WO2020130411A1 - Method for manufacturing chlorinated polyvinyl chloride resin - Google Patents

Method for manufacturing chlorinated polyvinyl chloride resin Download PDF

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Publication number
WO2020130411A1
WO2020130411A1 PCT/KR2019/016774 KR2019016774W WO2020130411A1 WO 2020130411 A1 WO2020130411 A1 WO 2020130411A1 KR 2019016774 W KR2019016774 W KR 2019016774W WO 2020130411 A1 WO2020130411 A1 WO 2020130411A1
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Prior art keywords
polyvinyl chloride
chlorinated polyvinyl
chloride resin
chlorination reaction
reactor
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PCT/KR2019/016774
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French (fr)
Korean (ko)
Inventor
홍기원
이우영
진선정
남궁지은
편원범
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한화솔루션 주식회사
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Priority to CN201980082334.9A priority Critical patent/CN113195549B/en
Publication of WO2020130411A1 publication Critical patent/WO2020130411A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/02—Neutralisation of the polymerisation mass, e.g. killing the catalyst also removal of catalyst residues

Definitions

  • the present invention relates to a method for producing a chlorinated polyvinyl chloride resin.
  • Chlorinated polyvinyl chloride (CPVC) resin is produced by chlorinating polyvinyl chloride (PVC) resin.
  • CPVC resin has relatively good mechanical properties, heat resistance and chemical resistance due to its high chlorine content compared to PVC, and is used for various purposes such as hot and cold water pipes, industrial pipes, sprinkler pipes, and adhesives.
  • the chlorination proceeds through a photoreaction that irradiates ultraviolet rays in a reactor in which PVC resin and chlorine are introduced.
  • the chlorination corresponds to a main process for determining the productivity of the CPVC resin
  • various attempts have been made to increase the efficiency of the chlorination.
  • methods are known to increase the output of the UV light source, adjust the ultraviolet wavelength range, or adjust the stirring conditions of the reactants.
  • the present invention is to provide a method capable of producing a chlorinated polyvinyl chloride resin without sacrificing either the reaction efficiency or the properties of the resin.
  • a method for producing a chlorinated polyvinyl chloride resin is provided.
  • the “target total output” of the ultraviolet light source means the total output of the ultraviolet light source required to smoothly perform any chlorination reaction as a light reaction by ultraviolet irradiation.
  • CPVC chlorinated polyvinyl chloride
  • the efficiency of the chlorination reaction and the physical properties of the CPVC resin are in a trade-off relationship that is difficult to improve at the same time.
  • the manufacturing method of the CPVC resin according to the present invention makes it possible to provide the CPVC resin without sacrificing any one of the efficiency of the chlorination reaction and the properties of the resin.
  • CPVC chlorinated polyvinyl chloride
  • a method for producing CPVC resin is provided.
  • a step of obtaining CPVC resin by irradiating ultraviolet rays in a reactor in which vinyl chloride resin and chlorine is introduced is performed.
  • the vinyl chloride-based resin may be polyvinyl chloride (PVC) resin or PVC-containing copolymer resin.
  • the vinyl chloride-based resin may be used in a slurry state containing a solvent.
  • the solvent one known to be suitable for the chlorination reaction may be used.
  • water deionized water
  • alcohol or the like may be preferably used as the solvent.
  • the slurry prefferably contains the vinyl chloride-based resin in an amount of 10 to 35% by weight relative to the solvent for securing the efficiency of the chlorination reaction.
  • oxygen in the reactor must be removed.
  • degassing in the reactor may be performed in an appropriate manner.
  • the chlorination reaction it is preferable to maintain the pressure of chlorine introduced into the reactor between 0.5 and 4.0 bar. And, the chlorination reaction may be performed under a temperature of 50 to 95 °C.
  • the chlorination reaction is initiated by irradiating ultraviolet rays in a reactor in which a vinyl chloride resin and chlorine are introduced.
  • the ultraviolet light source may be a light source irradiating ultraviolet light having a wavelength range of 260 to 430 nm.
  • the ultraviolet light source may be at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, mercury lamp, and metal halide lamp.
  • the chlorination reaction step is based on the target total power (W) of W/(n+0.3) to W/(n-0.3) irradiated with n outputs (however, n ⁇ It is preferably performed by photoreaction using the ultraviolet light source of 2).
  • n (but n ⁇ 2) light sources having an output of W/(n+0.3) to W/(n-0.3) are used.
  • W target total output
  • n but n ⁇ 2 light sources having an output of W/(n+0.3) to W/(n-0.3) are used.
  • the target total power for performing the chlorination reaction is set to 100 W, compared to using one light source of 100 W, two light sources of 44 to 58 W, or three light sources of 31 to 37 W, or The use of four light sources of 24 to 27 W or five light sources of 19 to 21 W is advantageous for obtaining CPVC resins of excellent physical properties with shortened chlorination reaction time.
  • the target total power for performing the chlorination reaction is set to 450 W, compared to using one light source of 450 W, two light sources of 196 to 264 W, or three light sources of 137 to 166 W, Alternatively, using four light sources of 105 to 121 W or five light sources of 85 to 95 W is advantageous for obtaining a CPVC resin having excellent physical properties with a shortened chlorination reaction time.
  • the target total power for performing the chlorination reaction is set to 500 W, compared to using one light source of 500 W, two light sources of 218 to 294 W, or three light sources of 152 to 185 W Alternatively, using four light sources of 117 to 135 W or five light sources of 95 to 106 W is advantageous for obtaining CPVC resins having excellent physical properties with shortened chlorination reaction time.
  • the total output power of the light source is too low compared to the target total power, so that the chlorination reaction efficiency may be reduced.
  • the total output power of the light source is too high compared to the target total output power, thereby deteriorating physical properties of the CPVC resin.
  • the chlorination reaction step is performed while variably adjusting the output of the ultraviolet light source in the range of W/(n+0.3) to W/(n-0.3) of the target total output W. Can.
  • the output of the ultraviolet light source may be adjusted once or several times from the time when the introduction of chlorine into the reactor starts to the end of the chlorination reaction step.
  • the number of ns irradiated with the output of W/(n-0.3) is based on the target total output (W). (However, it is performed by photoreaction using an ultraviolet light source of n ⁇ 2);
  • n numbers are irradiated with the output of W/(n+0.3) based on the target total output (W). It can be performed by photoreaction using an ultraviolet light source.
  • a photoinitiator such as peroxyester, hydroperoxide, and dialkyl peroxide may be further added to the chlorination reaction.
  • the solvent is added to re-slurry and transferred to the next step.
  • the step of reacting the CPVC slurry obtained in the chlorination reaction step with a neutralizing agent is performed.
  • the neutralization step is a step for increasing the pH of the CPVC slurry to improve stability and to minimize the amount of residual HCl in CPVC.
  • neutralizing agent a compound well known in the art to which the present invention pertains may be used.
  • the neutralizing agent is a group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium percarbonate, and potassium percarbonate It may be one or more compounds selected from.
  • the neutralizing agent may be used in an amount such that the CPVC slurry is pH 6.0 to pH 8.0.
  • the neutralizing agent may be used in 1 to 20 parts by weight based on 100 parts by weight of the CPVC slurry.
  • the neutralizing agent may be added in powder or solution form.
  • neutralization efficiency may be increased through stirring.
  • the neutralization reaction is carried out at a temperature below the boiling point of the solvent contained in the CPVC slurry.
  • the neutralization reaction step may be performed under a temperature of 20 to 80 °C.
  • the neutralized CPVC slurry is dehydrated to remove solvent and impurities.
  • the CPVC cake obtained through the dehydration can be dried to finally obtain a powdery CPVC resin.
  • a method capable of producing a chlorinated polyvinyl chloride resin without sacrificing any one of a trade-off reaction efficiency and a property of the resin is provided.
  • a polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry.
  • 3.5 L of the polyvinyl chloride slurry was charged to a 5 L volume cylindrical reactor.
  • the slurry was stirred at a constant speed of 400 to 1000 rpm while degassing was performed until the pressure inside the reactor became ⁇ 0.9 bar or more.
