrogen-containing ionic components and nitrogen-containing nonionic components.
  • the alkylene oxide may be ethylene oxide, propylene oxide, butylene oxide, and the like. Specifically, the alkylene oxide may be propylene oxide.
  • the step of purifying the alkylene oxide crude composition is performed prior to performing one or more purification methods selected from the group consisting of an adsorbent use method, an electrochemical method, and a distillation method, in particular, an adsorbent.
  • an adsorbent use method
  • an electrochemical method electrochemical method
  • a distillation method in particular, an adsorbent.
  • an adsorbent Before performing the purification method using the alkylene oxide crude composition may be passed through a bead section.
  • the bead section includes a plurality of beads having an average diameter of 1 to 5 mm.
  • the bead section may include a plurality of beads having an average diameter of 1.5 to 4 mm or 2 to 3 mm, but is not limited thereto.
  • the number of beads per unit volume of the beads included in the bead section is 100 to 100,000 pieces / L.
  • the number of beads per unit volume of the bead section may be 1,000 to 80,000 pieces / L, 5,000 to 70,000 pieces / L, 10,000 to 50,000 pieces / L, and 15,000 to 40,000 pieces / L, but is not limited thereto. no.
  • the space velocity through which the alkylene oxide crude composition passes through the bead section is greater than 0 to 10 h ⁇ 1 or less. Specifically, the space velocity through which the alkylene oxide crude composition passes through the bead section is 0.2 to 5 h -1 , 0.2 to 3 h -1 , 0.2 to 2 h -1 , 0.5 to 2 h -1 or 0.8 to 1.5 h -1 , but is not limited thereto.
  • the beads included in the bead section may include an inactive material based on silicalite.
  • the bead section serves to induce an even dispersion before the alkylene oxide crude composition enters the subsequent purification methods, particularly the adsorbent.
  • the step of purifying the alkylene oxide crude composition may use one or more purification methods selected from the group consisting of an adsorbent usage method, an electrochemical method, and a distillation method.
  • the crude alkylene oxide composition may be passed through an adsorbent.
  • the method of using the adsorbent may be a zeolite-based molecular sieve (Mol-Sieve) or natural clay (Natural Clay).
  • the zeolite-based molecular sieve may have a structure selected from the group consisting of zeolite A, zeolite X, zeolite beta, zeolite Y, zeolite L and ZSM-12.
  • the molecular sieve collectively refers to silicon aluminum oxide, and may be an octagonal geometric structure having an inlet of a fine hole made of an oxygen atom ring and intersecting another hole bent at regular intervals between the holes, but is not limited thereto. .
  • the pore size of the molecular sieve is greater than 2.3 mm 2 and less than 10 mm 2.
  • the pore size of the molecular sieve may be 3 to 10 ⁇ , 3 to 7.5 ⁇ , 3 to 5 ⁇ , 3.5 to 4.5 ⁇ , 3.8 to 4.2 ⁇ or 3.9 to 4.1 ⁇ , but is not limited thereto.
  • the shape of the pores of the molecular sieve may be octagonal.
  • the molecular sieve has an octagonal microporous shape, and the commercialized product may be manufactured into a spherical, pellet, extruded or the like of about 2 mm by physically bonding the molecular sieve.
  • the molecular sieve can be adsorbed by selecting impurities smaller than the octagonal fine pores.
  • the negative charge (acid point) of the zeolite series itself of the molecular sieve can adsorb the cationic component present in the alkylene oxide bath composition.
  • the natural clay may be selected from the group consisting of montmorillonite, kaolinite, sepiolite, bentonite, and diatomite.
  • the space velocity through which the alkylene oxide crude composition passes through the adsorbent is greater than 0 to 10 h ⁇ 1 or less. Specifically, the space velocity through which the alkylene oxide crude composition passes through the molecular sieve is 0.2 to 5 h -1 , 0.2 to 3 h -1 , 0.2 to 2 h -1 , 0.5 to 2 h -1 or 0.8 to 1.5 h -1 , but is not limited thereto.
  • a certain amount of a Pd / C catalyst is coated on a graphite foil to produce two electrodes, and then connected to equipment that applies voltage.
  • causative substances such as ionic components, which increase the CPR value, can be removed by being adsorbed to the electrode.
  • a voltage of 0.85 V may be applied between the two electrodes to maintain it for 2 hours, but is not limited thereto.
  • the distillation method by using the alkylene oxide crude composition using a low-boiling-point material distillation column (Light purge column), it is possible to remove causative substances that increase the CPR value such as ionic components.
  • the alkylene oxide composition purified using the above purification method includes an ionic component including a cationic component and an anionic component. At this time, the description of the type of the ionic component is as described in the alkylene oxide crude composition.
  • the purified alkylene oxide composition may include a non-ionic component and a solvent in addition to the ionic component, and the description thereof is also as described in the alkylene oxide crude composition.
  • the ionic component contains 10 to 70% by weight of the cationic component based on the total weight of the ionic component. do.
  • the ionic component may include 20 to 70% by weight, 30 to 70% by weight, 40 to 60% by weight, or 45 to 55% by weight based on the total weight of the ionic component. It is not limited.
  • the purified alkylene oxide composition and the content of NH 4 + is contained within and wherein the purified alkylene oxide composition of the NH 4 + is from 0.05 to 2.5 ppm.
  • the content of NH 4 + contained in the purified alkylene oxide composition may be 0.1 to 2 ppm, 0.1 to 1 ppm, 0.2 to 0.8 ppm, 0.2 to 0.6 ppm, or 0.4 to 0.6 ppm, but is not limited thereto. It is not.
  • the purified alkylene oxide composition NO 2 - is the amount of 0.1 to 5 ppm - and include, the NO 2 contained in the purified alkylene oxide composition a.
  • the content of NO 2 ⁇ contained in the purified alkylene oxide composition may be 0.1 to 3 ppm or 0.25 to 0.75 ppm, but is not limited thereto.
  • the purified alkylene oxide composition has a CPR of 0 to 2.
  • the CPR of the purified alkylene oxide composition may be 0 to 1.5, 0 to 1.2, 0 to 0.8, 0 to 0.5, 0.1 to 0.5, 0.1 to 0.3 or 0.1 to 0.2, but is not limited thereto.
  • the CPR of the purified alkylene oxide composition is within the above range, it not only facilitates the control of reactivity in the manufacturing process of a rear end product using it as a raw material, but also satisfies the product CPR standard with the lowered CPR value of the product itself. It is advantageous.
  • the purified alkylene oxide composition has a basicity of 0 to 4.
  • the basicity of the purified alkylene oxide composition may be 0 to 3, 0 to 2.4, 0 to 1.6 or 0 to 1.0, but is not limited thereto.
  • Nitrogen content of the purified alkylene oxide composition is 0.1 to 5 ppm. Specifically, the nitrogen content of the purified alkylene oxide composition may be 0.1 to 3 ppm, 0.1 to 2 ppm, 0.2 to 1.5 ppm or 0.4 to 1.1 ppm, but is not limited thereto.
  • step (2) a step of reacting the purified alkylene oxide composition with a polyhydric alcohol is performed (step (2)).
  • the polyhydric alcohol may be at least one selected from the group consisting of glycerol, propylene glycol, sucrose, sorbitol, and triethanolamine.
  • the step (2) may be performed by further comprising at least one selected from the group consisting of catalysts, neutralizing agents and antioxidants.
  • the catalyst may be at least one selected from the group consisting of calcium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, imidazole, cesium hydroxide and phosphazene, but is not limited thereto. By using the catalyst, it is possible to suppress the generation of monool due to side reactions and reduce the process cost.
  • the polyol composition may be obtained through the step (2) (step (3)).
  • the polyurethane composition may be obtained by reacting the polyol composition with isocyanate.
  • the polyurethane composition is prepared by using a polyol composition having a low CPR, and thus has a low CPR, and can improve tear strength, tensile strength, elongation, breathability, and resilience.
  • the isocyanate is a compound represented by the general formula of R- (NCO) n, R is alkyl or phenyl, and n may be 2 to 5.
  • the isocyanate is, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane -1,3-diisocyanate, hydrogen-substituted methylene diphenyl diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, di Phenylmethane-1,5-diisocyanate, diphenylmethane-4,4'-diisocyanate, methylenediphenyldiisocyanate (MDI), modified polyisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-
  • the polyurethane composition may further include additives such as foam stabilizers, curing agents, reaction regulators, cell regulators, polymerization inhibitors, flame retardants, surfactants, and hardness improvers.
  • additives such as foam stabilizers, curing agents, reaction regulators, cell regulators, polymerization inhibitors, flame retardants, surfactants, and hardness improvers.
  • polyether silane may be used, and the polyether silane may be a crosslinked polymer polymerized with ethylene oxide, propylene oxide, etc. on the silane basic structure.
  • the polyurethane may further include a foaming agent to have a foam form.
  • An organic metal catalyst or an amine catalyst can be used for the reaction of the polyol composition and the isocyanate.
  • the organometallic catalysts include di-n-octyltin-mercaptide, tin (III) carboxylate, tin (III) acetate, tin (III) octoate, tin (III) ethylhexate, tin (III) laurate , Dibutyl tin dilaurate, dibutyl tin maleate, dioctyl tin diacetate, and the like, but are not limited thereto.
  • amine catalyst triethyleneamine, tributyleneamine, N-methylmorpholine, N-ethylmorpholine, N, N'-tetramethylethylenediamine, pentamethyl-diethylenetriamine, 1,4-diazabi Cyclo [2,2,2] octane, N-methyl-N'-dimethyl-aminoethyl piperazine, bis-dimethylaminoalkyl piperazine, N, N-dimethylbenzylamide, bis-N, N'-diethylamino Ethyl adipate, N, N'-dimethyl-phenylethylamide, 1,2-dimethyl-imidazole, and the like, but is not limited thereto.
  • Embodiments provide a propylene glycol composition having a low nitrogen content by selectively removing ionic or nonionic components.
  • the nitrogen content of the propylene glycol composition according to one embodiment is less than 0.4 ppm.
  • the nitrogen content of the propylene glycol composition according to another embodiment is 0.3 ppm or less.
  • the nitrogen content of the propylene glycol composition according to another embodiment is 0.2 ppm or less.
  • the nitrogen content of the propylene glycol composition may be 0 ppm or more, 0.05 ppm or more, or 0.1 ppm or more.
  • the nitrogen content of the propylene glycol composition is 0.1 or more to less than 0.4 ppm, 0.1 to 0.38 ppm, 0.1 to 0.36 ppm, 0.1 to 0.34 ppm, 0.1 to 0.32 ppm, 0.1 to 0.3 ppm, 0.1 to 0.28 ppm, 0.1 To 0.26 ppm, 0.1 to 0.24 ppm, 0.1 to 0.22 ppm or 0.1 to 0.2 ppm, but is not limited thereto.
  • the propylene glycol composition may include an ionic component, a nonionic component and a solvent.
  • the propylene glycol composition may include an ionic component, that is, a cationic component and an anionic component.
  • the cationic component may be one or more selected from the group consisting of NH 2 + , NH 4 + and molecular sieves having the functional group.
  • the cationic component may include NH 4 + .
  • the cationic component may include NH 2 + and NH 4 + .
  • the cationic component but be made of a NH 4 +, but is not limited to such.
  • the anionic component is NO 2 - can be at least one member selected from the group consisting of the minute, and with it to the functional group itself -, NO 3.
  • the anionic component is NO 2 - can include.
  • the anionic component is NO 2 - can include - and NO 3.
  • the anionic component may be made of NO 2 ⁇ , but is not limited thereto.
  • the ionic component may include a nitrogen-containing ionic component.
  • the ionic component is NH 2 +, NH 4 +, NO 2 - it can include at least one selected from the group consisting of - and NO 3.
  • the ionic component is NH 2 +, NH 4 +, NO 2 - can be made of at least one selected from the group consisting of - and NO 3.
  • the propylene glycol composition may include a non-ionic component in addition to the ionic component.
  • the non-ionic component may include an amine-based component.
  • the amine-based component is diisopropylamine, diethylamine, triethylamine, diethanolamine, dimethylethylamine, methyldiethanolamine ), Trimethylamine (Trimethylamine) and monoisopropylamine (monoisopropylamine) may include one or more selected from the group consisting of.
  • the reason for increasing the nitrogen content of the propylene glycol composition is due to the nitrogen-containing ionic component and nitrogen-containing nonionic component in propylene oxide.
  • the propylene oxide crude composition may include a solvent.
  • the solvent may include one or more selected from the group consisting of water, methanol, acetaldehyde, propionaldehyde, methyl formate and dimethoxymethane.
  • the odor index of the propylene glycol composition according to one embodiment is less than 3.
  • the odor strength index of the propylene glycol composition according to another embodiment is 1 or less.
  • the odor intensity index of the propylene glycol composition may be 0 to less than 3, 0 to 2, 0 to 1 or 0 to 0.5, but is not limited thereto.
  • the odor index is an odor of the composition measured by the following criteria.
  • the propylene glycol composition according to one embodiment includes at least one selected from the group consisting of mono propylene glycol, dipropylene glycol and tripropylene glycol.
  • the content of the mono propylene glycol may be 60 to 80% by weight based on the total weight of the propylene glycol composition. Specifically, it may be 65 to 80% by weight, 65 to 75% by weight or 65 to 70% by weight, but is not limited thereto.
  • the content of the dipropylene glycol may be 20 to 30% by weight based on the total weight of the propylene glycol composition. Specifically, it may be 22 to 30% by weight, 22 to 28% by weight, or 22 to 25% by weight, but is not limited thereto.
  • Method for producing a propylene glycol composition comprises the steps of (1) purifying the alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with water; And (3) obtaining a propylene glycol composition; wherein the nitrogen content of the propylene glycol composition is less than 0.4 ppm.
  • step 1 a step of purifying the alkylene oxide crude composition is performed (step 1).
  • step (1) The description of step (1) is as described above.
  • step (2) a step of reacting the purified alkylene oxide composition with water is performed.
  • the propylene glycol composition may be prepared by reacting an alkylene oxide composition and water at 100 to 200 ° C, as shown in Scheme 1 below.
  • a propylene glycol composition can be obtained by performing a purification process using the boiling point difference through the step (2) (step (3)) .