  • a chlorination reaction was performed by operating one group of a UV mercury lamp (wavelength range of 260 to 430 nm, arc length 8 cm) of 100 W, a light source provided in the reactor.
  • the UV mercury lamp was installed so that the arc length was immersed in the slurry on the central axis of the reactor, and emitted UV light radially.
  • the chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
  • Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it.
  • the neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
  • a polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry.
  • 3.5 L of the polyvinyl chloride slurry was charged to a 5 L volume cylindrical reactor.
  • the slurry was stirred at a constant speed of 400 to 1000 rpm while degassing was performed until the pressure inside the reactor became ⁇ 0.9 bar or more.
  • the target total power for the chlorination reaction was set to 100 W, and two groups of 50 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 8 cm), a light source provided in the reactor, were operated to perform a chlorination reaction.
  • the two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
  • the chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
  • Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it.
  • the neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
  • Example 1 Except that the chlorination reaction was performed by setting the target total power for the chlorination reaction to 100 W and operating two groups of 60 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 8 cm), a light source provided in the reactor. Then, a chlorinated polyvinyl chloride resin was obtained in the same manner as in Example 1.
  • the target total power for the chlorination reaction is set to 100 W, and the chlorination reaction is performed by operating three groups of 37 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 8 cm), which are light sources provided in the reactor. Then, a chlorinated polyvinyl chloride resin was obtained in the same manner as in Example 1.
  • a polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry.
  • 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
  • Degassing was performed until the pressure in the reactor became ⁇ 0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
  • a chlorination reaction was performed by operating one group of a 450 W UV mercury lamp (wavelength range of 260 to 430 nm, arc length 14.5 cm) as a light source provided in the reactor.
  • the UV mercury lamp was installed so that the arc length was immersed in the slurry on the central axis of the reactor, and emitted UV light radially.
  • the chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
  • Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it.
  • the neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
  • a polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry.
  • 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
  • Degassing was performed until the pressure in the reactor became ⁇ 0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
  • the target total power for the chlorination reaction was set to 450 W, and two groups of 200 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 14.5 cm), a light source provided in the reactor, were operated to perform a chlorination reaction.
  • the two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
  • the chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
  • Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it.
  • the neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
  • a polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry.
  • 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
  • Degassing was performed until the pressure in the reactor became ⁇ 0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
  • the target total power for the chlorination reaction was set to 450 W, and two groups of 250 W UV LED lamps (wavelength range of 260 to 430 nm, arc length 14.5 cm), a light source provided in the reactor, were operated to perform a chlorination reaction.
  • the two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
  • the chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
  • Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it.
  • the neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
  • a polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry.
  • 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
  • Degassing was performed until the pressure in the reactor became ⁇ 0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
  • the target total power for the chlorination reaction was set to 450 W, and two groups of 250 W UV LED lamps (wavelength range of 260 to 430 nm, arc length 14.5 cm), a light source provided in the reactor, were operated to perform a chlorination reaction.
  • the two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
  • the chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
  • Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it.
  • the neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
  • Vicat softening temperature (VST) was measured according to KS M ISO 306:2015 (50°C, load 50 N).
  • Chlorine content The content of Cl element was measured using an elemental analyzer.
  • the method of manufacturing lab scales according to Examples 1 and 2 can obtain CPVC having physical properties equal to or higher than those of Comparative Example 1, while obtaining chlorination reaction time and total reaction time. It was confirmed that each can be shortened by about 11% or more.
  • the pilot scale manufacturing method according to Example 4 despite applying a lamp total power higher than the target total power (450 W), compared with the method of Comparative Example 2, CPVC with a reaction time reduced by 20% or more without deterioration of physical properties. It was confirmed that it can be obtained.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
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Abstract

The present invention relates to a method for manufacturing a chlorinated polyvinyl chloride resin. Provided according to the present invention is a method capable of manufacturing a chlorinated polyvinyl chloride resin with sacrificing neither resin properties nor reaction efficiency, which are in a trade-off relationship.

Description

염소화 폴리염화비닐 수지의 제조 방법Method for producing chlorinated polyvinyl chloride resin
본 발명은 염소화 폴리염화비닐 수지의 제조 방법에 관한 것이다.The present invention relates to a method for producing a chlorinated polyvinyl chloride resin.
염소화 폴리염화비닐(CPVC) 수지는 폴리염화비닐(PVC) 수지를 염소화하여 제조된다.Chlorinated polyvinyl chloride (CPVC) resin is produced by chlorinating polyvinyl chloride (PVC) resin.
CPVC 수지는 PVC 대비 높은 염소 함량으로 인해 기계적 물성, 내열성 및 내화학성이 상대적으로 우수하며, 냉온수관, 산업용 배관, 스프링쿨러용 배관, 접착제 등 다양한 용도로 사용된다.CPVC resin has relatively good mechanical properties, heat resistance and chemical resistance due to its high chlorine content compared to PVC, and is used for various purposes such as hot and cold water pipes, industrial pipes, sprinkler pipes, and adhesives.
일반적으로, 상기 염소화는 PVC 수지와 염소가 도입된 반응기 내에 자외선을 조사하는 광 반응을 통해 진행된다.In general, the chlorination proceeds through a photoreaction that irradiates ultraviolet rays in a reactor in which PVC resin and chlorine are introduced.
상기 염소화는 CPVC 수지의 생산성을 결정하는 주요 공정에 해당하기 때문에, 상기 염소화의 효율을 높이기 위한 다양한 시도가 이루어지고 있다. 예를 들어, 상기 염소화를 수행함에 있어서 UV 광원의 출력을 높이거나, 자외선 파장 범위를 조절하거나, 또는 반응물의 교반 조건을 조절하는 방법들이 알려져 있다.Since the chlorination corresponds to a main process for determining the productivity of the CPVC resin, various attempts have been made to increase the efficiency of the chlorination. For example, in performing the chlorination, methods are known to increase the output of the UV light source, adjust the ultraviolet wavelength range, or adjust the stirring conditions of the reactants.
그런데, 일반적으로 상기 염소화의 효율을 높이기 위해 UV 광원의 출력을 높일 경우, 제조된 CPVC 수지의 착색이 심화하고 열 안정성 등의 물성이 저하하는 문제점이 있다.However, in general, when increasing the output of the UV light source in order to increase the efficiency of the chlorination, there is a problem that the coloring of the produced CPVC resin is increased and physical properties such as thermal stability are deteriorated.
반대로, 상기 UV 광원의 출력을 낮출 경우 상대적으로 우수한 착색성과 물성을 갖는 CPVC 수지를 제조할 수 있지만, 상기 염소화의 속도가 느려져 생산성이 저하되는 문제점이 있다.On the contrary, when the output of the UV light source is lowered, a CPVC resin having relatively excellent coloring properties and properties can be produced, but there is a problem in that productivity is lowered due to a slower rate of chlorination.
이처럼 상기 염소화의 효율과 CPVC 수지의 물성은 트레이드-오프(trade-off)의 관계에 있다. 따라서, 상기 염소화의 효율과 수지의 물성 중 어느 하나를 희생하지 않고 CPVC를 제조할 수 있는 방법이 여전히 요구되고 있다.As such, the efficiency of chlorination and the physical properties of CPVC resin are in a trade-off relationship. Therefore, there is still a need for a method capable of producing CPVC without sacrificing either the efficiency of chlorination or the properties of the resin.
본 발명은 반응 효율과 수지의 물성 중 어느 하나를 희생하지 않고 염소화 폴리염화비닐 수지를 제조할 수 있는 방법을 제공하기 위한 것이다.The present invention is to provide a method capable of producing a chlorinated polyvinyl chloride resin without sacrificing either the reaction efficiency or the properties of the resin.
본 발명의 일 구현 예에 따르면,According to an embodiment of the present invention,
염화비닐계 수지와 염소가 도입된 반응기 내에 자외선을 조사하여 염소화 폴리염화비닐 수지를 얻는 염소화 반응 단계, 및Chlorination reaction step of obtaining a chlorinated polyvinyl chloride resin by irradiating ultraviolet rays in a reactor in which the vinyl chloride resin and chlorine are introduced, and
상기 염소화 폴리염화비닐 수지를 중화제와 반응시키는 중화 반응 단계를 포함하고;A neutralization reaction step of reacting the chlorinated polyvinyl chloride resin with a neutralizing agent;
상기 염소화 반응 단계는, 타겟 총 출력(W)을 기준으로 W/(n+0.3) 내지 W/(n-0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행되는,In the chlorination reaction step, light using n (but n≥2) ultraviolet light sources irradiated with outputs of W/(n+0.3) to W/(n-0.3) based on the target total output (W) Carried out in reaction,
염소화 폴리염화비닐 수지의 제조 방법이 제공된다.A method for producing a chlorinated polyvinyl chloride resin is provided.
이하, 발명의 구현 예에 따른 염소화 폴리염화비닐 수지의 제조 방법에 대하여 보다 상세히 설명한다.Hereinafter, a method of manufacturing a chlorinated polyvinyl chloride resin according to an embodiment of the present invention will be described in more detail.
본 명세서 명시적인 언급이 없는 한, 전문용어는 단지 특정 구현예를 언급하기 위한 것이며, 본 발명을 한정하는 것을 의도하지 않는다.Unless expressly stated in this specification, the terminology is only for referring to specific embodiments and is not intended to limit the present invention.
본 명세서에서 사용되는 단수 형태들은 문구들이 이와 명백히 반대의 의미를 나타내지 않는 한 복수 형태들도 포함한다.Singular forms used herein include plural forms unless the phrases clearly indicate the opposite.
본 명세서에서 사용되는 "포함"의 의미는 특정 특성, 영역, 정수, 단계, 동작, 요소 또는 성분을 구체화하며, 다른 특정 특성, 영역, 정수, 단계, 동작, 요소, 또는 성분의 부가를 제외시키는 것은 아니다.As used herein, the meaning of "comprising" embodies a particular characteristic, region, integer, step, action, element or component, and excludes the addition of another particular characteristic, region, integer, step, action, element, or component. It is not.
본 명세서에서 자외선 광원의 "타겟 총 출력"은, 임의의 염소화 반응을 자외선 조사에 의한 광 반응으로 원활하게 수행하기 위해 요구되는 자외선 광원의 총 출력을 의미한다.In the present specification, the “target total output” of the ultraviolet light source means the total output of the ultraviolet light source required to smoothly perform any chlorination reaction as a light reaction by ultraviolet irradiation.
본 발명자들의 계속적인 연구 결과, 염화비닐계 수지를 염소와 반응시켜 염소화 폴리염화비닐(CPVC) 수지를 얻는 염소화 반응에 있어서, 타겟 총 출력(W)을 기준으로 W/(n+0.3) 내지 W/(n-0.3)의 출력을 갖는 n 개(단, n≥2)의 자외선 광원을 이용하여 광 반응으로 수행할 경우, 보다 단축된 염소화 반응 시간으로 우수한 물성을 갖는 CPVC 수지를 얻을 수 있음이 확인되었다.As a result of continuous research by the present inventors, in the chlorination reaction to obtain a chlorinated polyvinyl chloride (CPVC) resin by reacting the vinyl chloride-based resin with chlorine, W/(n+0.3) to W based on the target total output (W) It is possible to obtain CPVC resin with excellent physical properties with shorter chlorination reaction time when performing by photoreaction using n (but n≥2) ultraviolet light sources having an output of /(n-0.3) Was confirmed.
일반적으로 상기 염소화 반응의 효율과 CPVC 수지의 물성은 동시에 향상시키기 어려운 트레이드-오프(trade-off)의 관계에 있다. 그런데, 본 발명에 따른 CPVC 수지의 제조 방법은 상기 염소화 반응의 효율과 수지의 물성 중 어느 하나를 희생하지 않고 CPVC 수지의 제공을 가능하게 한다.In general, the efficiency of the chlorination reaction and the physical properties of the CPVC resin are in a trade-off relationship that is difficult to improve at the same time. However, the manufacturing method of the CPVC resin according to the present invention makes it possible to provide the CPVC resin without sacrificing any one of the efficiency of the chlorination reaction and the properties of the resin.
발명의 일 구현 예에 따르면,According to one embodiment of the invention,
염화비닐계 수지와 염소가 도입된 반응기 내에 자외선을 조사하여 염소화 폴리염화비닐(CPVC) 수지를 얻는 염소화 반응 단계, 및Chlorination reaction step of obtaining a chlorinated polyvinyl chloride (CPVC) resin by irradiating ultraviolet rays in a reactor in which a vinyl chloride resin and chlorine are introduced, and
상기 CPVC 수지를 중화제와 반응시키는 중화 반응 단계를 포함하고;A neutralization reaction step of reacting the CPVC resin with a neutralizing agent;
상기 염소화 반응 단계는, 타겟 총 출력(W)을 기준으로 W/(n+0.3) 내지 W/(n-0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행되는,In the chlorination reaction step, light using n (but n≥2) ultraviolet light sources irradiated with outputs of W/(n+0.3) to W/(n-0.3) based on the target total output (W) Carried out in reaction,
CPVC 수지의 제조 방법이 제공된다.A method for producing CPVC resin is provided.
이하, 상기 CPVC 수지의 제조 방법에 포함될 수 있는 각 단계에 대하여 설명한다.Hereinafter, each step that may be included in the manufacturing method of the CPVC resin will be described.
(1) 염소화 반응 단계(1) Chlorination reaction step
염화비닐계 수지와 염소가 도입된 반응기 내에 자외선을 조사하여 CPVC 수지를 얻는 단계가 수행된다.A step of obtaining CPVC resin by irradiating ultraviolet rays in a reactor in which vinyl chloride resin and chlorine is introduced is performed.
상기 염화비닐계 수지는 폴리염화비닐(PVC) 수지 또는 PVC 함유 공중합체 수지일 수 있다.The vinyl chloride-based resin may be polyvinyl chloride (PVC) resin or PVC-containing copolymer resin.
상기 염화비닐계 수지는 용매를 함유한 슬러리 상태로 사용될 수 있다.The vinyl chloride-based resin may be used in a slurry state containing a solvent.
상기 용매로는 염소화 반응에 적합한 것으로 알려진 것이 사용될 수 있다. 일 예로, 상기 용매로는 물(탈이온수), 알코올 등이 바람직하게 사용될 수 있다.As the solvent, one known to be suitable for the chlorination reaction may be used. For example, water (deionized water), alcohol, or the like may be preferably used as the solvent.
상기 슬러리는 상기 용매에 대하여 상기 염화비닐계 수지를 10 내지 35 중량%로 함유하는 것이 염소화 반응의 효율 확보를 위해 바람직하다.It is preferable for the slurry to contain the vinyl chloride-based resin in an amount of 10 to 35% by weight relative to the solvent for securing the efficiency of the chlorination reaction.
상기 염소화 반응을 수행하기에 앞서, 상기 반응기 내부의 산소가 제거되어야 한다. 이를 위하여 적절한 방법으로 상기 반응기 내부의 탈기가 수행될 수 있다.Before performing the chlorination reaction, oxygen in the reactor must be removed. For this, degassing in the reactor may be performed in an appropriate manner.
상기 염소화 반응을 수행함에 있어서, 반응기에 투입되는 염소의 압력은 0.5 내지 4.0 bar 사이를 유지하는 것이 바람직하다. 그리고, 상기 염소화 반응은 50 내지 95 ℃의 온도 하에서 수행될 수 있다.In performing the chlorination reaction, it is preferable to maintain the pressure of chlorine introduced into the reactor between 0.5 and 4.0 bar. And, the chlorination reaction may be performed under a temperature of 50 to 95 ℃.
상기 염소화 반응은 염화비닐계 수지와 염소가 도입된 반응기 내에 자외선을 조사함으로써 개시된다.The chlorination reaction is initiated by irradiating ultraviolet rays in a reactor in which a vinyl chloride resin and chlorine are introduced.