  • 100 g of the purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
  • 100 g of a purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
  • 100 g of the purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
  • a polyol composition D was obtained in the same manner as in Example 1, except that 100 g of the alkylene oxide crude composition in Example 1-1 was used without purification.
  • a polyol composition E was obtained in the same manner as in Example 1-2, except that 100 g of the alkylene oxide crude composition in Example 1-2 was used without purification.
  • a polyol composition F was obtained in the same manner as in Example 1-3, except that 100 g of the alkylene oxide crude composition in Example 1-3 was used without purification.
  • Example 1-1 Example 1-2
  • Example 1-3 Comparative Example 1-1 Comparative Example 1-2 Comparative Example 1-3 CPR of alkylene oxide crude composition 8.0 8.0 8.0 8.0 8.0 CPR of purified alkylene oxide composition 0.1 0.1 0.1 8.0 8.0 8.0 No purification step CPR of polyol composition 0.4 0.6 0.8 2.4 3.0 3.4 Nitrogen content of polyol composition (ppm) 0.3 0.2 0.3 0.57 0.5 0.43
  • the nitrogen content of the polyol composition subjected to the purification step of the alkylene oxide composition of Examples 1-1 to 1-3 is based on the nitrogen content of the polyol composition of Comparative Examples 1-1 to 1-3 without performing the purification step. It can be seen that it is low.
  • Non-foam composition G (NCO%: 5.6).
  • a raw material is injected into a continuous foaming line or container using a low pressure / high pressure foamer. And through the foaming and aging process to prepare a polyurethane composition H of a reproducible shape.
  • the polyol composition C After mixing the polyol composition C with a polymer polyol, a blowing agent, a surfactant, and an isocyanate, the polyol composition C is injected into a mold of a certain shape using a low pressure / high pressure foamer and foamed, A polyurethane composition I having a reproducible shape was prepared through a demolding and aging process.
  • a polyurethane composition J was prepared in the same manner as in Example 2-1, except that the polyol composition D was used instead of the polyol composition A.
  • a polyurethane composition K was prepared in the same manner as in Example 2-2, except that the polyol composition E was used instead of the polyol composition B.
  • Polyurethane composition L was prepared in the same manner as in Example 2-3, except that polyol composition F was used instead of polyol composition C.
  • Non-foam composition is mixed with 25 ml of methanol, and then an atomic absorption spectrophotometer (Atomic Absorption Spectroscopy) equipment is used. And analyzed.
  • each composition was put in a Nessler tube to transmit light and measure the color compared to a standard material.
  • the polyurethane composition was compressed in an oven at 70 ° C to 80 ° C for 50% of the thickness, respectively, and pressure was applied for 22 hours. 30 minutes after releasing the pressure, the thickness change value was measured based on the initial thickness.
  • the Non-foam composition of Example 2-1 has a lower CPR and color value than the Non-foam composition of Comparative Example 2-1, and thus it can be seen that the quality is excellent.
  • Example 2-2 is superior to the polyurethane composition of Comparative Example 2-2, having excellent tear strength, tensile strength, elongation, and breathability.
  • Example 2-3 compared to the polyurethane composition of Comparative Example 2-3, tear strength, tensile strength, elongation, rebound elasticity and resilience according to external impact (high temperature, high pressure) (Comp. Set%) ) It can be seen that this is excellent.
  • 100 g of a purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
  • propylene oxide composition and water were reacted in a tube reactor. Thereafter, the remaining water was distilled to obtain propylene glycol composition A.
  • the propylene glycol composition B was obtained in the same experiment as in Example 3-1, except that 100 g of the alkylene oxide crude composition in Example 3-1 was used without purification.
  • the odor intensity index of each composition was measured according to the following criteria.
  • Example 3-1 Comparative Example 3-1 CPR of purified alkylene oxide composition 0 0.5 No purification step Nitrogen content in purified alkylene oxide composition (ppm) 0 0.4 No purification step Odor of propylene glycol composition 1.0 3.0 Nitrogen content in propylene glycol composition (ppm) 0.2 0.4
  • the nitrogen content and odor of the propylene glycol composition after the alkylene oxide purification step of Example 3-1 is lower than that of Comparative Example 3-1 without performing the alkylene oxide purification step. Can be.

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Abstract

The implemented embodiments relate to a polyol composition, a propylene glycol composition and a preparation method thereof. The controlled polymerization rate (CPR) of the polyol composition is less than 2.4, and thus a polyol composition appropriate for the application to a following procedure can be obtained. The nitrogen content of the propylene glycol composition is less than 0.4 ppm, and thus a propylene glycol composition appropriate for the application to a following procedure and having enhanced quality can be obtained.

Description

폴리올 조성물, 프로필렌 글리콜 조성물 및 이의 제조 방법Polyol composition, propylene glycol composition and method for manufacturing the same
구현예는 이온계 성분이 선택적으로 제거된 폴리올 조성물, 프로필렌 글리콜 조성물 및 이의 제조 방법에 관한 것이다. Embodiments relate to polyol compositions, propylene glycol compositions, and methods of making the ionic components selectively removed.
폴리올 조성물은 다양한 공업 분야에서 이용되고 있는데, 폴리우레탄 조성물, 폴리우레탄 엘라스토머 등의 폴리우레탄 수지의 원료로 주로 사용되고 있다. Polyol compositions are used in various industrial fields, and are mainly used as raw materials for polyurethane resins such as polyurethane compositions and polyurethane elastomers.
그 중, 프로필렌 글리콜 조성물은 불포화 폴리에스터 수지, 화장품, 연고 등의 의약품, 부동액, 계면 활성제, 고급 극성 용제의 원료 등 그 응용 분야가 광범위한 원료이다.Among them, the propylene glycol composition is a raw material that has a wide range of application fields, such as raw materials for pharmaceuticals such as unsaturated polyester resins, cosmetics, ointments, antifreezes, surfactants, and high-grade polar solvents.
이러한 폴리올 조성물은 다가 알코올 등의 활성 수소 화합물에 알킬렌 옥사이드를 부가 중합시켜 제조될 수 있다. 활성 수소 화합물의 양에 대해서 비교적 다량의 알킬렌 옥사이드를 부가 중합시키게 되므로, 생성된 폴리올 조성물에는 알킬렌 옥사이드로부터 유입되어 후속 공정 등에 영향을 줄 수 있는 불순물이 포함될 수 있다. The polyol composition may be prepared by addition polymerization of an alkylene oxide to an active hydrogen compound such as polyhydric alcohol. Since a relatively large amount of alkylene oxide is additionally polymerized with respect to the amount of the active hydrogen compound, the resulting polyol composition may contain impurities that may be introduced from the alkylene oxide and affect subsequent processes.
마찬가지로, 프로필렌 글리콜 조성물 역시, 일반적으로 프로필렌 옥사이드(propylene oxide)과 물을 1:1의 몰비로 반응시켜 제조되므로, 생성된 프로필렌 글리콜 조성물에는 프로필렌 옥사이드로부터 유입되어 후속 공정 등에 영향을 줄 수 있는 불순물이 포함될 수 있다. Likewise, since the propylene glycol composition is also generally prepared by reacting propylene oxide with water in a molar ratio of 1: 1, the resulting propylene glycol composition contains impurities that may flow into propylene oxide and affect subsequent processes, etc. Can be included.
이에, 프로필렌 옥사이드를 포함하는 알킬렌 옥사이드 및 이로부터 제조된 폴리올 조성물 내에 어떤 불순물이 포함되어 있는지, 이와 같은 불순물이 폴리올의 물성에 어떠한 영향을 미치며, 이 불순물을 선택적으로 제거하는 방법이 무엇인지에 대한 연구가 계속되고 있다. Accordingly, the alkylene oxide containing propylene oxide and what impurities are contained in the polyol composition prepared therefrom, how these impurities affect the physical properties of the polyol, and how to selectively remove these impurities Research is continuing.
구현예는 이온계 또는 비이온계 불순물이 선택적으로 제거되어 낮은 CPR(Controlled Polymerization Rate)을 가짐으로써, 후속 공정에 적용하기에 적합한 폴리올 조성물 및 이의 제조 방법을 제공하고자 한다. The embodiment is intended to provide a polyol composition suitable for application in a subsequent process and a method for manufacturing the same, by selectively removing ionic or nonionic impurities to have a low CPR (Controlled Polymerization Rate).
또 다른 구현예는 이온계 또는 비이온계 불순물이 선택적으로 제거되어 낮은 질소(Nitrogen) 함량을 가짐으로써, 후속 공정에 적용하기에 적합한 고품질의 프로필렌 글리콜 조성물 및 이의 제조 방법을 제공하고자 한다.Another embodiment is to provide a high quality propylene glycol composition suitable for application in a subsequent process and a method for manufacturing the same, by selectively removing ionic or nonionic impurities to have a low nitrogen (Nitrogen) content.
일 구현예에 따른 폴리올 조성물의 CPR은 2.4 미만이다. The CPR of the polyol composition according to one embodiment is less than 2.4.
일 구현예에 따른 폴리올 조성물의 제조 방법은 (1) 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계; (2) 상기 정제된 알킬렌 옥사이드 조성물과 다가 알코올을 반응시키는 단계; 및 (3) 폴리올 조성물을 얻는 단계;를 포함하고, 상기 폴리올 조성물의 CPR은 2.4 미만이다. A method for preparing a polyol composition according to an embodiment includes (1) purifying an alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with a polyhydric alcohol; And (3) obtaining a polyol composition. The CPR of the polyol composition is less than 2.4.
일 구현예에 따른 프로필렌 글리콜 조성물의 질소(Nitrogen) 함량은 0.4 ppm 미만이다. The nitrogen content of the propylene glycol composition according to one embodiment is less than 0.4 ppm.
일 구현예에 따른 프로필렌 글리콜 조성물의 제조 방법은 (1) 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계; (2) 상기 정제된 알킬렌 옥사이드 조성물과 물을 반응시키는 단계; 및 (3) 프로필렌 글리콜 조성물을 얻는 단계;를 포함하고, 상기 프로필렌 글리콜 조성물의 질소 함량이 0.4 ppm 미만이다. Method for producing a propylene glycol composition according to one embodiment comprises the steps of (1) purifying the alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with water; And (3) obtaining a propylene glycol composition. The nitrogen content of the propylene glycol composition is less than 0.4 ppm.
구현예에 따른 폴리올 조성물은 낮은 CPR을 가짐으로써, 후속 공정으로 생성되는 폴리우레탄 조성물의 품질을 향상시킬 수 있다. The polyol composition according to the embodiment has a low CPR, thereby improving the quality of the polyurethane composition produced in a subsequent process.
구현예에 따른 프로필렌 글리콜 조성물은 낮은 질소 함량을 가짐으로써, 품질 향상은 물론, 후속 공정에 적용하기에 적합하다. The propylene glycol composition according to the embodiment has a low nitrogen content, thereby improving the quality and is suitable for application in a subsequent process.
이하, 구현예를 통해 발명을 상세하게 설명한다. 구현예는 이하에서 개시된 내용에 한정되는 것이 아니라 발명의 요지가 변경되지 않는 한, 다양한 형태로 변형될 수 있다.Hereinafter, the invention will be described in detail through embodiments. The embodiments are not limited to the contents disclosed below, and may be modified in various forms as long as the gist of the invention is not changed.
본 명세서에 있어서, 어떤 부분이 어떤 구성요소를 "포함" 한다고 할 때, 이는 특별히 반대되는 기재가 없는 한, 다른 구성요소를 제외하는 것이 아니라 다른 구성 요소를 더 포함할 수 있는 것을 의미한다.In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not exclude other components, unless otherwise stated.
또한, 본 명세서에 기재된 구성성분의 양, 반응 조건 등을 나타내는 모든 숫자 및 표현은 특별한 기재가 없는 한 모든 경우에 "약"이라는 용어로써 수식되는 것으로 이해하여야 한다.In addition, it should be understood that all numbers and expressions indicative of the amount of ingredients, reaction conditions, and the like described in this specification are modified in all cases with the term "about" unless otherwise specified.
폴리올 조성물 Polyol composition
구현예는 이온계 또는 비이온계 성분이 선택적으로 제거되어 낮은 CPR(Controlled Polymerization Rate)을 갖는 폴리올 조성물을 제공한다. 폴리올의 CPR 값이 낮을수록, 폴리올을 이용하여 제조될 수 있는 폴리우레탄의 물성을 향상시킬 수 있는 장점이 있다. The embodiment provides a polyol composition having a low Controlled Polymerization Rate (CPR) by selectively removing ionic or nonionic components. The lower the CPR value of the polyol, the better the physical properties of the polyurethane that can be prepared using the polyol.
구체적으로, 상기 CPR은 조성물 내의 염기성 물질의 양을 표시하는 지표로서, ASTM D6437의 실험방법에 의거하여 조성물 30 g을 메탄올 100 ml와 섞은 후 중화적정한 염산(농도:0.001N)의 양을 수치화한 결과이다. 상기 폴리올 조성물 내의 이온계 또는 비이온계 불순물이 효과적으로 제거됨에 따라 CPR 값이 낮아질 수 있다. Specifically, the CPR is an index indicating the amount of the basic substance in the composition. According to the test method of ASTM D6437, 30 g of the composition is mixed with 100 ml of methanol, and the amount of neutralized titrated hydrochloric acid (concentration: 0.001 N) is quantified. Is the result. The CPR value may be lowered as ionic or nonionic impurities in the polyol composition are effectively removed.
일 구현예에 따른 폴리올 조성물의 CPR은 2.4 미만이다. 다른 일 구현예에 따른 폴리올 조성물의 CPR은 2.0 이하이다. 또 다른 일 구현예에 따른 폴리올 조성물의 CPR은 0.8 이하이다.The CPR of the polyol composition according to one embodiment is less than 2.4. The CPR of the polyol composition according to another embodiment is 2.0 or less. The CPR of the polyol composition according to another embodiment is 0.8 or less.