상기 자외선 광원은 파장 범위 260 내지 430 nm의 자외선을 조사하는 광원일 수 있다.The ultraviolet light source may be a light source irradiating ultraviolet light having a wavelength range of 260 to 430 nm.
그리고, 상기 자외선 광원은 자외선 LED, 유기 EL, 무기 EL, 수은 램프, 및 메탈할라이드 램프로 이루어진 군에서 선택된 1종 이상의 광원일 수 있다.In addition, the ultraviolet light source may be at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, mercury lamp, and metal halide lamp.
특히, 발명의 구현 예에 따르면, 상기 염소화 반응 단계는 타겟 총 출력(W)을 기준으로 W/(n+0.3) 내지 W/(n-0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행되는 것이 바람직하다.In particular, according to an embodiment of the invention, the chlorination reaction step is based on the target total power (W) of W/(n+0.3) to W/(n-0.3) irradiated with n outputs (however, n≥ It is preferably performed by photoreaction using the ultraviolet light source of 2).
구체적으로, 타겟 총 출력(W)을 갖는 1 개의 광원을 이용하는 것에 비하여, W/(n+0.3) 내지 W/(n-0.3)의 출력을 갖는 n 개(단, n≥2)의 광원을 이용할 경우, 염소화 반응 시간의 단축이 가능하면서도, 총 출력을 높이더라도 수지의 물성 저하를 방지할 수 있다.Specifically, compared to using one light source having a target total output W, n (but n≥2) light sources having an output of W/(n+0.3) to W/(n-0.3) are used. When used, it is possible to shorten the chlorination reaction time, but it is possible to prevent deterioration of the properties of the resin even if the total output is increased.
일 예로, 염소화 반응 수행을 위한 타겟 총 출력을 100 W로 설정한 경우, 100 W의 광원 1 개를 이용하는 것에 비하여, 44 내지 58 W의 광원 2 개, 혹은 31 내지 37 W의 광원 3 개, 혹은 24 내지 27 W의 광원 4 개, 혹은 19 내지 21 W의 광원 5 개를 이용하는 것이 단축된 염소화 반응 시간으로 우수한 물성의 CPVC 수지를 얻는데 유리하다.For example, when the target total power for performing the chlorination reaction is set to 100 W, compared to using one light source of 100 W, two light sources of 44 to 58 W, or three light sources of 31 to 37 W, or The use of four light sources of 24 to 27 W or five light sources of 19 to 21 W is advantageous for obtaining CPVC resins of excellent physical properties with shortened chlorination reaction time.
다른 일 예로, 염소화 반응 수행을 위한 타겟 총 출력을 450 W로 설정한 경우, 450 W의 광원 1 개를 이용하는 것에 비하여, 196 내지 264 W의 광원 2 개, 혹은 137 내지 166 W의 광원 3 개, 혹은 105 내지 121 W의 광원 4 개, 혹은 85 내지 95 W의 광원 5 개를 이용하는 것이 단축된 염소화 반응 시간으로 우수한 물성의 CPVC 수지를 얻는데 유리하다.As another example, when the target total power for performing the chlorination reaction is set to 450 W, compared to using one light source of 450 W, two light sources of 196 to 264 W, or three light sources of 137 to 166 W, Alternatively, using four light sources of 105 to 121 W or five light sources of 85 to 95 W is advantageous for obtaining a CPVC resin having excellent physical properties with a shortened chlorination reaction time.
또 다른 일 예로, 염소화 반응 수행을 위한 타겟 총 출력을 500 W로 설정한 경우, 500 W의 광원 1 개를 이용하는 것에 비하여, 218 내지 294 W의 광원 2 개, 혹은 152 내지 185 W의 광원 3 개, 혹은 117 내지 135 W의 광원 4 개, 혹은 95 내지 106 W의 광원 5 개를 이용하는 것이 단축된 염소화 반응 시간으로 우수한 물성의 CPVC 수지를 얻는데 유리하다.As another example, when the target total power for performing the chlorination reaction is set to 500 W, compared to using one light source of 500 W, two light sources of 218 to 294 W, or three light sources of 152 to 185 W Alternatively, using four light sources of 117 to 135 W or five light sources of 95 to 106 W is advantageous for obtaining CPVC resins having excellent physical properties with shortened chlorination reaction time.
다만, 타겟 총 출력(W)을 기준으로 W/(n+0.3) 미만의 출력을 갖는 n 개의 광원을 이용할 경우 광원의 총 출력이 타겟 총 출력 대비 너무 낮아 염소화 반응 효율이 저하할 수 있다. 그리고, 타겟 총 출력(W)을 기준으로 W/(n-0.3) 초과의 출력을 갖는 n 개의 광원을 이용할 경우 광원의 총 출력이 타겟 총 출력 대비 너무 높아 CPVC 수지의 물성이 열악해질 수 있다.However, when using n light sources having an output of less than W/(n+0.3) based on the target total power W, the total output power of the light source is too low compared to the target total power, so that the chlorination reaction efficiency may be reduced. In addition, when using n light sources having an output greater than W/(n-0.3) based on the target total output W, the total output power of the light source is too high compared to the target total output power, thereby deteriorating physical properties of the CPVC resin.
발명의 구현 예에 따르면, 상기 염소화 반응 단계는, 상기 자외선 광원의 출력을 타겟 총 출력(W)의 W/(n+0.3) 내지 W/(n-0.3)의 범위에서 가변적으로 조절하면서 수행될 수 있다.According to an embodiment of the invention, the chlorination reaction step is performed while variably adjusting the output of the ultraviolet light source in the range of W/(n+0.3) to W/(n-0.3) of the target total output W. Can.
예를 들어, 상기 자외선 광원의 출력은 반응기에 염소의 도입이 시작되는 시점부터 상기 염소화 반응 단계가 종료될 때까지 한 차례 또는 여러 차례 조절될 수 있다.For example, the output of the ultraviolet light source may be adjusted once or several times from the time when the introduction of chlorine into the reactor starts to the end of the chlorination reaction step.
일 예로, 상기 염소화 반응 단계는,For example, the chlorination reaction step,
i) 염화비닐계 수지가 도입된 반응기에 염소의 도입이 시작되는 시점부터 염소의 도입이 종료되는 시점까지 타겟 총 출력(W)을 기준으로 W/(n-0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행되고;i) From the start point of the introduction of chlorine to the end of the introduction of chlorine to the reactor in which the vinyl chloride-based resin has been introduced, the number of ns irradiated with the output of W/(n-0.3) is based on the target total output (W). (However, it is performed by photoreaction using an ultraviolet light source of n≥2);
ii) 염소의 도입이 종료되는 시점부터 상기 염소화 반응 단계가 종료되는 시점까지 타겟 총 출력(W)을 기준으로 W/(n+0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행될 수 있다.ii) From the point at which the introduction of chlorine is ended to the point at which the chlorination reaction step is completed, n numbers (however, n≥2) are irradiated with the output of W/(n+0.3) based on the target total output (W). It can be performed by photoreaction using an ultraviolet light source.
상기 염소화 반응에는, 필요에 따라, 퍼옥시에스터(peroxyester), 하이드로퍼옥사이드(hydroperoxide) 및 디알킬퍼옥사이드(dialkyl peroxide)와 같은 광 개시제가 더 투입될 수 있다.If necessary, a photoinitiator such as peroxyester, hydroperoxide, and dialkyl peroxide may be further added to the chlorination reaction.
상기 반응기에 투입되는 염소의 양이 목표치에 도달하면 상기 염소화 반응을 종료한다.When the amount of chlorine input to the reactor reaches a target value, the chlorination reaction is terminated.
상기 염소화 반응 종료 후 얻어지는 슬러리에 대해 충분한 양의 질소로 미반응 잔류 염소를 제거한다.Unreacted residual chlorine is removed with a sufficient amount of nitrogen for the slurry obtained after the chlorination reaction is completed.
그리고, 얻어진 슬러리를 탈수하여 불순물을 제거한 후, 용매를 투입하여 재슬러리화하여 다음 단계로 전달한다.Then, after removing the impurities by dewatering the obtained slurry, the solvent is added to re-slurry and transferred to the next step.
(2) 중화 반응 단계(2) neutralization reaction step
상기 염소화 반응 단계에서 얻은 상기 CPVC 슬러리를 중화제와 반응시키는 단계가 수행된다.The step of reacting the CPVC slurry obtained in the chlorination reaction step with a neutralizing agent is performed.
상기 중화 반응 단계는, 상기 CPVC 슬러리의 pH를 높여 안정성을 향상시키고 CPVC 내 잔류 HCl의 양을 최소화하기 위한 단계이다.The neutralization step is a step for increasing the pH of the CPVC slurry to improve stability and to minimize the amount of residual HCl in CPVC.
상기 중화제로는 본 발명이 속하는 기술분야에서 잘 알려진 화합물이 사용될 수 있다.As the neutralizing agent, a compound well known in the art to which the present invention pertains may be used.
예를 들어, 상기 중화제는 소듐 하이드록사이드, 포타슘 하이드록사이드, 리튬 하이드록사이드, 소듐 카보네이트, 포타슘 카보네이트, 칼슘 카보네이트, 소듐 바이카보네이트, 포타슘 바이카보네이트, 소듐 퍼카보네이트, 및 포타슘 퍼카보네이트로 이루어진 군에서 선택된 1종 이상의 화합물일 수 있다.For example, the neutralizing agent is a group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium percarbonate, and potassium percarbonate It may be one or more compounds selected from.
상기 중화 반응 단계에서, 상기 중화제는 상기 CPVC 슬러리가 pH 6.0 내지 pH 8.0이 되도록 하는 양으로 사용될 수 있다. 일 예로, 상기 중화제는 상기 CPVC 슬러리 100 중량부에 대하여 1 내지 20 중량부로 사용될 수 있다.In the neutralization reaction step, the neutralizing agent may be used in an amount such that the CPVC slurry is pH 6.0 to pH 8.0. For example, the neutralizing agent may be used in 1 to 20 parts by weight based on 100 parts by weight of the CPVC slurry.
상기 중화제는 분말 또는 용액 형태로 투입될 수 있다.The neutralizing agent may be added in powder or solution form.
상기 중화제 투입 시에는 교반을 통해 중화 효율을 높일 수 있다.When the neutralizing agent is added, neutralization efficiency may be increased through stirring.
상기 중화 반응은 상기 CPVC 슬러리에 포함된 용매의 끓는 점 미만의 온도에서 수행된다. 일 예로, 상기 중화 반응 단계는 20 내지 80 ℃의 온도 하에서 수행될 수 있다.The neutralization reaction is carried out at a temperature below the boiling point of the solvent contained in the CPVC slurry. For example, the neutralization reaction step may be performed under a temperature of 20 to 80 ℃.
중화가 완료된 CPVC 슬러리를 탈수하여 용매 및 불순물을 제거한다.The neutralized CPVC slurry is dehydrated to remove solvent and impurities.
상기 탈수를 통해 얻은 CPVC 케이크를 건조하여, 최종적으로 분말상의 CPVC 수지를 얻을 수 있다.The CPVC cake obtained through the dehydration can be dried to finally obtain a powdery CPVC resin.
본 발명에 따르면, 트레이드-오프(trade-off)의 관계에 있는 반응 효율과 수지의 물성 중 어느 하나를 희생하지 않고 염소화 폴리염화비닐 수지를 제조할 수 있는 방법이 제공된다.According to the present invention, there is provided a method capable of producing a chlorinated polyvinyl chloride resin without sacrificing any one of a trade-off reaction efficiency and a property of the resin.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예들을 제시한다. 그러나 하기의 실시예들은 본 발명을 예시하기 위한 것일 뿐, 본 발명을 이들만으로 한정하는 것은 아니다.Hereinafter, preferred embodiments are presented to help understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.
비교예 1Comparative Example 1
중합도 1000인 폴리염화비닐 및 탈이온수를 혼합하여 20 중량% 폴리염화비닐 슬러리를 제조하였다. 상기 폴리염화비닐 슬러리 3.5 L를 5 L 부피의 원기둥형 반응기에 투입하였다. 투입된 상기 슬러리를 400 내지 1000 rpm의 일정한 속도로 교반하면서 반응기 내부의 압력이 - 0.9 bar 이상이 될 때까지 탈기를 진행하였다.A polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry. 3.5 L of the polyvinyl chloride slurry was charged to a 5 L volume cylindrical reactor. The slurry was stirred at a constant speed of 400 to 1000 rpm while degassing was performed until the pressure inside the reactor became −0.9 bar or more.
반응기를 40 ℃로 승온한 후 염소 투입을 시작하였다. 반응기 내에 구비된 광원인 100 W의 UV 수은 램프(260 내지 430 nm의 파장 범위, arc length 8 cm) 1 기를 가동하여 염소화 반응을 실시하였다. 상기 UV 수은 램프는 반응기의 중심축 상에 상기 아크 길이(arc length)가 상기 슬러리 내에 잠기도록 설치되었고, 방사상으로 UV 광을 방출하였다.After the reactor was heated to 40° C., chlorine was introduced. A chlorination reaction was performed by operating one group of a UV mercury lamp (wavelength range of 260 to 430 nm, arc length 8 cm) of 100 W, a light source provided in the reactor. The UV mercury lamp was installed so that the arc length was immersed in the slurry on the central axis of the reactor, and emitted UV light radially.
상기 염소화 반응은 0.5 내지 4.0 bar의 압력 및 50 내지 95 ℃의 온도 하에서 진행되었다. 상기 염소화 반응 중 투입된 염소가 목표치에 도달하면 반응을 종료하였다.The chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
반응 종료 후 얻어진 염소화 폴리염화비닐 슬러리에 대해 충분한 질소로 미반응 잔류 염소를 제거하였다. 상기 염소화 폴리염화비닐 슬러리를 탈수한 후 다시 탈이온수로 슬러리를 제조하였다.After the reaction was completed, unreacted residual chlorine was removed with sufficient nitrogen for the obtained chlorinated polyvinyl chloride slurry. After dehydrating the chlorinated polyvinyl chloride slurry, a slurry was prepared again with deionized water.
상기 염소화 폴리염화비닐 슬러리에 소듐 하이드록사이드를 혼합하여 중화하였다. 중화된 상기 염소화 폴리염화비닐 슬러리를 탈수 및 건조하여 분말상의 염소화 폴리염화비닐 수지를 얻었다.Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it. The neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
실시예 1Example 1
중합도 1000인 폴리염화비닐 및 탈이온수를 혼합하여 20 중량% 폴리염화비닐 슬러리를 제조하였다. 상기 폴리염화비닐 슬러리 3.5 L를 5 L 부피의 원기둥형 반응기에 투입하였다. 투입된 상기 슬러리를 400 내지 1000 rpm의 일정한 속도로 교반하면서 반응기 내부의 압력이 - 0.9 bar 이상이 될 때까지 탈기를 진행하였다.A polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry. 3.5 L of the polyvinyl chloride slurry was charged to a 5 L volume cylindrical reactor. The slurry was stirred at a constant speed of 400 to 1000 rpm while degassing was performed until the pressure inside the reactor became −0.9 bar or more.