또한, 상기 폴리올 조성물의 CPR은 0 이상이다. 나아가, 상기 폴리올 조성물의 CPR은 0.1 이상, 0.26 이상 또는 0.3 이상이다. 예를 들어, 상기 폴리올 조성물의 CPR은 0 이상 2.4 미만, 0 내지 2.3, 0 내지 2.2, 0 내지 2.1, 0 내지 2.0, 0 내지 1.9, 0 내지 1.8, 0 내지 1.7, 0 내지 1.6, 0 내지 1.5, 0 내지 1.4, 0 내지 1.3, 0 내지 1.2, 0 내지 1.1, 0 내지 1.0, 0 내지 0.9, 0 내지 0.8, 0.2 내지 0.8, 0.3 내지 0.8, 0.4 내지 0.8일 수 있으나, 이에 한정되는 것은 아니다. In addition, the CPR of the polyol composition is 0 or more. Furthermore, the CPR of the polyol composition is 0.1 or more, 0.26 or more, or 0.3 or more. For example, the CPR of the polyol composition is 0 or more and less than 2.4, 0 to 2.3, 0 to 2.2, 0 to 2.1, 0 to 2.0, 0 to 1.9, 0 to 1.8, 0 to 1.7, 0 to 1.6, 0 to 1.5 , 0 to 1.4, 0 to 1.3, 0 to 1.2, 0 to 1.1, 0 to 1.0, 0 to 0.9, 0 to 0.8, 0.2 to 0.8, 0.3 to 0.8, 0.4 to 0.8, but is not limited thereto.
일 구현예에 따른 폴리올 조성물의 질소(Nitrogen) 함량은 0.43 ppm 미만이다. 다른 일 구현예에 따른 폴리올 조성물의 질소 함량은 0.3 ppm 이하이다. 예를 들어, 폴리올 조성물의 질소 함량은 0.2 내지 0.4 ppm, 0.2 내지 0.38 pm, 0.2 내지 0.36pm, 0.2 내지 0.34pm, 0.2 내지 0.32pm 또는 0.2 내지 0.3ppm일 수 있으나, 이에 한정되는 것은 아니다. The nitrogen content of the polyol composition according to one embodiment is less than 0.43 ppm. The nitrogen content of the polyol composition according to another embodiment is 0.3 ppm or less. For example, the nitrogen content of the polyol composition may be 0.2 to 0.4 ppm, 0.2 to 0.38 pm, 0.2 to 0.36 pm, 0.2 to 0.34 pm, 0.2 to 0.32 pm or 0.2 to 0.3 ppm, but is not limited thereto.
상기 폴리올 조성물은 이온계 성분, 비이온계 성분 및 용매를 포함할 수 있다.The polyol composition may include an ionic component, a nonionic component and a solvent.
상기 폴리올 조성물은 이온계 성분 즉, 양이온계 성분 및 음이온계 성분을 포함할 수 있다. The polyol composition may include an ionic component, that is, a cationic component and an anionic component.
구체적으로, 상기 양이온계 성분은 NH2 +, NH4 + 및 이를 작용기로 가진 분자체들로 이루어진 군으로부터 선택된 1 종 이상일 수 있다. 예를 들어, 상기 양이온계 성분은 NH4 +를 포함할 수 있다. 또 다른 예로서, 상기 양이온계 성분은 NH2 + 및 NH4 +를 포함할 수 있다. 예를 들어, 상기 양이온계 성분은 NH4 +로 이루어질 수 있으나, 이에 한정되는 것은 아니다.Specifically, the cationic component may be one or more selected from the group consisting of NH 2 + , NH 4 + and molecular sieves having the functional group. For example, the cationic component may include NH 4 + . As another example, the cationic component may include NH 2 + and NH 4 + . For example, the cationic component, but be made of a NH 4 +, but is not limited to such.
또한, 상기 음이온계 성분은 NO2 -, NO3 - 및 이를 작용기로 가진 분자체들로 이루어진 군으로부터 선택된 1 종 이상일 수 있다. 예를 들어, 상기 음이온계 성분은 NO2 -를 포함할 수 있다. 또 다른 예로서, 상기 음이온계 성분은 NO2 - 및 NO3 -를 포함할 수 있다. 예를 들어, 상기 음이온계 성분은 NO2 -로 이루어질 수 있으나, 이에 한정되는 것은 아니다.Further, the anionic component is NO 2 - can be at least one member selected from the group consisting of the minute, and with it to the functional group itself -, NO 3. For example, the anionic component is NO 2 - can include. As yet another example, the anionic component is NO 2 - can include - and NO 3. For example, the anionic component may be made of NO 2 − , but is not limited thereto.
상기 이온계 성분은 질소 함유 이온계 성분을 포함할 수 있다.The ionic component may include a nitrogen-containing ionic component.
예를 들어, 상기 이온계 성분은 NH2 +, NH4 +, NO2 - 및 NO3 -로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 또는, 상기 이온계 성분은 NH2 +, NH4 +, NO2 - 및 NO3 -로 이루어진 군으로부터 선택된 1종 이상으로 이루어질 수 있다.For example, the ionic component is NH 2 +, NH 4 +, NO 2 - it can include at least one selected from the group consisting of - and NO 3. Alternatively, the ionic component is NH 2 +, NH 4 +, NO 2 - can be made of at least one selected from the group consisting of - and NO 3.
또한, 상기 폴리올 조성물은 이온계 성분 이외에 비이온계 성분을 포함할 수 있다.In addition, the polyol composition may include a nonionic component in addition to the ionic component.
예를 들어, 상기 비이온계 성분은 아민계 성분을 포함할 수 있다.For example, the non-ionic component may include an amine-based component.
구체적으로, 상기 아민계 성분은 디이소프로필아민(diisopropylamine), 디에틸아민(diethylamine), 트리에틸아민(trimethylamine), 디에탄올아민(diethanolamine), 디메틸에틸아민(dimethylethylamine), 메틸디에탄올아민(methyldiethanolamine), 트리메틸아민(Trimethylamine) 및 모노이소프로필아민(monoisopropylamine)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.Specifically, the amine component is diisopropylamine (diisopropylamine), diethylamine (diethylamine), triethylamine (dimethylamine), diethanolamine (diethanolamine), dimethylethylamine (dimethylethylamine), methyldiethanolamine (methyldiethanolamine ), Trimethylamine (Trimethylamine) and monoisopropylamine (monoisopropylamine) may include one or more selected from the group consisting of.
상기 폴리올 조성물의 질소 함량을 높이는 요인은 알킬렌 옥사이드 내의 상기 질소 함유 이온계 성분 및 질소 함유 비이온계 성분 때문이다. The factor that increases the nitrogen content of the polyol composition is due to the nitrogen-containing ionic component and nitrogen-containing nonionic component in the alkylene oxide.
또한, 상기 폴리올 조성물은 용매를 포함할 수 있다.In addition, the polyol composition may include a solvent.
구체적으로, 상기 용매는 물, 메탄올, 아세트알데히드(acetaldehyde), 프로피온알데히드(propionaldehyde), 메틸포메이트(methyl formate) 및 디메톡시메탄(dimethoxymethane)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.Specifically, the solvent may include one or more selected from the group consisting of water, methanol, acetaldehyde, propionaldehyde, methyl formate and dimethoxymethane.
폴리올 조성물의 제조 방법Manufacturing method of polyol composition
일 구현예에 따른 폴리올 조성물의 제조 방법은 (1) 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계; (2) 상기 정제된 알킬렌 옥사이드 조성물과 다가 알코올을 반응시키는 단계; 및 (3) 폴리올 조성물을 얻는 단계;를 포함하고, 상기 폴리올 조성물의 CPR은 2.4 미만이다. A method for preparing a polyol composition according to an embodiment includes (1) purifying an alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with a polyhydric alcohol; And (3) obtaining a polyol composition. The CPR of the polyol composition is less than 2.4.
먼저, 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계를 수행한다(단계 1)First, a step of purifying the alkylene oxide crude composition is performed (step 1).
상기 알킬렌 옥사이드 조(粗) 조성물(crude composition)이란, 알킬렌 옥사이드 제조 공정에 의해 제조된 직후의 조성물로서, 후속 공정에서 불필요한 이온계 성분 등을 포함하고 있는 조성물을 의미한다.The alkylene oxide crude composition is a composition immediately after being prepared by an alkylene oxide production process, and means a composition containing unnecessary ionic components and the like in a subsequent process.
상기 알킬렌 옥사이드 조 조성물은 알킬렌 옥사이드, 이온계 성분, 비이온계 성분 및 용매를 포함할 수 있다.The alkylene oxide crude composition may include an alkylene oxide, an ionic component, a nonionic component and a solvent.
상기 알킬렌 옥사이드 조 조성물은 이온계 성분을 포함할 수 있다. 상기 이온계 성분은 양이온계 성분 또는 음이온계 성분일 수 있다. The alkylene oxide crude composition may include an ionic component. The ionic component may be a cationic component or an anionic component.
일 구현예에 따르면, 상기 이온계 성분은 NH4 +를 포함하고, 상기 알킬렌 옥사이드 조 조성물 내에 포함된 NH4 +의 함량이 0.1 내지 5 ppm이다. 구체적으로, 상기 이온계 성분은 NH4 +를 포함하고, 상기 알킬렌 옥사이드 조 조성물 내에 포함된 NH4 +의 함량이 0.1 내지 3 ppm, 0.1 내지 2.5 ppm, 0.3 내지 2 ppm 또는 0.5 내지 1.5 ppm일 수 있으나, 이에 한정되는 것은 아니다.According to one embodiment, the ionic component includes NH 4 + , and the content of NH 4 + included in the alkylene oxide crude composition is 0.1 to 5 ppm. Specifically, the ionic component contains NH 4 + , and the content of NH 4 + contained in the alkylene oxide crude composition is 0.1 to 3 ppm, 0.1 to 2.5 ppm, 0.3 to 2 ppm, or 0.5 to 1.5 ppm. However, it is not limited thereto.
일 구현예에 따르면, 상기 이온계 성분은 NO2 -를 포함하고, 상기 알킬렌 옥사이드 조 조성물 내에 포함된 NO2 -의 함량이 0.1 내지 5 ppm이다. 구체적으로, 상기 이온계 성분은 NO2 -를 포함하고, 상기 알킬렌 옥사이드 조 조성물 내에 포함된 NO2 -의 함량이 0.1 내지 3 ppm, 0.1 내지 1 ppm 또는 0.25 내지 0.75 ppm일 수 있으나, 이에 한정되는 것은 아니다.According to one embodiment, the ionic component is NO 2 - content of 0.1 to 5 ppm - NO 2 contained in the crude alkylene oxide composition, comprising: a. Specifically, the ionic component is NO 2 - and wherein the alkylene oxides with NO 2 contained in the crude composition to - may be a range of 0.1 to 3 ppm content of 0.1 to 1 ppm or from 0.25 to 0.75 ppm, this limited It does not work.
상기 이온계 성분은 질소 함유 이온계 성분을 포함할 수 있다.The ionic component may include a nitrogen-containing ionic component.
예를 들어, 상기 이온계 성분은 NH2 +, NH4 +, NO2 - 및 NO3 -로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 또는, 상기 이온계 성분은 NH2 +, NH4 +, NO2 - 및 NO3 -로 이루어진 군으로부터 선택된 1종 이상으로 이루어질 수 있다.For example, the ionic component is NH 2 +, NH 4 +, NO 2 - it can include at least one selected from the group consisting of - and NO 3. Alternatively, the ionic component is NH 2 +, NH 4 +, NO 2 - can be made of at least one selected from the group consisting of - and NO 3.
상기 이온계 성분은 상기 이온계 성분의 총 중량을 기준으로 양이온계 성분을 30 내지 90 중량% 포함한다. 구체적으로, 상기 이온계 성분은 상기 이온계 성분의 총 중량을 기준으로 양이온계 성분을 40 내지 90 중량%, 50 내지 90 중량% 또는 50 내지 80 중량% 포함할 수 있다. 더욱 구체적으로, 상기 이온계 성분은 상기 이온계 성분의 총 중량을 기준으로 양이온계 성분을 60 내지 80 중량% 포함할 수 있으나, 이에 한정되는 것은 아니다.The ionic component contains 30 to 90% by weight of the cationic component based on the total weight of the ionic component. Specifically, the ionic component may include 40 to 90% by weight, 50 to 90% by weight, or 50 to 80% by weight based on the total weight of the ionic component. More specifically, the ionic component may include 60 to 80% by weight of the cationic component based on the total weight of the ionic component, but is not limited thereto.
상기 알킬렌 옥사이드 조 조성물은 이온계 성분 이외에 비이온계 성분을 포함할 수 있다. 상기 비이온계 성분에 대한 내용은 앞서 폴리올 조성물에서 진술한 바와 동일하다. The alkylene oxide crude composition may include a nonionic component in addition to the ionic component. The contents of the nonionic component are the same as those stated in the polyol composition.
또한, 상기 알킬렌 옥사이드 조 조성물은 용매를 포함할 수 있다.In addition, the alkylene oxide crude composition may include a solvent.
구체적으로, 상기 용매는 물, 메탄올, 아세트알데히드(acetaldehyde), 프로피온알데히드(propionaldehyde), 메틸포메이트(methyl formate) 및 디메톡시메탄(dimethoxymethane)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.Specifically, the solvent may include one or more selected from the group consisting of water, methanol, acetaldehyde, propionaldehyde, methyl formate and dimethoxymethane.
예를 들어, 상기 알킬렌 옥사이드 조 조성물은 디메톡시메탄(DMM) 및 메틸포메이트(MF)를 포함하고, 상기 디메톡시메탄(DMM) 및 메틸포메이트(MF)의 함량이 10 내지 3,000 ppm, 10 내지 1,000 ppm, 10 내지 500 ppm 또는 20 내지 100 ppm일 수 있으나, 이에 한정되는 것은 아니다.For example, the alkylene oxide crude composition includes dimethoxymethane (DMM) and methyl formate (MF), and the content of the dimethoxymethane (DMM) and methyl formate (MF) is 10 to 3,000 ppm, It may be 10 to 1,000 ppm, 10 to 500 ppm or 20 to 100 ppm, but is not limited thereto.
상기 알킬렌 옥사이드 조 조성물의 CPR(Controlled Polymerization Rate)은 0.2 내지 20이다. 구체적으로, 상기 알킬렌 옥사이드 조 조성물의 CPR은 0.2 내지 10, 0.2 내지 5, 0.2 내지 2, 0.5 내지 3, 0.5 내지 2 또는 0.8 내지 1.5일 수 있으나, 이에 한정되는 것은 아니다.The CPR (Controlled Polymerization Rate) of the alkylene oxide crude composition is 0.2 to 20. Specifically, the CPR of the alkylene oxide crude composition may be 0.2 to 10, 0.2 to 5, 0.2 to 2, 0.5 to 3, 0.5 to 2 or 0.8 to 1.5, but is not limited thereto.