반응기를 40 ℃로 승온한 후 염소 투입을 시작하였다. 염소화 반응을 위한 타겟 총 출력을 100 W로 설정하고, 반응기 내에 구비된 광원인 50 W의 UV 수은 램프(260 내지 430 nm의 파장 범위, arc length 8 cm) 2 기를 가동하여 염소화 반응을 실시하였다. 상기 2 기의 UV 수은 램프는 상기 아크 길이(arc length)가 상기 슬러리 내에 잠기도록 반응기의 중심축 상에 서로 대칭으로 설치되었고, 방사상으로 UV 광을 방출하였다.After the reactor was heated to 40° C., chlorine was introduced. The target total power for the chlorination reaction was set to 100 W, and two groups of 50 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 8 cm), a light source provided in the reactor, were operated to perform a chlorination reaction. The two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
상기 염소화 반응은 0.5 내지 4.0 bar의 압력 및 50 내지 95 ℃의 온도 하에서 진행되었다. 상기 염소화 반응 중 투입된 염소가 목표치에 도달하면 반응을 종료하였다.The chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
반응 종료 후 얻어진 염소화 폴리염화비닐 슬러리에 대해 충분한 질소로 미반응 잔류 염소를 제거하였다. 상기 염소화 폴리염화비닐 슬러리를 탈수한 후 다시 탈이온수로 슬러리를 제조하였다.After the reaction was completed, unreacted residual chlorine was removed with sufficient nitrogen for the obtained chlorinated polyvinyl chloride slurry. After dehydrating the chlorinated polyvinyl chloride slurry, a slurry was prepared again with deionized water.
상기 염소화 폴리염화비닐 슬러리에 소듐 하이드록사이드를 혼합하여 중화하였다. 중화된 상기 염소화 폴리염화비닐 슬러리를 탈수 및 건조하여 분말상의 염소화 폴리염화비닐 수지를 얻었다.Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it. The neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
비교예 2Comparative Example 2
염소화 반응을 위한 타겟 총 출력을 100 W로 설정하고, 반응기 내에 구비된 광원인 60 W의 UV 수은 램프(260 내지 430 nm의 파장 범위, arc length 8 cm) 2 기를 가동하여 염소화 반응을 실시한 것을 제외하고, 상기 실시예 1과 동일한 방법으로 염소화 폴리염화비닐 수지를 얻었다.Except that the chlorination reaction was performed by setting the target total power for the chlorination reaction to 100 W and operating two groups of 60 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 8 cm), a light source provided in the reactor. Then, a chlorinated polyvinyl chloride resin was obtained in the same manner as in Example 1.
실시예 2Example 2
염소화 반응을 위한 타겟 총 출력을 100 W로 설정하고, 반응기 내에 구비된 광원인 37 W의 UV 수은 램프(260 내지 430 nm의 파장 범위, arc length 8 cm) 3 기를 가동하여 염소화 반응을 실시한 것을 제외하고, 상기 실시예 1과 동일한 방법으로 염소화 폴리염화비닐 수지를 얻었다.The target total power for the chlorination reaction is set to 100 W, and the chlorination reaction is performed by operating three groups of 37 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 8 cm), which are light sources provided in the reactor. Then, a chlorinated polyvinyl chloride resin was obtained in the same manner as in Example 1.
비교예 3Comparative Example 3
중합도 1000인 폴리염화비닐 및 탈이온수를 혼합하여 20 중량% 폴리염화비닐 슬러리를 제조하였다. 상기 폴리염화비닐 슬러리 140 L를 200 L 부피의 원기둥형 반응기에 투입하였다.A polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry. 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
투입된 상기 슬러리를 350 내지 800 rpm의 일정한 속도로 교반하면서 반응기 내부의 압력이 - 0.9 bar 이상이 될 때까지 탈기를 진행하였다. 탈기 후 반응기 내부 압력이 - 0.9 bar를 5 분 이상 유지되는 것이 확인되면 반응기 승온을 실시하였다.Degassing was performed until the pressure in the reactor became −0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
반응기 온도가 40 ℃에 이르러 염소 투입을 시작하였다. 반응기 내에 구비된 광원인 450 W의 UV 수은 램프(260 내지 430 nm의 파장 범위, arc length 14.5 cm) 1 기를 가동하여 염소화 반응을 실시하였다. 상기 UV 수은 램프는 반응기의 중심축 상에 상기 아크 길이(arc length)가 상기 슬러리 내에 잠기도록 설치되었고, 방사상으로 UV 광을 방출하였다.When the reactor temperature reached 40°C, chlorine was introduced. A chlorination reaction was performed by operating one group of a 450 W UV mercury lamp (wavelength range of 260 to 430 nm, arc length 14.5 cm) as a light source provided in the reactor. The UV mercury lamp was installed so that the arc length was immersed in the slurry on the central axis of the reactor, and emitted UV light radially.
상기 염소화 반응은 0.5 내지 4.0 bar의 압력 및 50 내지 95 ℃의 온도 하에서 진행되었다. 상기 염소화 반응 중 투입된 염소가 목표치에 도달하면 반응을 종료하였다.The chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
반응 종료 후 얻어진 염소화 폴리염화비닐 슬러리에 대해 충분한 질소로 미반응 잔류 염소를 제거하였다. 상기 염소화 폴리염화비닐 슬러리를 탈수한 후 다시 탈이온수로 슬러리를 제조하였다.After the reaction was completed, unreacted residual chlorine was removed with sufficient nitrogen for the obtained chlorinated polyvinyl chloride slurry. After dehydrating the chlorinated polyvinyl chloride slurry, a slurry was prepared again with deionized water.
상기 염소화 폴리염화비닐 슬러리에 소듐 하이드록사이드를 혼합하여 중화하였다. 중화된 상기 염소화 폴리염화비닐 슬러리를 탈수 및 건조하여 분말상의 염소화 폴리염화비닐 수지를 얻었다.Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it. The neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
실시예 3Example 3
중합도 1000인 폴리염화비닐 및 탈이온수를 혼합하여 20 중량% 폴리염화비닐 슬러리를 제조하였다. 상기 폴리염화비닐 슬러리 140 L를 200 L 부피의 원기둥형 반응기에 투입하였다.A polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry. 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
투입된 상기 슬러리를 350 내지 800 rpm의 일정한 속도로 교반하면서 반응기 내부의 압력이 - 0.9 bar 이상이 될 때까지 탈기를 진행하였다. 탈기 후 반응기 내부 압력이 - 0.9 bar를 5 분 이상 유지되는 것이 확인되면 반응기 승온을 실시하였다.Degassing was performed until the pressure in the reactor became −0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
반응기 온도가 40 ℃에 이르러 염소 투입을 시작하였다. 염소화 반응을 위한 타겟 총 출력을 450 W로 설정하고, 반응기 내에 구비된 광원인 200 W의 UV 수은 램프(260 내지 430 nm의 파장 범위, arc length 14.5 cm) 2 기를 가동하여 염소화 반응을 실시하였다. 상기 2 기의 UV 수은 램프는 상기 아크 길이(arc length)가 상기 슬러리 내에 잠기도록 반응기의 중심축 상에 서로 대칭으로 설치되었고, 방사상으로 UV 광을 방출하였다.When the reactor temperature reached 40°C, chlorine was introduced. The target total power for the chlorination reaction was set to 450 W, and two groups of 200 W UV mercury lamps (wavelength range of 260 to 430 nm, arc length 14.5 cm), a light source provided in the reactor, were operated to perform a chlorination reaction. The two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
상기 염소화 반응은 0.5 내지 4.0 bar의 압력 및 50 내지 95 ℃의 온도 하에서 진행되었다. 상기 염소화 반응 중 투입된 염소가 목표치에 도달하면 반응을 종료하였다.The chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
반응 종료 후 얻어진 염소화 폴리염화비닐 슬러리에 대해 충분한 질소로 미반응 잔류 염소를 제거하였다. 상기 염소화 폴리염화비닐 슬러리를 탈수한 후 다시 탈이온수로 슬러리를 제조하였다.After the reaction was completed, unreacted residual chlorine was removed with sufficient nitrogen for the obtained chlorinated polyvinyl chloride slurry. After dehydrating the chlorinated polyvinyl chloride slurry, a slurry was prepared again with deionized water.
상기 염소화 폴리염화비닐 슬러리에 소듐 하이드록사이드를 혼합하여 중화하였다. 중화된 상기 염소화 폴리염화비닐 슬러리를 탈수 및 건조하여 분말상의 염소화 폴리염화비닐 수지를 얻었다.Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it. The neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
실시예 4Example 4
중합도 1000인 폴리염화비닐 및 탈이온수를 혼합하여 20 중량% 폴리염화비닐 슬러리를 제조하였다. 상기 폴리염화비닐 슬러리 140 L를 200 L 부피의 원기둥형 반응기에 투입하였다.A polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry. 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
투입된 상기 슬러리를 350 내지 800 rpm의 일정한 속도로 교반하면서 반응기 내부의 압력이 - 0.9 bar 이상이 될 때까지 탈기를 진행하였다. 탈기 후 반응기 내부 압력이 - 0.9 bar를 5 분 이상 유지되는 것이 확인되면 반응기 승온을 실시하였다.Degassing was performed until the pressure in the reactor became −0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
반응기 온도가 40 ℃에 이르러 염소 투입을 시작하였다. 염소화 반응을 위한 타겟 총 출력을 450 W로 설정하고, 반응기 내에 구비된 광원인 250 W의 UV LED 램프(260 내지 430 nm의 파장 범위, arc length 14.5 cm) 2 기를 가동하여 염소화 반응을 실시하였다. 상기 2 기의 UV 수은 램프는 상기 아크 길이(arc length)가 상기 슬러리 내에 잠기도록 반응기의 중심축 상에 서로 대칭으로 설치되었고, 방사상으로 UV 광을 방출하였다.When the reactor temperature reached 40°C, chlorine was introduced. The target total power for the chlorination reaction was set to 450 W, and two groups of 250 W UV LED lamps (wavelength range of 260 to 430 nm, arc length 14.5 cm), a light source provided in the reactor, were operated to perform a chlorination reaction. The two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
상기 염소화 반응은 0.5 내지 4.0 bar의 압력 및 50 내지 95 ℃의 온도 하에서 진행되었다. 상기 염소화 반응 중 투입된 염소가 목표치에 도달하면 반응을 종료하였다.The chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
반응 종료 후 얻어진 염소화 폴리염화비닐 슬러리에 대해 충분한 질소로 미반응 잔류 염소를 제거하였다. 상기 염소화 폴리염화비닐 슬러리를 탈수한 후 다시 탈이온수로 슬러리를 제조하였다.After the reaction was completed, unreacted residual chlorine was removed with sufficient nitrogen for the obtained chlorinated polyvinyl chloride slurry. After dehydrating the chlorinated polyvinyl chloride slurry, a slurry was prepared again with deionized water.
상기 염소화 폴리염화비닐 슬러리에 소듐 하이드록사이드를 혼합하여 중화하였다. 중화된 상기 염소화 폴리염화비닐 슬러리를 탈수 및 건조하여 분말상의 염소화 폴리염화비닐 수지를 얻었다.Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it. The neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
실시예 5Example 5
중합도 1000인 폴리염화비닐 및 탈이온수를 혼합하여 20 중량% 폴리염화비닐 슬러리를 제조하였다. 상기 폴리염화비닐 슬러리 140 L를 200 L 부피의 원기둥형 반응기에 투입하였다.A polyvinyl chloride and deionized water having a polymerization degree of 1000 were mixed to prepare a 20% by weight polyvinyl chloride slurry. 140 L of the polyvinyl chloride slurry was charged into a 200 L volume cylindrical reactor.
투입된 상기 슬러리를 350 내지 800 rpm의 일정한 속도로 교반하면서 반응기 내부의 압력이 - 0.9 bar 이상이 될 때까지 탈기를 진행하였다. 탈기 후 반응기 내부 압력이 - 0.9 bar를 5 분 이상 유지되는 것이 확인되면 반응기 승온을 실시하였다.Degassing was performed until the pressure in the reactor became −0.9 bar or more while stirring the injected slurry at a constant speed of 350 to 800 rpm. After degassing, it was confirmed that the reactor internal pressure was maintained at-0.9 bar for 5 minutes or more, and the reactor was heated.
반응기 온도가 40 ℃에 이르러 염소 투입을 시작하였다. 염소화 반응을 위한 타겟 총 출력을 450 W로 설정하고, 반응기 내에 구비된 광원인 250 W의 UV LED 램프(260 내지 430 nm의 파장 범위, arc length 14.5 cm) 2 기를 가동하여 염소화 반응을 실시하였다. 상기 2 기의 UV 수은 램프는 상기 아크 길이(arc length)가 상기 슬러리 내에 잠기도록 반응기의 중심축 상에 서로 대칭으로 설치되었고, 방사상으로 UV 광을 방출하였다.When the reactor temperature reached 40°C, chlorine was introduced. The target total power for the chlorination reaction was set to 450 W, and two groups of 250 W UV LED lamps (wavelength range of 260 to 430 nm, arc length 14.5 cm), a light source provided in the reactor, were operated to perform a chlorination reaction. The two UV mercury lamps were installed symmetrically to each other on the central axis of the reactor such that the arc length was submerged in the slurry, and radiated UV light radially.
염소의 투입이 종료됨과 동시에 상기 광원인 2 기의 UV LED 램프의 출력을 각각 200 W로 낮추었다.At the same time as the chlorine input was completed, the output of the two UV LED lamps as the light source was lowered to 200 W, respectively.
상기 염소화 반응은 0.5 내지 4.0 bar의 압력 및 50 내지 95 ℃의 온도 하에서 진행되었다. 상기 염소화 반응 중 투입된 염소가 목표치에 도달하면 반응을 종료하였다.The chlorination reaction was carried out under a pressure of 0.5 to 4.0 bar and a temperature of 50 to 95 °C. When the chlorine added during the chlorination reaction reaches the target value, the reaction was terminated.
반응 종료 후 얻어진 염소화 폴리염화비닐 슬러리에 대해 충분한 질소로 미반응 잔류 염소를 제거하였다. 상기 염소화 폴리염화비닐 슬러리를 탈수한 후 다시 탈이온수로 슬러리를 제조하였다.After the reaction was completed, unreacted residual chlorine was removed with sufficient nitrogen for the obtained chlorinated polyvinyl chloride slurry. After dehydrating the chlorinated polyvinyl chloride slurry, a slurry was prepared again with deionized water.
상기 염소화 폴리염화비닐 슬러리에 소듐 하이드록사이드를 혼합하여 중화하였다. 중화된 상기 염소화 폴리염화비닐 슬러리를 탈수 및 건조하여 분말상의 염소화 폴리염화비닐 수지를 얻었다.Sodium hydroxide was mixed with the chlorinated polyvinyl chloride slurry to neutralize it. The neutralized chlorinated polyvinyl chloride slurry was dehydrated and dried to obtain a powdered chlorinated polyvinyl chloride resin.
시험예Test example
상기 실시예 및 비교예에서 얻은 각각의 염소화 폴리염화비닐 수지 100 중량부에 대하여, 열안정제(tin계열) 2 중량부, 충격보강제(MBS) 8 중량부, 활제(paraffin 및 polyester계열) 5 중량부, 및 필러(이산화타이타늄) 3 중량부를 혼합하여 CPVC 컴파운드 조성물을 제조하였다. 상기 CPVC 컴파운드 조성물을 T-다이 압출하여 두께 3 mm의 시트를 얻었다.100 parts by weight of each of the chlorinated polyvinyl chloride resins obtained in Examples and Comparative Examples, 2 parts by weight of a heat stabilizer (tin-based), 8 parts by weight of an impact modifier (MBS), and 5 parts by weight of a lubricant (paraffin and polyester) , And a filler (titanium dioxide) 3 parts by weight to prepare a CPVC compound composition. The CPVC compound composition was T-die extruded to obtain a sheet having a thickness of 3 mm.
상기 시트에 대해 다음의 특성을 평가하였다.The following properties were evaluated for the sheet.
(1) 가공 착색: UV-2600 UV-Vis Spectrometer (SHIMADZU)를 이용하여 백색도(white index, WI)와 황색도(yellow index, YI)(1) Process coloring: whiteness (white index, WI) and yellowness index (YI) using UV-2600 UV-Vis Spectrometer (SHIMADZU)
(2) 열 안정성: Mathis oven을 이용하여 195 ℃에서 10 분에 23 mm의 속도로 시트를 꺼내 탄화하는데 까지 걸리는 시간(분)을 측정하여 정적 열 안정성을 평가하였다.(2) Thermal Stability: Static heat stability was evaluated by measuring the time (minutes) to take out and carbonize a sheet at a rate of 23 mm at 10 minutes at 195°C using a Mathis oven.