상기 알킬렌 옥사이드 조 조성물의 CPR이 적정 범위를 만족하지 않는 경우, 이를 원료로 하는 후단 제품의 제조 과정에서 반응성 제어가 어려움은 물론, 이를 원료로 하는 후단 제품의 CPR 값이 제품 CPR 규격을 벗어나게 된다. 따라서, 알킬렌 옥사이드 조 조성물의 CPR 값이 적정 범위를 만족할 경우, 제품의 품질을 향상시킬 수 있다. 구체적으로, 알킬렌 옥사이드 조 조성물의 CPR 값을 최대 2.0 이하로 유지하는 것이 더욱 유리하다.If the CPR of the alkylene oxide crude composition does not satisfy the appropriate range, it is difficult to control the reactivity in the process of manufacturing the subsequent product using the raw material, and the CPR value of the latter product using the raw material exceeds the product CPR standard. . Therefore, when the CPR value of the alkylene oxide crude composition satisfies an appropriate range, product quality may be improved. Specifically, it is more advantageous to maintain the CPR value of the alkylene oxide crude composition at a maximum of 2.0 or less.
구체적으로, 앞서 언급한 이온계 불순물 중 양이온계 불순물이 음이온계 불순물보다 상대적으로 많음에 따라 불순물들끼리 중화된 이후에도 남아있는 양이온계 불순물이 상기 알킬렌 옥사이드 조 조성물의 CPR 값을 높이는 요인이 된다.Specifically, as the number of cationic impurities among the aforementioned ionic impurities is relatively higher than that of the anionic impurities, the remaining cationic impurities are factors that increase the CPR value of the alkylene oxide crude composition even after the impurities are neutralized.
상기 알킬렌 옥사이드 조 조성물의 질소(Nitrogen) 함량은 0.2 내지 10 ppm이다. 구체적으로, 상기 알킬렌 옥사이드 조 조성물의 질소 함량은 0.2 내지 7 ppm, 0.2 내지 5 ppm, 0.2 내지 3 ppm 또는 0.2 내지 2 ppm이다. 더욱 구체적으로, 상기 알킬렌 옥사이드 조 조성물의 질소 함량은 0.5 내지 1.8 ppm, 1.0 내지 1.8 ppm 또는 1.2 내지 1.8 ppm일 수 있으나, 이에 한정되는 것은 아니다.Nitrogen content of the alkylene oxide crude composition is 0.2 to 10 ppm. Specifically, the nitrogen content of the alkylene oxide crude composition is 0.2 to 7 ppm, 0.2 to 5 ppm, 0.2 to 3 ppm or 0.2 to 2 ppm. More specifically, the nitrogen content of the alkylene oxide crude composition may be 0.5 to 1.8 ppm, 1.0 to 1.8 ppm or 1.2 to 1.8 ppm, but is not limited thereto.
상기 알킬렌 옥사이드 조 조성물의 질소 함량을 높이는 요인은 앞서 언급한 질소 함유 이온계 성분 및 질소 함유 비이온계 성분 때문이다.The factors that increase the nitrogen content of the alkylene oxide crude composition are due to the aforementioned nitrogen-containing ionic components and nitrogen-containing nonionic components.
상기 알킬렌 옥사이드는 에틸렌 옥사이드, 프로필렌 옥사이드, 부틸렌 옥사이드 등일 수 있다. 구체적으로, 상기 알킬렌 옥사이드는 프로필렌 옥사이드일 수 있다.The alkylene oxide may be ethylene oxide, propylene oxide, butylene oxide, and the like. Specifically, the alkylene oxide may be propylene oxide.
일 구현예에 따르면, 상기 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계는 흡착제 이용법, 전기 화학법 및 증류법(Distillation)으로 이루어진 군에서 선택되는 1종 이상의 정제 방법을 수행하기 전에, 특히 흡작제를 이용한 정제 방법을 수행하기 전에 상기 알킬렌 옥사이드 조 조성물을 비드 구간에 통과시킬 수 있다. According to one embodiment, the step of purifying the alkylene oxide crude composition is performed prior to performing one or more purification methods selected from the group consisting of an adsorbent use method, an electrochemical method, and a distillation method, in particular, an adsorbent. Before performing the purification method using the alkylene oxide crude composition may be passed through a bead section.
상기 비드 구간은 1 내지 5 mm의 평균 직경을 갖는 복수개의 비드를 포함한다. 구체적으로, 상기 비드 구간은 1.5 내지 4 mm 또는 2 내지 3 mm의 평균 직경을 갖는 복수개의 비드를 포함할 수 있으나, 이에 한정되는 것은 아니다.The bead section includes a plurality of beads having an average diameter of 1 to 5 mm. Specifically, the bead section may include a plurality of beads having an average diameter of 1.5 to 4 mm or 2 to 3 mm, but is not limited thereto.
상기 비드 구간에 포함된 비드의 단위 부피당 개수가 100 내지 100,000 개/L이다. 구체적으로, 상기 비드 구간에 포함된 비드의 단위 부피당 개수는 1,000 내지 80,000 개/L, 5,000 내지 70,000 개/L, 10,000 내지 50,000 개/L, 15,000 내지 40,000 개/L일 수 있으나, 이에 한정되는 것은 아니다.The number of beads per unit volume of the beads included in the bead section is 100 to 100,000 pieces / L. Specifically, the number of beads per unit volume of the bead section may be 1,000 to 80,000 pieces / L, 5,000 to 70,000 pieces / L, 10,000 to 50,000 pieces / L, and 15,000 to 40,000 pieces / L, but is not limited thereto. no.
또한, 상기 알킬렌 옥사이드 조 조성물을 비드 구간에 통과시키는 공간 속도는 0 초과 내지 10 h-1 이하이다. 구체적으로, 상기 알킬렌 옥사이드 조 조성물을 비드 구간에 통과시키는 공간 속도는 0.2 내지 5 h-1, 0.2 내지 3 h-1, 0.2 내지 2 h-1, 0.5 내지 2 h-1 또는 0.8 내지 1.5 h-1일 수 있으나, 이에 한정되는 것은 아니다.In addition, the space velocity through which the alkylene oxide crude composition passes through the bead section is greater than 0 to 10 h −1 or less. Specifically, the space velocity through which the alkylene oxide crude composition passes through the bead section is 0.2 to 5 h -1 , 0.2 to 3 h -1 , 0.2 to 2 h -1 , 0.5 to 2 h -1 or 0.8 to 1.5 h -1 , but is not limited thereto.
상기 비드 구간에 포함된 비드는 실리칼라이트를 원료로 하는 비활성 물질을 포함할 수 있다.The beads included in the bead section may include an inactive material based on silicalite.
상기 비드 구간은 알킬렌 옥사이드 조 조성물이 후단의 정제 방법들, 특히 흡착제로 들어가기 전 고른 분산을 유도하는 역할을 수행한다.The bead section serves to induce an even dispersion before the alkylene oxide crude composition enters the subsequent purification methods, particularly the adsorbent.
일 구현예에 따르면, 상기 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계는 흡착제 이용법, 전기 화학법 및 증류법(Distillation)으로 이루어진 군에서 선택되는 1종 이상의 정제 방법을 사용할 수 있다. According to one embodiment, the step of purifying the alkylene oxide crude composition may use one or more purification methods selected from the group consisting of an adsorbent usage method, an electrochemical method, and a distillation method.
일 구현예에 따르면, 상기 알킬렌 옥사이드 조 조성물을 흡착제에 통과시킬 수 있다. According to one embodiment, the crude alkylene oxide composition may be passed through an adsorbent.
일 구현예에 따르면, 상기 흡착제 이용법은 제올라이트계 분자체(Mol-Sieve) 또는 네추럴 클레이(Natural Clay)를 이용할 수 있다. According to one embodiment, the method of using the adsorbent may be a zeolite-based molecular sieve (Mol-Sieve) or natural clay (Natural Clay).
상기 제올라이트계 분자체는 제올라이트 A, 제올라이트 X, 제올라이트 베타, 제올라이트 Y, 제올라이트 L 및 ZSM-12로 이루어진 군으로부터 선택된 구조를 가질 수 있다. The zeolite-based molecular sieve may have a structure selected from the group consisting of zeolite A, zeolite X, zeolite beta, zeolite Y, zeolite L and ZSM-12.
상기 분자체는 규소 알루미늄 산화물을 총칭하며, 산소원자 고리로 이뤄진 미세한 구멍의 입구를 가지고 이 구멍들 사이에서 일정 간격으로 꺾인 다른 구멍과 교차하는 팔각형 형태의 기하학적 구조일 수 있으나, 이에 한정되는 것은 아니다.The molecular sieve collectively refers to silicon aluminum oxide, and may be an octagonal geometric structure having an inlet of a fine hole made of an oxygen atom ring and intersecting another hole bent at regular intervals between the holes, but is not limited thereto. .
이때, 상기 분자체의 기공의 크기는 2.3 Å 초과 내지 10 Å 미만이다. 구체적으로, 상기 분자체의 기공의 크기는 3 내지 10 Å, 3 내지 7.5 Å, 3 내지 5 Å, 3.5 내지 4.5 Å, 3.8 내지 4.2 Å 또는 3.9 내지 4.1 Å 일 수 있으나, 이에 한정되는 것은 아니다.At this time, the pore size of the molecular sieve is greater than 2.3 mm 2 and less than 10 mm 2. Specifically, the pore size of the molecular sieve may be 3 to 10 Å, 3 to 7.5 Å, 3 to 5 Å, 3.5 to 4.5 Å, 3.8 to 4.2 Å or 3.9 to 4.1 Å, but is not limited thereto.
또한, 상기 분자체의 기공의 모양은 팔각 형태일 수 있다. 구체적으로, 상기 분자체는 팔각 형태의 미세 다공을 가지게 되며, 상업화 제품은 분자체들이 물리적으로 결합하여 약 2 mm 정도의 구형, 펠렛(pellet), 압출형(extrudate)등으로 제작될 수 있다.In addition, the shape of the pores of the molecular sieve may be octagonal. Specifically, the molecular sieve has an octagonal microporous shape, and the commercialized product may be manufactured into a spherical, pellet, extruded or the like of about 2 mm by physically bonding the molecular sieve.
상기 분자체는 팔각형 모양의 미세 다공보다 작은 불순물들을 선별하여 흡착할 수 있다. 또는, 상기 분자체의 제올라이트 계열 자체의 음전하(산점)가 알킬렌 옥사이드 조 조성물에 존재하는 양이온계 성분을 흡착할 수 있다.The molecular sieve can be adsorbed by selecting impurities smaller than the octagonal fine pores. Alternatively, the negative charge (acid point) of the zeolite series itself of the molecular sieve can adsorb the cationic component present in the alkylene oxide bath composition.
상기 네추럴 클레이(Natural Clay)는 몬모릴로나이트(Montmorillonite), 카올리나이트(Kaolinite), 세피올라이트(Sepiolite), 벤토나이트(Bentonite) 및 규조토(Diatomite)로 이루어진 군으로부터 선택될 수 있다. The natural clay may be selected from the group consisting of montmorillonite, kaolinite, sepiolite, bentonite, and diatomite.
상기 알킬렌 옥사이드 조 조성물을 흡착체에 통과시키는 공간 속도는 0 초과 내지 10 h-1 이하이다. 구체적으로, 상기 알킬렌 옥사이드 조 조성물을 분자체에 통과시키는 공간 속도는 0.2 내지 5 h-1, 0.2 내지 3 h-1, 0.2 내지 2 h-1, 0.5 내지 2 h-1 또는 0.8 내지 1.5 h-1일 수 있으나, 이에 한정되는 것은 아니다.The space velocity through which the alkylene oxide crude composition passes through the adsorbent is greater than 0 to 10 h −1 or less. Specifically, the space velocity through which the alkylene oxide crude composition passes through the molecular sieve is 0.2 to 5 h -1 , 0.2 to 3 h -1 , 0.2 to 2 h -1 , 0.5 to 2 h -1 or 0.8 to 1.5 h -1 , but is not limited thereto.
상기 전기 화학법은 그래파이트 포일(graphite foil)에 Pd/C 촉매를 일정량 코팅하여 두 개의 전극을 제작한 후, 전압을 가하는 장비와 연결한다. 상기 알킬렌 옥사이드 조 조성물이 담긴 반응기에 상기 두 개의 전극을 침지하고, 일정 시간 동안 일정 전압을 걸어 유지함으로써, 이온계 성분 등 CPR 값을 상승시키는 원인물질들이 전극에 흡착되어 제거될 수 있다. 예를 들어, 상기 두 개의 전극 사이에 0.85 V의 전압을 걸어 2시간 동안 유지할 수 있으나, 이에 한정되는 것은 아니다. In the electrochemical method, a certain amount of a Pd / C catalyst is coated on a graphite foil to produce two electrodes, and then connected to equipment that applies voltage. By immersing the two electrodes in a reactor containing the alkylene oxide bath composition and maintaining a constant voltage for a certain period of time, causative substances, such as ionic components, which increase the CPR value, can be removed by being adsorbed to the electrode. For example, a voltage of 0.85 V may be applied between the two electrodes to maintain it for 2 hours, but is not limited thereto.
상기 증류법은 상기 알킬렌 옥사이드 조 조성물을 저비점 물질 증류탑(Light purge column)을 이용함으로써, 이온계 성분 등 CPR 값을 상승시키는 원인물질들을 제거할 수 있다.In the distillation method, by using the alkylene oxide crude composition using a low-boiling-point material distillation column (Light purge column), it is possible to remove causative substances that increase the CPR value such as ionic components.
상기 정제 방법을 사용하여 정제된 알킬렌 옥사이드 조성물은 양이온계 성분 및 음이온계 성분을 포함하는 이온계 성분을 포함한다. 이 때, 이온계 성분의 종류에 대한 설명은 상기 알킬렌 옥사이드 조 조성물에 기재된 바와 같다. The alkylene oxide composition purified using the above purification method includes an ionic component including a cationic component and an anionic component. At this time, the description of the type of the ionic component is as described in the alkylene oxide crude composition.
또한, 상기 정제된 알킬렌 옥사이드 조성물은 이온계 성분 이외에 비이온계 성분 및 용매를 포함할 수 있고, 이에 대한 설명 또한 상기 알킬렌 옥사이드 조 조성물에 기재된 바와 같다.In addition, the purified alkylene oxide composition may include a non-ionic component and a solvent in addition to the ionic component, and the description thereof is also as described in the alkylene oxide crude composition.
상기 정제된 알킬렌 옥사이드 조성물이 양이온계 성분 및 음이온계 성분을 포함하는 이온계 성분을 포함하는 경우, 상기 이온계 성분은 이온계 성분의 총 중량을 기준으로 양이온계 성분을 10 내지 70 중량% 포함한다. 구체적으로, 상기 이온계 성분은 이온계 성분의 총 중량을 기준으로 양이온계 성분을 20 내지 70 중량%, 30 내지 70 중량%, 40 내지 60 중량% 또는 45 내지 55 중량% 포함할 수 있으나, 이에 한정되는 것은 아니다.When the purified alkylene oxide composition includes an ionic component including a cationic component and anionic component, the ionic component contains 10 to 70% by weight of the cationic component based on the total weight of the ionic component. do. Specifically, the ionic component may include 20 to 70% by weight, 30 to 70% by weight, 40 to 60% by weight, or 45 to 55% by weight based on the total weight of the ionic component. It is not limited.
예를 들어, 상기 정제된 알킬렌 옥사이드 조성물은 NH4 +를 포함하고, 상기 정제된 알킬렌 옥사이드 조성물 내에 포함된 NH4 +의 함량은 0.05 내지 2.5 ppm이다. 구체적으로, 상기 정제된 알킬렌 옥사이드 조성물 내에 포함된 NH4 +의 함량은 0.1 내지 2 ppm, 0.1 내지 1 ppm, 0.2 내지 0.8 ppm, 0.2 내지 0.6 ppm 또는 0.4 내지 0.6 ppm일 수 있으나, 이에 한정되는 것은 아니다.For example, the purified alkylene oxide composition and the content of NH 4 + is contained within and wherein the purified alkylene oxide composition of the NH 4 + is from 0.05 to 2.5 ppm. Specifically, the content of NH 4 + contained in the purified alkylene oxide composition may be 0.1 to 2 ppm, 0.1 to 1 ppm, 0.2 to 0.8 ppm, 0.2 to 0.6 ppm, or 0.4 to 0.6 ppm, but is not limited thereto. It is not.
또한, 상기 정제된 알킬렌 옥사이드 조성물은 NO2 -를 포함하고, 상기 정제된 알킬렌 옥사이드 조성물 내에 포함된 NO2 -의 함량이 0.1 내지 5 ppm이다. 구체적으로, 상기 정제된 알킬렌 옥사이드 조성물 내에 포함된 NO2 -의 함량이 0.1 내지 3 ppm 또는 0.25 내지 0.75 ppm일 수 있으나, 이에 한정되는 것은 아니다.In addition, the purified alkylene oxide composition NO 2 - is the amount of 0.1 to 5 ppm - and include, the NO 2 contained in the purified alkylene oxide composition a. Specifically, the content of NO 2 − contained in the purified alkylene oxide composition may be 0.1 to 3 ppm or 0.25 to 0.75 ppm, but is not limited thereto.
상기 정제된 알킬렌 옥사이드 조성물의 CPR은 0 내지 2이다. 구체적으로, 상기 정제된 알킬렌 옥사이드 조성물의 CPR은 0 내지 1.5, 0 내지 1.2, 0 내지 0.8, 0 내지 0.5, 0.1 내지 0.5, 0.1 내지 0.3 또는 0.1 내지 0.2일 수 있으나, 이에 한정되는 것은 아니다.The purified alkylene oxide composition has a CPR of 0 to 2. Specifically, the CPR of the purified alkylene oxide composition may be 0 to 1.5, 0 to 1.2, 0 to 0.8, 0 to 0.5, 0.1 to 0.5, 0.1 to 0.3 or 0.1 to 0.2, but is not limited thereto.
상기 정제된 알킬렌 옥사이드 조성물의 CPR이 상기 범위인 경우, 이를 원료로 하는 후단 제품의 제조 과정에서 반응성 제어를 수월하게 할 뿐만 아니라 만들어진 제품의 낮아진 CPR 값 자체로도 제품 CPR 규격을 만족한다는 점에서 유리하다.In the case where the CPR of the purified alkylene oxide composition is within the above range, it not only facilitates the control of reactivity in the manufacturing process of a rear end product using it as a raw material, but also satisfies the product CPR standard with the lowered CPR value of the product itself. It is advantageous.
상기 정제된 알킬렌 옥사이드 조성물의 염기도는 0 내지 4이다. 구체적으로, 상기 정제된 알킬렌 옥사이드 조성물의 염기도는 0 내지 3, 0 내지 2.4, 0 내지 1.6 또는 0 내지 1.0일 수 있으나, 이에 한정되는 것은 아니다.The purified alkylene oxide composition has a basicity of 0 to 4. Specifically, the basicity of the purified alkylene oxide composition may be 0 to 3, 0 to 2.4, 0 to 1.6 or 0 to 1.0, but is not limited thereto.
상기 정제된 알킬렌 옥사이드 조성물의 질소(Nitrogen) 함량은 0.1 내지 5 ppm이다. 구체적으로, 상기 정제된 알킬렌 옥사이드 조성물의 질소 함량은 0.1 내지 3 ppm, 0.1 내지 2 ppm, 0.2 내지 1.5 ppm 또는 0.4 내지 1.1 ppm일 수 있으나, 이에 한정되는 것은 아니다.Nitrogen content of the purified alkylene oxide composition is 0.1 to 5 ppm. Specifically, the nitrogen content of the purified alkylene oxide composition may be 0.1 to 3 ppm, 0.1 to 2 ppm, 0.2 to 1.5 ppm or 0.4 to 1.1 ppm, but is not limited thereto.
이후, 상기 정제된 알킬렌 옥사이드 조성물과 다가 알코올을 반응시키는 단계를 수행한다(단계 (2)).Thereafter, a step of reacting the purified alkylene oxide composition with a polyhydric alcohol is performed (step (2)).
일 구현예에 따르면, 상기 다가 알코올은 글리세롤, 프로필렌 글리콜, 수크로우즈(sucrose), 소비톨(sorbitol) 및 트리에탄올아민으로 이루어진 군으로부터 선택되는 1종 이상일 수 있다. According to one embodiment, the polyhydric alcohol may be at least one selected from the group consisting of glycerol, propylene glycol, sucrose, sorbitol, and triethanolamine.
일 구현예에 따르면, 상기 단계 (2)는 촉매, 중화제 및 산화 방지제로 이루어진 군으로부터 선택되는 1종 이상을 더 포함하여 수행될 수 있다. According to one embodiment, the step (2) may be performed by further comprising at least one selected from the group consisting of catalysts, neutralizing agents and antioxidants.
상기 촉매는 수산화칼슘, 수산화나트륨, 수산화칼륨, 수산화바륨, 이미다졸, 수산화세슘 및 포스파젠으로 이루어진 군으로부터 선택되는 1종 이상일 수 있으나, 이에 한정되는 것은 아니다. 상기 촉매를 사용함으로써, 부반응으로 인한 모노올의 발생을 억제하고 공정비용을 절감할 수 있다.The catalyst may be at least one selected from the group consisting of calcium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, imidazole, cesium hydroxide and phosphazene, but is not limited thereto. By using the catalyst, it is possible to suppress the generation of monool due to side reactions and reduce the process cost.
이후, 상기 단계 (2)를 거쳐 폴리올 조성물을 얻을 수 있다(단계 (3)).Thereafter, the polyol composition may be obtained through the step (2) (step (3)).
상기 폴리올 조성물에 대한 설명은 상술한 바와 같다. The description of the polyol composition is as described above.
일 구현예에 따르면, 상기 폴리올 조성물을 이소시아네이트와 반응시켜 폴리우레탄 조성물을 얻을 수 있다. According to one embodiment, the polyurethane composition may be obtained by reacting the polyol composition with isocyanate.
상기 폴리우레탄 조성물은 CPR이 낮은 폴리올 조성물을 사용하여 제조됨으로써, CPR이 낮고, 인열 강도, 인장 강도, 연신율, 통기성, 반발 탄성 등을 개선할 수 있다. The polyurethane composition is prepared by using a polyol composition having a low CPR, and thus has a low CPR, and can improve tear strength, tensile strength, elongation, breathability, and resilience.
상기 이소시아네이트는 R-(NCO)n의 일반식으로 표시되는 화합물로서, R은 알킬 또는 페닐이고, n은 2 내지 5일 수 있다. The isocyanate is a compound represented by the general formula of R- (NCO) n, R is alkyl or phenyl, and n may be 2 to 5.
상기 이소시아네이트는 예를 들어, 에틸렌디이소시아네이트, 1,4-테트라메틸렌디이소시아네이트, 1,6-헥사메틸렌디이소시아네이트, 1,12-도데칸디이소시이네이트, 사이클로부탄-1,3-디이소시아네이트, 사이클로헥산-1,3-디이소시아네이트, 수소치환된 메틸렌디페닐디이소시아네이트, 1,3-페닐렌디이소시아네이트, 1,4-페닐렌디이소시아네이트, 2,4-톨루엔디이소시아네이트, 2,6-톨루엔디이소시아네이트, 디페닐메탄-1,5-디이소시아네이트, 디페닐메탄-4,4'-디이소시아네이트, 메틸렌디페닐디이소시아네이트(MDI), 변성 폴리이소시아네이트, 2,4-헥사하이드로톨루엔디이소시아네이트, 2,6-헥사하이드로톨루엔디이소시아네이트, 퍼클로리네이트이소시아네이트, m- 이소시아나토페닐설포닐이소시아네이트 및 p-이소시아나토페닐설포닐이소시아네이트 중에서 선택되는 1종 이상일 수 있으나, 이에 한정되는 것은 아니다. The isocyanate is, for example, ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecanediisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane -1,3-diisocyanate, hydrogen-substituted methylene diphenyl diisocyanate, 1,3-phenylenediisocyanate, 1,4-phenylenediisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, di Phenylmethane-1,5-diisocyanate, diphenylmethane-4,4'-diisocyanate, methylenediphenyldiisocyanate (MDI), modified polyisocyanate, 2,4-hexahydrotoluene diisocyanate, 2,6-hexa Choose from hydrotoluene diisocyanate, perchlorinate isocyanate, m-isocyanatophenylsulfonyl isocyanate and p-isocyanatophenylsulfonyl isocyanate. It may be one or more, but is not limited thereto.
상기 폴리우레탄 조성물은 정포제, 경화제, 반응조절제, 셀조절제, 중합억제제, 난연제, 계면활성제, 경도향상제 등의 첨가제를 추가로 포함할 수 있다.The polyurethane composition may further include additives such as foam stabilizers, curing agents, reaction regulators, cell regulators, polymerization inhibitors, flame retardants, surfactants, and hardness improvers.
상기 정포제로는 폴리에테르 실란을 사용할 수 있으며, 상기 폴리에테르 실란은 실란 기본 구조에 에틸렌옥사이드, 프로필렌옥사이드 등으로 중합된 고분자가 가교된 것일 수 있다. 또한, 상기 폴리우레탄은 발포제를 추가로 포함하여 폼(foam) 형태를 가질 수 있다.As the antifoaming agent, polyether silane may be used, and the polyether silane may be a crosslinked polymer polymerized with ethylene oxide, propylene oxide, etc. on the silane basic structure. In addition, the polyurethane may further include a foaming agent to have a foam form.
상기 폴리올 조성물 및 이소시아네이트의 반응에는 유기 금속 촉매 또는 아민 촉매를 사용할 수 있다.An organic metal catalyst or an amine catalyst can be used for the reaction of the polyol composition and the isocyanate.
상기 유기 금속 촉매로는 디-n-옥틸주석-머캅타이드, 주석(III) 카복실레이트, 주석(III) 아세테이트, 주석 (III) 옥토에이트, 주석(III) 에틸헥소에이트, 주석(III) 라우레이트, 디부틸주석디라우레이트, 디부틸주석말레이트, 디옥틸주석디아세테이트 등이 있으나, 이에 한정되는 것은 아니다. The organometallic catalysts include di-n-octyltin-mercaptide, tin (III) carboxylate, tin (III) acetate, tin (III) octoate, tin (III) ethylhexate, tin (III) laurate , Dibutyl tin dilaurate, dibutyl tin maleate, dioctyl tin diacetate, and the like, but are not limited thereto.
상기 아민 촉매로는 트리에틸렌아민, 트리부틸렌아민, N-메틸모폴린, N-에틸모폴린, N,N'-테트라메틸에틸렌디아민, 펜타메틸-디에틸렌트리아민, 1,4-디아자바이사이클로[2,2,2]옥탄, N-메틸-N'-디메틸-아미노에틸 피페라진, 비스-디메틸아미노알킬피페라진, N,N-디메틸벤질아미드, 비스-N,N'-디에틸아미노에틸아디페이트, N,N'-디메틸-페닐에틸아미드, 1,2-디메틸-이미다졸 등이 있으나, 이에 한정되는 것은 아니다. As the amine catalyst, triethyleneamine, tributyleneamine, N-methylmorpholine, N-ethylmorpholine, N, N'-tetramethylethylenediamine, pentamethyl-diethylenetriamine, 1,4-diazabi Cyclo [2,2,2] octane, N-methyl-N'-dimethyl-aminoethyl piperazine, bis-dimethylaminoalkyl piperazine, N, N-dimethylbenzylamide, bis-N, N'-diethylamino Ethyl adipate, N, N'-dimethyl-phenylethylamide, 1,2-dimethyl-imidazole, and the like, but is not limited thereto.
프로필렌 글리콜 조성물Propylene glycol composition
구현예는 이온계 또는 비이온계 성분이 선택적으로 제거되어 낮은 질소 함량을 갖는 프로필렌 글리콜 조성물을 제공한다. 프로필렌 글리콜의 질소 함량이 낮을수록, 프로필렌 글리콜을 이용하여 제조될 수 있는 후속 공정에서 제조되는 물질들의 물성의 향상시킬 수 있는 장점이 있다. Embodiments provide a propylene glycol composition having a low nitrogen content by selectively removing ionic or nonionic components. The lower the nitrogen content of propylene glycol, the better the physical properties of materials produced in a subsequent process that can be produced using propylene glycol.