(3) Vicat 연화점: KS M ISO 306:2015에 의거하여 Vicat softening temperature (VST)를 측정하였다 (50 ℃, 하중 50 N).(3) Vicat softening point: Vicat softening temperature (VST) was measured according to KS M ISO 306:2015 (50°C, load 50 N).
(4) 염소 함량: 원소분석기(elemental analyzer)를 이용하여 Cl 원소의 함량을 측정하였다.(4) Chlorine content: The content of Cl element was measured using an elemental analyzer.
Figure PCTKR2019016774-appb-T000001
Figure PCTKR2019016774-appb-T000001
상기 표 1을 참고하면, 상기 실시예 1 및 2에 따른 랩(lab) 스케일의 제법은 상기 비교예 1의 제법에 비하여 동등한 수준 이상의 물성을 갖는 CPVC를 얻을 수 있으면서도 염소화 반응 시간 및 총 반응 시간을 각각 약 11 % 이상만큼 단축시킬 수 있는 것으로 확인되었다.Referring to Table 1, the method of manufacturing lab scales according to Examples 1 and 2 can obtain CPVC having physical properties equal to or higher than those of Comparative Example 1, while obtaining chlorination reaction time and total reaction time. It was confirmed that each can be shortened by about 11% or more.
상기 비교예 2에서는 상기 실시예 1에 비하여 염소화 반응 시간 및 총 반응 시간이 단축되었으나, CPVD의 황색도가 높고 열 안정성이 떨어지는 것으로 확인되었다.In Comparative Example 2, the chlorination reaction time and total reaction time were shorter than in Example 1, but it was confirmed that the yellowness of CPVD was high and the thermal stability was poor.
Figure PCTKR2019016774-appb-T000002
Figure PCTKR2019016774-appb-T000002
상기 표 2를 참고하면, 상기 실시예 3에 따른 파일럿 스케일의 제법은 상기 비교예 2의 제법에 비하여 염소화 반응 시간을 약 11 % 만큼 단축시키면서도 우수한 열안정성을 갖는 CPVC를 얻을 수 있는 것으로 확인되었다.Referring to Table 2, it was confirmed that the manufacturing method of the pilot scale according to Example 3 can obtain CPVC having excellent thermal stability while reducing the chlorination reaction time by about 11% compared to the method of Comparative Example 2.
상기 실시예 4에 따른 파일럿 스케일의 제법은 타겟 총 출력(450 W) 보다 높은 램프 총 출력을 적용하였음에도 불구하고 상기 비교예 2의 제법에 비하여 물성의 저하 없이 20 % 이상 단축된 반응 시간으로 CPVC를 얻을 수 있는 것으로 확인되었다.The pilot scale manufacturing method according to Example 4, despite applying a lamp total power higher than the target total power (450 W), compared with the method of Comparative Example 2, CPVC with a reaction time reduced by 20% or more without deterioration of physical properties. It was confirmed that it can be obtained.
그리고, 상기 실시예 5에 따른 파일럿 스케일의 제법은 상기 비교예 2의 제법에 비하여 향상된 열 안정성을 갖는 CPVC를 25 % 만큼 단축된 염소화 반응 시간으로 얻을 수 있는 것으로 확인되었다.In addition, it was confirmed that the manufacturing method of the pilot scale according to Example 5 can obtain CPVC having improved thermal stability with a reduction in chlorination reaction time by 25% compared to the method of Comparative Example 2.

Claims (7)

  1. 염화비닐계 수지와 염소가 도입된 반응기 내에 자외선을 조사하여 염소화 폴리염화비닐 수지를 얻는 염소화 반응 단계, 및Chlorination reaction step of obtaining a chlorinated polyvinyl chloride resin by irradiating ultraviolet rays in a reactor in which the vinyl chloride resin and chlorine are introduced, and
    상기 염소화 폴리염화비닐 수지를 중화제와 반응시키는 중화 반응 단계를 포함하고;A neutralization reaction step of reacting the chlorinated polyvinyl chloride resin with a neutralizing agent;
    상기 염소화 반응 단계는, 타겟 총 출력(W)을 기준으로 W/(n+0.3) 내지 W/(n-0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행되는,In the chlorination reaction step, light using n (but n≥2) ultraviolet light sources irradiated with outputs of W/(n+0.3) to W/(n-0.3) based on the target total output (W) Carried out in reaction,
    염소화 폴리염화비닐 수지의 제조 방법.Method for producing chlorinated polyvinyl chloride resin.
  2. 제 1 항에 있어서,According to claim 1,
    상기 염소화 반응 단계는,The chlorination reaction step,
    i) 염화비닐계 수지가 도입된 반응기에 염소의 도입이 시작되는 시점부터 염소의 도입이 종료되는 시점까지 W/(n-0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행되고,i) n (but n≥2) UV rays irradiated with the output of W/(n-0.3) from the time when the introduction of chlorine starts to the time when the introduction of chlorine ends in the reactor in which the vinyl chloride resin is introduced It is performed by light reaction using a light source,
    ii) 염소의 도입이 종료되는 시점부터 상기 염소화 반응 단계가 종료되는 시점까지 W/(n+0.3)의 출력으로 조사하는 n 개(단, n≥2)의 자외선 광원을 이용한 광 반응으로 수행되는,ii) From the time when the introduction of chlorine ends to the time when the chlorination reaction step ends, it is performed by photoreaction using n (but n≥2) ultraviolet light sources irradiated with the output of W/(n+0.3). ,
    염소화 폴리염화비닐 수지의 제조 방법.Method for producing chlorinated polyvinyl chloride resin.
  3. 제 1 항에 있어서,According to claim 1,
    상기 염소화 반응 단계는 50 내지 95 ℃의 온도 하에서 수행되는, 염소화 폴리염화비닐 수지의 제조 방법.The chlorination reaction step is carried out under a temperature of 50 to 95 ℃, the production method of chlorinated polyvinyl chloride resin.
  4. 제 1 항에 있어서,According to claim 1,
    상기 자외선 광원은 파장 범위 260 내지 430 nm의 자외선을 조사하는 광원인, 염소화 폴리염화비닐 수지의 제조 방법.The ultraviolet light source is a method for producing a chlorinated polyvinyl chloride resin, which is a light source for irradiating ultraviolet rays having a wavelength range of 260 to 430 nm.
  5. 제 1 항에 있어서,According to claim 1,
    상기 자외선 광원은 자외선 LED, 유기 EL, 무기 EL, 수은 램프, 및 메탈할라이드 램프로 이루어진 군에서 선택된 1종 이상의 광원인, 염소화 폴리염화비닐 수지의 제조 방법.The ultraviolet light source is a method of manufacturing a chlorinated polyvinyl chloride resin, which is at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, mercury lamp, and metal halide lamp.
  6. 제 1 항에 있어서,According to claim 1,
    상기 중화제는 소듐 하이드록사이드, 포타슘 하이드록사이드, 리튬 하이드록사이드, 소듐 카보네이트, 포타슘 카보네이트, 칼슘 카보네이트, 소듐 바이카보네이트, 포타슘 바이카보네이트, 소듐 퍼카보네이트, 및 포타슘 퍼카보네이트로 이루어진 군에서 선택된 1종 이상의 화합물인, 염소화 폴리염화비닐 수지의 제조 방법.The neutralizing agent is one selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, potassium bicarbonate, sodium percarbonate, and potassium percarbonate. The above compound, a method for producing a chlorinated polyvinyl chloride resin.
  7. 제 1 항에 있어서,According to claim 1,
    상기 중화 반응 단계는 20 내지 80 ℃의 온도 하에서 수행되는, 염소화 폴리염화비닐 수지의 제조 방법.The neutralization reaction step is carried out under a temperature of 20 to 80 ℃, chlorinated polyvinyl chloride resin production method.
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