일 구현예에 따른 프로필렌 글리콜 조성물의 질소(Nitrogen) 함량은 0.4 ppm 미만이다. 다른 일 구현예에 따른 프로필렌 글리콜 조성물의 질소 함량은 0.3 ppm 이하이다. 또 다른 일 구현예에 따른 프로필렌 글리콜 조성물의 질소 함량은 0.2 ppm 이하이다. 또한, 상기 프로필렌 글리콜 조성물의 질소 함량은 0 ppm 이상, 0.05 ppm 이상 또는 0.1 ppm 이상일 수 있다. The nitrogen content of the propylene glycol composition according to one embodiment is less than 0.4 ppm. The nitrogen content of the propylene glycol composition according to another embodiment is 0.3 ppm or less. The nitrogen content of the propylene glycol composition according to another embodiment is 0.2 ppm or less. Further, the nitrogen content of the propylene glycol composition may be 0 ppm or more, 0.05 ppm or more, or 0.1 ppm or more.
예를 들어, 상기 프로필렌 글리콜 조성물의 질소 함량은 0.1 이상 내지 0.4 ppm 미만, 0.1 내지 0.38 ppm, 0.1 내지 0.36 ppm, 0.1 내지 0.34 ppm, 0.1 내지 0.32 ppm, 0.1 내지 0.3 ppm, 0.1 내지 0.28 ppm, 0.1 내지 0.26 ppm, 0.1 내지 0.24 ppm, 0.1 내지 0.22 ppm 또는 0.1 내지 0.2 ppm 일 수 있으나, 이에 한정되는 것은 아니다. For example, the nitrogen content of the propylene glycol composition is 0.1 or more to less than 0.4 ppm, 0.1 to 0.38 ppm, 0.1 to 0.36 ppm, 0.1 to 0.34 ppm, 0.1 to 0.32 ppm, 0.1 to 0.3 ppm, 0.1 to 0.28 ppm, 0.1 To 0.26 ppm, 0.1 to 0.24 ppm, 0.1 to 0.22 ppm or 0.1 to 0.2 ppm, but is not limited thereto.
상기 프로필렌 글리콜 조성물은 이온계 성분, 비이온계 성분 및 용매를 포함할 수 있다.The propylene glycol composition may include an ionic component, a nonionic component and a solvent.
상기 프로필렌 글리콜 조성물은 이온계 성분 즉, 양이온계 성분 및 음이온계 성분을 포함할 수 있다. The propylene glycol composition may include an ionic component, that is, a cationic component and an anionic component.
구체적으로, 상기 양이온계 성분은 NH2 +, NH4 + 및 이를 작용기로 가진 분자체들로 이루어진 군으로부터 선택된 1 종 이상일 수 있다. 예를 들어, 상기 양이온계 성분은 NH4 +를 포함할 수 있다. 또 다른 예로서, 상기 양이온계 성분은 NH2 + 및 NH4 +를 포함할 수 있다. 예를 들어, 상기 양이온계 성분은 NH4 +로 이루어질 수 있으나, 이에 한정되는 것은 아니다.Specifically, the cationic component may be one or more selected from the group consisting of NH 2 + , NH 4 + and molecular sieves having the functional group. For example, the cationic component may include NH 4 + . As another example, the cationic component may include NH 2 + and NH 4 + . For example, the cationic component, but be made of a NH 4 +, but is not limited to such.
또한, 상기 음이온계 성분은 NO2 -, NO3 - 및 이를 작용기로 가진 분자체들로 이루어진 군으로부터 선택된 1 종 이상일 수 있다. 예를 들어, 상기 음이온계 성분은 NO2 -를 포함할 수 있다. 또 다른 예로서, 상기 음이온계 성분은 NO2 - 및 NO3 -를 포함할 수 있다. 예를 들어, 상기 음이온계 성분은 NO2 -로 이루어질 수 있으나, 이에 한정되는 것은 아니다.Further, the anionic component is NO 2 - can be at least one member selected from the group consisting of the minute, and with it to the functional group itself -, NO 3. For example, the anionic component is NO 2 - can include. As yet another example, the anionic component is NO 2 - can include - and NO 3. For example, the anionic component may be made of NO 2 − , but is not limited thereto.
상기 이온계 성분은 질소 함유 이온계 성분을 포함할 수 있다.The ionic component may include a nitrogen-containing ionic component.
예를 들어, 상기 이온계 성분은 NH2 +, NH4 +, NO2 - 및 NO3 -로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다. 또는, 상기 이온계 성분은 NH2 +, NH4 +, NO2 - 및 NO3 -로 이루어진 군으로부터 선택된 1종 이상으로 이루어질 수 있다.For example, the ionic component is NH 2 +, NH 4 +, NO 2 - it can include at least one selected from the group consisting of - and NO 3. Alternatively, the ionic component is NH 2 +, NH 4 +, NO 2 - can be made of at least one selected from the group consisting of - and NO 3.
또한, 상기 프로필렌 글리콜 조성물은 이온계 성분 이외에 비이온계 성분을 포함할 수 있다.Further, the propylene glycol composition may include a non-ionic component in addition to the ionic component.
예를 들어, 상기 비이온계 성분은 아민계 성분을 포함할 수 있다.For example, the non-ionic component may include an amine-based component.
구체적으로, 상기 아민계 성분은 디이소프로필아민(diisopropylamine), 디에틸아민(diethylamine), 트리에틸아민(trimethylamine), 디에탄올아민(diethanolamine), 디메틸에틸아민(dimethylethylamine), 메틸디에탄올아민(methyldiethanolamine), 트리메틸아민(Trimethylamine) 및 모노이소프로필아민(monoisopropylamine)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.Specifically, the amine-based component is diisopropylamine, diethylamine, triethylamine, diethanolamine, dimethylethylamine, methyldiethanolamine ), Trimethylamine (Trimethylamine) and monoisopropylamine (monoisopropylamine) may include one or more selected from the group consisting of.
상기 프로필렌 글리콜 조성물의 질소 함량을 높이는 요인은 프로필렌 옥사이드 내의 상기 질소 함유 이온계 성분 및 질소 함유 비이온계 성분 때문이다. The reason for increasing the nitrogen content of the propylene glycol composition is due to the nitrogen-containing ionic component and nitrogen-containing nonionic component in propylene oxide.
또한, 상기 프로필렌 옥사이드 조 조성물은 용매를 포함할 수 있다.In addition, the propylene oxide crude composition may include a solvent.
구체적으로, 상기 용매는 물, 메탄올, 아세트알데히드(acetaldehyde), 프로피온알데히드(propionaldehyde), 메틸포메이트(methyl formate) 및 디메톡시메탄(dimethoxymethane)으로 이루어진 군으로부터 선택된 1종 이상을 포함할 수 있다.Specifically, the solvent may include one or more selected from the group consisting of water, methanol, acetaldehyde, propionaldehyde, methyl formate and dimethoxymethane.
일 구현예에 따른 프로필렌 글리콜 조성물의 냄새 강도 지수(odor index)는 3 미만이다. 다른 일 구현예에 따른 프로필렌 글리콜 조성물의 냄새 강도 지수는 1 이하이다. 구체적으로, 상기 프로필렌 글리콜 조성물의 냄새 강도 지수는 0 내지 3 미만, 0 내지 2, 0 내지 1 또는 0 내지 0.5일 수 있으나, 이에 한정되는 것은 아니다. The odor index of the propylene glycol composition according to one embodiment is less than 3. The odor strength index of the propylene glycol composition according to another embodiment is 1 or less. Specifically, the odor intensity index of the propylene glycol composition may be 0 to less than 3, 0 to 2, 0 to 1 or 0 to 0.5, but is not limited thereto.
상기 냄새 강도 지수(odor index)는 조성물의 냄새를 하기 기준에 의해 측정한 것이다. The odor index is an odor of the composition measured by the following criteria.
0: 무취0: Odorless
1.0: 숙련인에게만 감지된다. 1.0: Detected only by experienced personnel.
1.5 내지 2.0: 누구에게나 감지되나, 맡기 싫은 냄새는 아니다.1.5 to 2.0: Detected by anyone, but it is not an unpleasant smell.
2.5 내지 3.0: 누구에게나 감지되며, 비릿한 냄새가 난다.2.5 to 3.0: Detected by anyone and smells fishy.
일 구현예에 따른 프로필렌 글리콜 조성물은 모노 프로필렌 글리콜, 다이 프로필렌 글리콜 및 트리 프로필렌 글리콜로 이루어진 군으로부터 선택되는 1종 이상을 포함한다. The propylene glycol composition according to one embodiment includes at least one selected from the group consisting of mono propylene glycol, dipropylene glycol and tripropylene glycol.
상기 모노 프로필렌 글리콜의 함량은 상기 프로필렌 글리콜 조성물의 총 중량을 기준으로, 60 내지 80 중량%일 수 있다. 구체적으로, 65 내지 80 중량%, 65 내지 75 중량% 또는 65 내지 70 중량%일 수 있으나, 이에 한정되는 것은 아니다. The content of the mono propylene glycol may be 60 to 80% by weight based on the total weight of the propylene glycol composition. Specifically, it may be 65 to 80% by weight, 65 to 75% by weight or 65 to 70% by weight, but is not limited thereto.
상기 다이 프로필렌 글리콜의 함량은 상기 프로필렌 글리콜 조성물의 총 중량을 기준으로, 20 내지 30 중량%일 수 있다. 구체적으로, 22 내지 30 중량%, 22 내지 28 중량% 또는 22 내지 25 중량%일 수 있으나, 이에 한정되는 것은 아니다.The content of the dipropylene glycol may be 20 to 30% by weight based on the total weight of the propylene glycol composition. Specifically, it may be 22 to 30% by weight, 22 to 28% by weight, or 22 to 25% by weight, but is not limited thereto.
프로필렌 글리콜 조성물의 제조 방법Method for preparing propylene glycol composition
일 구현예에 따른 프로필렌 글리콜 조성물의 제조 방법은 (1) 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계; (2) 상기 정제된 알킬렌 옥사이드 조성물과 물을 반응시키는 단계; 및 (3) 프로필렌 글리콜 조성물을 얻는 단계;를 포함하고, 상기 프로필렌 글리콜 조성물의 질소(Nitrogen) 함량이 0.4 ppm 미만이다. Method for producing a propylene glycol composition according to one embodiment comprises the steps of (1) purifying the alkylene oxide crude composition; (2) reacting the purified alkylene oxide composition with water; And (3) obtaining a propylene glycol composition; wherein the nitrogen content of the propylene glycol composition is less than 0.4 ppm.
먼저, 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계를 수행한다(단계 1)First, a step of purifying the alkylene oxide crude composition is performed (step 1).
상기 단계 (1)에 대한 설명은 상술한 바와 같다. The description of step (1) is as described above.
이후, 상기 정제된 알킬렌 옥사이드 조성물과 물을 반응시키는 단계를 수행한다(단계 (2)).Then, a step of reacting the purified alkylene oxide composition with water is performed (step (2)).
상기 프로필렌 글리콜 조성물은 하기 반응식 1과 같이, 알킬렌 옥사이드 조성물 및 물을 100 내지 200℃에서 반응시켜 제조될 수 있다. The propylene glycol composition may be prepared by reacting an alkylene oxide composition and water at 100 to 200 ° C, as shown in Scheme 1 below.
[반응식 1][Scheme 1]
Figure PCTKR2018016754-appb-I000001
Figure PCTKR2018016754-appb-I000001
이후, 상기 단계 (2)를 거쳐 비점 차이를 이용한 정제공정을 거치면 프로필렌 글리콜 조성물을 얻을 수 있다(단계 (3)). Subsequently, a propylene glycol composition can be obtained by performing a purification process using the boiling point difference through the step (2) (step (3)) .
상기 프로필렌 글리콜 조성물에 대한 설명은 상술한 바와 같다. The description of the propylene glycol composition is as described above.
상기 내용을 하기 실시예에 의하여 더욱 상세하게 설명한다. 단, 하기 실시예는 본 발명을 예시하기 위한 것일 뿐, 실시예의 범위가 이들만으로 한정되는 것은 아니다.The above contents will be described in more detail by the following examples. However, the following examples are only for illustrating the present invention, and the scope of the examples is not limited to these.
<실시예><Example>
<실시예 1-1><Example 1-1>
알킬렌 옥사이드 조(粗) 조성물 100 g을 제올라이트계 분자체(Mol Sieve)를 이용하여, 정제된 프로필렌 옥사이드 조성물을 100 g 얻었다. 100 g of the purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
프로필렌 글리콜과 수산화칼륨을 넣어 혼합한 후, 상기 정제된 프로필렌 옥사이드 조성물과 반응시켰다. 이후, 중화조에서 중화제인 마그네솔을 넣어 K+이온을 중화시켜 여과하였다. 이후, 산화 방지제를 넣어 혼합한 후, 남은 물을 증류시켜 폴리올 조성물 A를 얻었다. After mixing with propylene glycol and potassium hydroxide, it was reacted with the purified propylene oxide composition. Subsequently, a neutralizing agent was added to the neutralizer to neutralize K + ions and filtered. Thereafter, after adding the antioxidant and mixing, the remaining water was distilled to obtain a polyol composition A.
<실시예 1-2><Example 1-2>
알킬렌 옥사이드 조(粗) 조성물 100 g을 제올라이트계 분자체(Mol Sieve)를 이용하여, 정제된 프로필렌 옥사이드 조성물을 100 g 얻었다. 100 g of a purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
글리세린과 수산화칼륨을 넣어 혼합한 후, 상기 정제된 프로필렌 옥사이드 조성물과 에틸렌 옥사이드를 동시에 투입하여 반응시켰다. 이후, 중화조에서 중화제인 마그네솔을 넣어 K+이온을 중화시켜 여과하였다. 이후, 산화 방지제를 넣어 혼합한 후, 남은 물을 증류시켜 폴리올 조성물 B를 얻었다. After mixing with glycerin and potassium hydroxide, the purified propylene oxide composition and ethylene oxide were simultaneously added to react. Subsequently, a neutralizing agent was added to the neutralizer to neutralize K + ions and filtered. Thereafter, after adding the antioxidant and mixing, the remaining water was distilled to obtain a polyol composition B.
<실시예 1-3><Example 1-3>
알킬렌 옥사이드 조(粗) 조성물 100 g을 제올라이트계 분자체(Mol Sieve)를 이용하여, 정제된 프로필렌 옥사이드 조성물을 100 g 얻었다. 100 g of the purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
글리세린과 수산화칼륨을 넣어 혼합한 후, 상기 정제된 프로필렌 옥사이드 조성물과 반응시켰다. 이후, 에틸렌 옥사이드를 넣어 반응시켰다. 이후, 중화조에서 중화제인 마그네솔을 넣어 K+이온을 중화시켜 여과하였다. 이후, 산화 방지제를 넣어 혼합한 후, 남은 물을 증류시켜 폴리올 조성물 C를 얻었다. After mixing with glycerin and potassium hydroxide, it was reacted with the purified propylene oxide composition. Then, ethylene oxide was added to react. Thereafter, a neutralizing agent was added to the neutralizer to neutralize K + ions and filtered. Thereafter, after adding the antioxidant and mixing, the remaining water was distilled to obtain a polyol composition C.
<비교예 1-1><Comparative Example 1-1>
실시예 1-1에서 알킬렌 옥사이드 조(粗) 조성물 100 g을 정제하지 않고 사용한 것을 제외하고, 상기 실시예 1과 동일하게 실험하여 폴리올 조성물 D를 얻었다. A polyol composition D was obtained in the same manner as in Example 1, except that 100 g of the alkylene oxide crude composition in Example 1-1 was used without purification.
<비교예 1-2><Comparative Example 1-2>
실시예 1-2에서 알킬렌 옥사이드 조(粗) 조성물 100 g을 정제하지 않고 사용한 것을 제외하고, 상기 실시예 1-2와 동일하게 실험하여 폴리올 조성물 E를 얻었다. A polyol composition E was obtained in the same manner as in Example 1-2, except that 100 g of the alkylene oxide crude composition in Example 1-2 was used without purification.
<비교예 1-3><Comparative Example 1-3>
실시예 1-3에서 알킬렌 옥사이드 조(粗) 조성물 100 g을 정제하지 않고 사용한 것을 제외하고, 상기 실시예 1-3과 동일하게 실험하여 폴리올 조성물 F를 얻었다. A polyol composition F was obtained in the same manner as in Example 1-3, except that 100 g of the alkylene oxide crude composition in Example 1-3 was used without purification.
<평가예 1-1: CPR 측정><Evaluation Example 1-1: CPR measurement>
ASTM D 6437(Standard Test Method for Polyurethane Raw materials)의 실험법에 의거하여, 각각의 조성물 30g을 메탄올 100ml에 혼합한 후, 0.001N 염산으로 중화 적정하여 소비되는 염산의 양을 계산하였다. According to the test method of ASTM D 6437 (Standard Test Method for Polyurethane Raw materials), 30 g of each composition was mixed in 100 ml of methanol, and then neutralized titration with 0.001 N hydrochloric acid to calculate the amount of hydrochloric acid consumed.
<평가예 1-2: 질소 함량 측정><Evaluation Example 1-2: nitrogen content measurement>
ASTM D 6437(Standard Test Method for Polyurethane Raw materials)의 실험법에 의거하여, 각각의 조성물 0.6g을 톨루엔 3g에 희석한 후, 산소 및 아르곤 상태에서 연소시켜 발생된 이산화질소가 방출하는 파장을 검출하여 정량 분석하였다. According to the test method of ASTM D 6437 (Standard Test Method for Polyurethane Raw materials), after diluting 0.6 g of each composition in 3 g of toluene, the wavelength emitted by nitrogen dioxide generated by burning in oxygen and argon is quantitatively analyzed Did.
상기 평가예 1-1 및 1-2의 결과를 하기 표 1에 기재하였다. The results of the evaluation examples 1-1 and 1-2 are shown in Table 1 below.
실시예1-1Example 1-1 실시예1-2Example 1-2 실시예1-3Example 1-3 비교예1-1Comparative Example 1-1 비교예1-2Comparative Example 1-2 비교예1-3Comparative Example 1-3
알킬렌 옥사이드 조(粗) 조성물의CPRCPR of alkylene oxide crude composition 8.08.0 8.08.0 8.08.0 8.08.0 8.08.0 8.08.0
정제된 알킬렌 옥사이드 조성물의CPRCPR of purified alkylene oxide composition 0.10.1 0.10.1 0.10.1 8.08.0 8.08.0 8.08.0
정제단계를 수행하지 않음No purification step
폴리올조성물의CPRCPR of polyol composition 0.40.4 0.60.6 0.80.8 2.42.4 3.03.0 3.43.4
폴리올조성물의질소 함량(ppm)Nitrogen content of polyol composition (ppm) 0.30.3 0.20.2 0.30.3 0.570.57 0.50.5 0.430.43
상기 표 1에서 보는 바와 같이, 실시예 1-1 내지 1-3의 알킬렌 옥사이드 조성물의 정제 단계를 거친 폴리올 조성물의 CPR이, 정제 단계를 수행하지 않은 비교예 1-1 내지 1-3의 폴리올 조성물의 CPR에 비하여 낮은 것을 알 수 있다. As shown in Table 1, CPR of the polyol composition after the purification step of the alkylene oxide composition of Examples 1-1 to 1-3, the polyol of Comparative Examples 1-1 to 1-3 without performing the purification step It can be seen that the composition is lower than the CPR.
또한, 실시예 1-1 내지 1-3의 알킬렌 옥사이드 조성물의 정제 단계를 거친 폴리올 조성물의 질소 함량이, 정제 단계를 수행하지 않은 비교예 1-1 내지 1-3의 폴리올 조성물의 질소 함량에 비하여 낮은 것을 알 수 있다. In addition, the nitrogen content of the polyol composition subjected to the purification step of the alkylene oxide composition of Examples 1-1 to 1-3 is based on the nitrogen content of the polyol composition of Comparative Examples 1-1 to 1-3 without performing the purification step. It can be seen that it is low.
<실시예 2-1><Example 2-1>
상기 폴리올 조성물 A, 이소시아네이트(Isocyanate) 및 체인 익스텐더(Chain-Extender)를 반응기에 투입한 후 80℃ 에서 교반시켜 Non-foam 조성물 G를 제조하였다(NCO%: 5.6).The polyol composition A, isocyanate (Isocyanate) and chain extender (Chain-Extender) was added to the reactor and stirred at 80 ° C. to prepare Non-foam composition G (NCO%: 5.6).
<실시예 2-2><Example 2-2>
상기 폴리올 조성물 B, 폴리머 폴리올(Polymer Polyol), 발포제(Blowing Agent), 계면활성제(Surfactant) 및 이소시아네이트(Isocyanate)를 함께 혼합한 후, 저압/고압 발포기를 사용하여 연속발포라인 또는 용기에 원재료를 주입하고 발포 및 숙성 과정을 거쳐 재현성 있는 모양의 폴리우레탄 조성물 H를 제조하였다. After mixing the polyol composition B, a polymer polyol, a blowing agent, a surfactant, and an isocyanate, a raw material is injected into a continuous foaming line or container using a low pressure / high pressure foamer. And through the foaming and aging process to prepare a polyurethane composition H of a reproducible shape.
<실시예 2-3><Example 2-3>
상기 폴리올 조성물 C를 폴리머 폴리올(Polymer Polyol), 발포제(Blowing Agent), 계면활성제(Surfactant) 및 이소시아네이트(Isocyanate)와 함께 혼합한 후, 저압/고압 발포기를 사용하여 일정한 형태의 금형에 주입하고 발포, 탈형 및 숙성 과정을 거쳐 재현성 있는 모양의 폴리우레탄 조성물 I를 제조하였다. After mixing the polyol composition C with a polymer polyol, a blowing agent, a surfactant, and an isocyanate, the polyol composition C is injected into a mold of a certain shape using a low pressure / high pressure foamer and foamed, A polyurethane composition I having a reproducible shape was prepared through a demolding and aging process.
<비교예 2-1><Comparative Example 2-1>
실시예 2-1에서 폴리올 조성물 A 대신에 폴리올 조성물 D를 사용한 것을 제외하고, 동일하게 실험하여 폴리우레탄 조성물 J를 제조하였다.A polyurethane composition J was prepared in the same manner as in Example 2-1, except that the polyol composition D was used instead of the polyol composition A.
<비교예 2-2><Comparative Example 2-2>
실시예 2-2에서 폴리올 조성물 B 대신에 폴리올 조성물 E를 사용한 것을 제외하고, 동일하게 실험하여 폴리우레탄 조성물 K를 제조하였다.A polyurethane composition K was prepared in the same manner as in Example 2-2, except that the polyol composition E was used instead of the polyol composition B.
<비교예 2-3><Comparative Example 2-3>
실시예 2-3에서 폴리올 조성물 C 대신에 폴리올 조성물 F를 사용한 것을 제외하고, 동일하게 실험하여 폴리우레탄 조성물 L을 제조하였다.Polyurethane composition L was prepared in the same manner as in Example 2-3, except that polyol composition F was used instead of polyol composition C.
<평가예 2-1: K+ 측정><Evaluation Example 2-1: K + Measurement>
ASTM D 4668(Test Method for Polyurethane Raw materials:Determination of Potassium in Polyol)의 실험법에 의거하여, Non-foam 조성물 2.0 g을 메탄올 25 ml와 혼합한 후, 원자 흡수 분광 광도계(Atomic Absorption Spectroscopy) 장비를 사용하여 분석했다. According to the test method of ASTM D 4668 (Test Method for Polyurethane Raw materials: Determination of Potassium in Polyol), 2.0 g of Non-foam composition is mixed with 25 ml of methanol, and then an atomic absorption spectrophotometer (Atomic Absorption Spectroscopy) equipment is used. And analyzed.
<평가예 2-2: CPR 측정><Evaluation Example 2-2: CPR measurement>
ASTM D 6437(Standard Test Method for Polyurethane Raw materials)의 실험법에 의거하여, Non-foam 조성물 30g을 메탄올 100ml에 혼합한 후, 0.001N 염산으로 중화 적정하여 소비되는 염산의 양을 계산하였다. According to the test method of ASTM D 6437 (Standard Test Method for Polyurethane Raw materials), 30 g of the non-foam composition was mixed with 100 ml of methanol, and then neutralized with 0.001 N hydrochloric acid to calculate the amount of hydrochloric acid consumed.
<평가예 2-3: Color 측정><Evaluation Example 2-3: Color measurement>
ASTM D 1209(Standard Test Method for Color of Clear Liquids Platium-Cobalt Scale) 실험법에 의거하여, 각각의 조성물을 Nessler tube에 담아 빛을 투과하여 표준물질과 비교하여 색상을 측정했다. According to the ASTM D 1209 (Standard Test Method for Color of Clear Liquids Platium-Cobalt Scale) test method, each composition was put in a Nessler tube to transmit light and measure the color compared to a standard material.
<평가예 2-4: 인열 강도(Tear Resistance) 측정><Evaluation Example 2-4: Tear Resistance Measurement>
상기 폴리우레탄 조성물의 인열 시편을 제작한 후, 양쪽 끝을 잡고 500 mm/min의 속도로 당길 때, 파단에 이를 때까지의 찢어지는 최대 인열 강도를 측정했다. After preparing a tear specimen of the polyurethane composition, when holding at both ends and pulling at a speed of 500 mm / min, the maximum tear strength to tear until the fracture was reached was measured.
<평가예 2-5: 인장 강도(Tensile Strength) 측정><Evaluation Example 2-5: Tensile Strength Measurement>
상기 폴리우레탄 조성물의 인장 시편을 제작한 후, 양쪽 끝을 잡고 500 mm/min의 속도로 당길 때, 변형에 이를 때까지의 최대 인장 강도를 측정했다. After preparing a tensile specimen of the polyurethane composition, when holding at both ends and pulling at a speed of 500 mm / min, the maximum tensile strength up to the deformation was measured.
<평가예 2-6: 연신율(Elongation)측정><Evaluation Example 2-6: Elongation Measurement>
상기 평가예 2-5에서, 상기 폴리우레탄 조성물의 인장 시편이 늘어나는 비율을 측정했다. 구체적으로, 길이가 10cm인 봉의 양 끝을 크기 F인 힘으로 잡아당겨 늘렸을 때에 봉의 길이가 L로 되었다면, 봉이 늘어난 길이 △L = L - 10으로 계산될 수 있다. In the evaluation example 2-5, the rate at which the tensile specimen of the polyurethane composition stretched was measured. Specifically, if the length of the rod is L when both ends of the rod having a length of 10 cm are stretched by a force of size F, the length of the rod can be calculated as ΔL = L-10.
<평가예 2-7: 통기성(Air flow resistivity) 측정><Evaluation Example 2-7: Air flow resistivity measurement>
상기 폴리우레탄 조성물에 공기를 통과시켰을 때, 통과한 공기의 정도를 측정했다.When air was passed through the polyurethane composition, the degree of air passed was measured.
<평가예 2-8: 반발 탄성(Resilience) 측정><Evaluation Example 2-8: Resilience measurement>
0.5 m에서 상기 폴리우레탄 조성물을 낙하시킨 후, 다시 솟아오르는 높이를 측정했다.After dropping the polyurethane composition at 0.5 m, the rising height was again measured.
<평가예 2-9: 복원력(comp. Set) 측정><Evaluation Example 2-9: Resilience (comp. Set) Measurement>
상기 폴리우레탄 조성물을 각각 70℃ 내지 80℃의 오븐에서 두께의 50%를 압축하여 22 시간 동안 압력을 가했다. 가압을 해소하고 30분 후, 초기 두께 기준으로 두께 변화 값을 측정했다. The polyurethane composition was compressed in an oven at 70 ° C to 80 ° C for 50% of the thickness, respectively, and pressure was applied for 22 hours. 30 minutes after releasing the pressure, the thickness change value was measured based on the initial thickness.
상기 평가예 2-1 내지 2-9의 결과를 하기 표 2에 나타내었다. The results of the evaluation examples 2-1 to 2-9 are shown in Table 2 below.
실시예2-1Example 2-1 비교예2-1Comparative Example 2-1 실시예2-2Example 2-2 비교예2-2Comparative Example 2-2 실시예2-3Example 2-3 비교예2-3Comparative Example 2-3
CPRCPR 0.40.4 1.41.4 -- -- -- --
Color(APHA)Color (APHA) 220220 250250 -- -- -- --
Tear(kg/cm)Tear (kg / cm) -- -- 0.440.44 0.420.42 1.081.08 0.970.97
Tensile(kg/cm2)Tensile (kg / cm 2 ) -- -- 0.800.80 0.700.70 1.831.83 1.711.71
Elongation(%)Elongation (%) -- -- 147147 122122 106106 102102
Air Flow(ft3/min)Air Flow (ft 3 / min) -- -- 3.133.13 2.342.34 -- --
Resilience(%)Resilience (%) -- -- 3737 3838 6262 6060
Comp. Set (%)Comp. Set (%) -- -- 55 55 6.36.3 7.07.0
상기 표 2에서 보는 바와 같이, 실시예 2-1의 Non-foam 조성물은 비교예 2-1의 Non-foam 조성물에 비하여, CPR 및 color 값이 낮으므로, 품질이 우수한 것을 알 수 있다. As shown in Table 2, the Non-foam composition of Example 2-1 has a lower CPR and color value than the Non-foam composition of Comparative Example 2-1, and thus it can be seen that the quality is excellent.
또한, 실시예 2-2의 폴리우레탄 조성물은 비교예 2-2의 폴리우레탄 조성물에 비하여, 인열 강도, 인장 강도, 연신율 및 통기성이 우수한 것을 알 수 있다. In addition, it can be seen that the polyurethane composition of Example 2-2 is superior to the polyurethane composition of Comparative Example 2-2, having excellent tear strength, tensile strength, elongation, and breathability.
나아가, 실시예 2-3의 폴리우레탄 조성물은 비교예 2-3의 폴리우레탄 조성물에 비하여, 인열 강도, 인장 강도, 연신율, 반발 탄성 및 외부 충격(고온, 고압)에 따른 복원력(Comp. set%) 이 우수한 것을 알 수 있다. Further, the polyurethane composition of Example 2-3, compared to the polyurethane composition of Comparative Example 2-3, tear strength, tensile strength, elongation, rebound elasticity and resilience according to external impact (high temperature, high pressure) (Comp. Set%) ) It can be seen that this is excellent.
즉, 실시예 2-1 내지 2-3의 정제단계를 거친 알킬렌 옥사이드 조성물로 제조한 폴리올 조성물의 경우, 후속 공정으로 다양한 Non-foam 및 폴리우레탄 조성물을 제조하였을 때, 물성 및 품질이 우수함을 확인하였다. That is, in the case of a polyol composition prepared with an alkylene oxide composition that has been subjected to the purification steps of Examples 2-1 to 2-3, when various Non-foam and polyurethane compositions are prepared in a subsequent process, physical properties and quality are excellent. Confirmed.
<실시예 3-1><Example 3-1>
알킬렌 옥사이드 조(粗) 조성물 100 g을 제올라이트계 분자체(Mol Sieve)를 이용하여, 정제된 프로필렌 옥사이드 조성물을 100 g 얻었다. 100 g of a purified propylene oxide composition was obtained by using 100 g of an alkylene oxide crude composition using a zeolite-based molecular sieve (Mol Sieve).
프로필렌 옥사이드 조성물과 물을 튜브 반응기에서 반응시켰다. 이후, 남은 물을 증류시켜 프로필렌 글리콜 조성물 A를 얻었다. The propylene oxide composition and water were reacted in a tube reactor. Thereafter, the remaining water was distilled to obtain propylene glycol composition A.
<비교예 3-1><Comparative Example 3-1>
실시예 3-1에서 알킬렌 옥사이드 조(粗) 조성물 100 g을 정제하지 않고 사용한 것을 제외하고, 상기 실시예 3-1과 동일하게 실험하여 프로필렌 글리콜 조성물 B를 얻었다. The propylene glycol composition B was obtained in the same experiment as in Example 3-1, except that 100 g of the alkylene oxide crude composition in Example 3-1 was used without purification.
<평가예 3-1: CPR 측정><Evaluation Example 3-1: CPR measurement>
ASTM D 6437(Standard Test Method for Polyurethane Raw materials)의 실험법에 의거하여, 각각의 조성물 30g을 메탄올 100ml에 혼합한 후, 0.001N 염산으로 중화 적정하여 소비되는 염산의 양을 계산하였다. According to the test method of ASTM D 6437 (Standard Test Method for Polyurethane Raw materials), 30 g of each composition was mixed in 100 ml of methanol, and then neutralized titration with 0.001 N hydrochloric acid to calculate the amount of hydrochloric acid consumed.
<평가예 3-2: 질소 함량 측정 ><Evaluation Example 3-2: Nitrogen content measurement>
ASTM D 6437(Standard Test Method for Polyurethane Raw materials)의 실험법에 의거하여, 각각의 조성물 0.6g을 톨루엔 3g에 희석한 후, 산소 및 아르곤 상태에서 연소시켜 발생된 이산화질소가 방출하는 파장을 검출하여 정량 분석하였다. According to the test method of ASTM D 6437 (Standard Test Method for Polyurethane Raw materials), after diluting 0.6 g of each composition in 3 g of toluene, the wavelength emitted by nitrogen dioxide generated by burning in oxygen and argon is quantitatively analyzed Did.
<평가예 3-3: 냄새 강도 지수(odor index) 측정><Evaluation Example 3-3: Measurement of odor index>
하기 기준에 의하여, 각각 조성물의 냄새 강도 지수를 측정하였다. The odor intensity index of each composition was measured according to the following criteria.
0: 무취0: Odorless
1.0: 숙련인에게만 감지된다. 1.0: Detected only by experienced personnel.
1.5 내지 2.0: 누구에게나 감지되나, 맡기 싫은 냄새는 아니다.1.5 to 2.0: Detected by anyone, but it is not an unpleasant smell.
2.5 내지 3.0: 누구에게나 감지되며, 비릿한 냄새가 난다.2.5 to 3.0: Detected by anyone and smells fishy.
상기 평가예 3-1 내지 3-3의 결과를 하기 표 3에 나타내었다. The results of the evaluation examples 3-1 to 3-3 are shown in Table 3 below.
실시예3-1Example 3-1 비교예3-1Comparative Example 3-1
정제된 알킬렌 옥사이드 조성물의 CPRCPR of purified alkylene oxide composition 00 0.50.5
정제단계를 수행하지 않음No purification step
정제된 알킬렌 옥사이드 조성물의 질소 함량(ppm)Nitrogen content in purified alkylene oxide composition (ppm) 00 0.40.4
정제단계를 수행하지 않음No purification step
프로필렌 글리콜 조성물의 odorOdor of propylene glycol composition 1.01.0 3.03.0
프로필렌 글리콜 조성물의 질소 함량 (ppm)Nitrogen content in propylene glycol composition (ppm) 0.20.2 0.40.4
상기 표 3에서 보는 바와 같이, 실시예 3-1의 알킬렌 옥사이드 정제 단계를 거친 프로필렌 글리콜 조성물의 질소 함량 및 odor은, 알킬렌 옥사이드 정제단계를 수행하지 않은 비교예 3-1에 비하여 낮은 것을 알 수 있다.As shown in Table 3, the nitrogen content and odor of the propylene glycol composition after the alkylene oxide purification step of Example 3-1 is lower than that of Comparative Example 3-1 without performing the alkylene oxide purification step. Can be.

Claims (21)

  1. CPR이 2.4 미만인, 폴리올 조성물.A polyol composition having a CPR less than 2.4.
  2. 제1항에 있어서, According to claim 1,
    상기 CPR이 2.0 이하인, 폴리올 조성물.The CPR is 2.0 or less, polyol composition.
  3. 제1항에 있어서, According to claim 1,
    상기 CPR이 0.8 이하인, 폴리올 조성물.The CPR is 0.8 or less, polyol composition.
  4. 제1항에 있어서, According to claim 1,
    상기 폴리올 조성물의 질소(Nitrogen) 함량이 0.43 ppm 미만인, 폴리올 조성물.The polyol composition has a nitrogen (Nitrogen) content of less than 0.43 ppm, polyol composition.
  5. 제1항에 있어서, According to claim 1,
    상기 폴리올 조성물의 질소 함량이 0.3 ppm 이하인, 폴리올 조성물.The polyol composition has a nitrogen content of 0.3 ppm or less, a polyol composition.
  6. (1) 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계;(1) purifying the alkylene oxide crude composition;
    (2) 상기 정제된 알킬렌 옥사이드 조성물과 다가 알코올을 반응시키는 단계; 및(2) reacting the purified alkylene oxide composition with a polyhydric alcohol; And
    (3) 폴리올 조성물을 얻는 단계;를 포함하고,(3) obtaining a polyol composition; including,
    상기 폴리올 조성물의 CPR이 2.4 미만인, 폴리올 조성물의 제조 방법. The polyol composition has a CPR of less than 2.4.
  7. 제6항에 있어서, The method of claim 6,
    상기 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계가 흡착제 이용법, 전기 화학법 및 증류법(Distillation)으로 이루어진 군에서 선택되는 1종 이상의 정제 방법을 사용하는 것인, 폴리올 조성물의 제조방법. The step of purifying the alkylene oxide crude composition is to use one or more purification methods selected from the group consisting of an adsorbent use method, an electrochemical method, and a distillation method.
  8. 제7항에 있어서, The method of claim 7,
    상기 흡착제 이용법이 제올라이트계 분자체(Mol-Sieve) 또는 네추럴 클레이(Natural Clay)를 이용한, 폴리올 조성물의 제조방법.The method of using the adsorbent is a method of producing a polyol composition using a zeolite-based molecular sieve (Mol-Sieve) or natural clay (Natural Clay).
  9. 제8항에 있어서, The method of claim 8,
    상기 제올라이트계 분자체가 제올라이트 A, 제올라이트 X, 제올라이트 베타, 제올라이트 Y, 제올라이트 L 및 ZSM-12로 이루어진 군으로부터 선택된 구조를 갖는, 폴리올 조성물의 제조방법.The zeolite-based molecular sieve has a structure selected from the group consisting of zeolite A, zeolite X, zeolite beta, zeolite Y, zeolite L and ZSM-12, a method for producing a polyol composition.
  10. 제8항에 있어서, The method of claim 8,
    상기 네추럴클레이(Natural Clay)는 몬모릴로나이트(Montmorillonite), 카올리나이트(Kaolinite), 세피올라이트(Sepiolite), 벤토나이트(Bentonite) 및 규조토(Diatomite)로 이루어진 군으로부터 선택되는, 폴리올 조성물의 제조방법.The natural clay is selected from the group consisting of montmorillonite, kaolinite, sepiolite, bentonite, and diatomite.
  11. 제6항에 있어서, The method of claim 6,
    상기 알킬렌 옥사이드가 프로필렌 옥사이드인, 폴리올 조성물의 제조 방법. Method for producing a polyol composition, wherein the alkylene oxide is propylene oxide.
  12. 제6항에 있어서, The method of claim 6,
    상기 다가 알코올이 글리세롤, 프로필렌 글리콜, 수크로우즈(Sucrose), 글리세린, 소비톨 및 트리에탄올아민으로 이루어진 군으로부터 선택되는 1종 이상인 것인, 폴리올 조성물의 제조 방법.The polyhydric alcohol is one or more selected from the group consisting of glycerol, propylene glycol, sucrose (Sucrose), glycerin, sorbitol and triethanolamine, a method for producing a polyol composition.
  13. 질소(Nitrogen) 함량이 0.4 ppm 미만인, 프로필렌 글리콜 조성물. Propylene glycol composition having a nitrogen content of less than 0.4 ppm.
  14. 제13항에 있어서, The method of claim 13,
    상기 질소 함량이 0.3 ppm 이하인, 프로필렌 글리콜 조성물. The nitrogen content is less than 0.3 ppm, propylene glycol composition.
  15. 제13항에 있어서, The method of claim 13,
    상기 질소 함량이 0.2 ppm 이하인, 프로필렌 글리콜 조성물. The nitrogen content is less than 0.2 ppm, propylene glycol composition.
  16. 제13항에 있어서, The method of claim 13,
    냄새 강도 지수(odor index)가 3 미만인, 프로필렌 글리콜 조성물.Propylene glycol composition having an odor index of less than 3.
  17. 제13항에 있어서, The method of claim 13,
    냄새 강도 지수(odor index)가 1 이하인, 프로필렌 글리콜 조성물.A propylene glycol composition having an odor index of 1 or less.
  18. 제13항에 있어서, The method of claim 13,
    상기 프로필렌 글리콜 조성물은 모노 프로필렌 글리콜, 다이 프로필렌 글리콜 및 트리 프로필렌 글리콜로 이루어진 군으로부터 선택되는 1종 이상을 포함하는, 프로필렌 글리콜 조성물. The propylene glycol composition comprises a propylene glycol composition comprising at least one selected from the group consisting of mono propylene glycol, dipropylene glycol and tripropylene glycol.
  19. 제18항에 있어서, The method of claim 18,
    상기 모노 프로필렌 글리콜의 함량이 상기 프로필렌 글리콜 조성물의 총 중량을 기준으로, 60 내지 80 중량%인, 프로필렌 글리콜 조성물.The content of the mono propylene glycol, based on the total weight of the propylene glycol composition, 60 to 80% by weight, propylene glycol composition.
  20. 제18항에 있어서, The method of claim 18,
    상기 다이 프로필렌 글리콜의 함량이 상기 프로필렌 글리콜 조성물의 총 중량을 기준으로, 20 내지 30 중량%인, 프로필렌 글리콜 조성물.Propylene glycol composition, the content of the dipropylene glycol is 20 to 30% by weight, based on the total weight of the propylene glycol composition.
  21. (1) 알킬렌 옥사이드 조(粗) 조성물을 정제하는 단계;(1) purifying the alkylene oxide crude composition;
    (2) 상기 정제된 알킬렌 옥사이드 조성물과 물을 반응시키는 단계; 및(2) reacting the purified alkylene oxide composition with water; And
    (3) 프로필렌 글리콜 조성물을 얻는 단계;를 포함하고,(3) obtaining a propylene glycol composition; including,
    상기 프로필렌 글리콜 조성물의 질소(Nitrogen) 함량이 0.4 ppm 미만인, 프로필렌 글리콜 조성물의 제조 방법. Nitrogen content of the propylene glycol composition is less than 0.4 ppm, the production method of the propylene glycol composition.
PCT/KR2018/016754 2018-10-31 2018-12-27 Polyol composition, propylene glycol composition and preparation method thereof WO2020091143A1 (en)

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