WO2020060028A1 - Vinyl chloride-based polymer and method for producing same - Google Patents

Vinyl chloride-based polymer and method for producing same Download PDF

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Publication number
WO2020060028A1
WO2020060028A1 PCT/KR2019/009907 KR2019009907W WO2020060028A1 WO 2020060028 A1 WO2020060028 A1 WO 2020060028A1 KR 2019009907 W KR2019009907 W KR 2019009907W WO 2020060028 A1 WO2020060028 A1 WO 2020060028A1
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Prior art keywords
vinyl chloride
equation
particle
polymerization
based polymer
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PCT/KR2019/009907
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French (fr)
Korean (ko)
Inventor
이세웅
안성용
김건지
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주식회사 엘지화학
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Priority claimed from KR1020190094160A external-priority patent/KR102178879B1/en
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to JP2020536046A priority Critical patent/JP7024093B2/en
Priority to US16/959,779 priority patent/US11186658B2/en
Priority to EP19863203.6A priority patent/EP3715387B1/en
Priority to CN201980007218.0A priority patent/CN111542552B/en
Publication of WO2020060028A1 publication Critical patent/WO2020060028A1/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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/02—Polymerisation in bulk
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers

Definitions

  • the present invention relates to a vinyl chloride-based polymer having an excellent blendability and processability improved by controlling the surface non-uniformity of particles.
  • the vinyl chloride-based polymer is a polymer containing 50% or more of vinyl chloride, and is inexpensive, easy to control hardness, and can be applied to most processing equipment, and has various application fields. In addition, it is widely used in various fields because it can provide molded articles excellent in physical and chemical properties, such as mechanical strength, weather resistance, and chemical resistance.
  • the vinyl chloride-based polymer is blended with the auxiliary materials and applied to various fields.
  • the bonding strength with the auxiliary material is poor, and as a result, the compounding property may be deteriorated and the processability may not be good.
  • the vinyl chloride-based polymer is manufactured and used through bulk polymerization, suspension polymerization, or emulsion polymerization as desired.
  • the production through bulk polymerization is not necessary because a polymerization process is performed without using a medium such as water and using a vinyl chloride monomer, an initiator, and other reaction additives, unlike suspension polymerization or emulsion polymerization, so a drying process is not necessary and thus the production cost It is relatively inexpensive and widely used in industry.
  • the present invention was devised to solve the problems of the prior art, and an object of the present invention is to provide a vinyl chloride-based polymer having excellent processability with a controlled surface non-uniformity of particles.
  • an object of the present invention is to provide a method for producing the vinyl chloride-based polymer.
  • the present invention provides a vinyl chloride-based polymer having a particle non-uniformity of 10 or more defined by the following equation (1).
  • Equation 1 X i is the standard deviation of the i-th particle, and is a value defined by Equation 2 below,
  • a n is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
  • D n is the n-th measurement diameter of the i-th particle
  • D 0 is the longest diameter in the i-th particle
  • n is an integer from 1 to 50.
  • the present invention is a step of forming a particle nucleus by adding a pre-polymerization initiator to the first vinyl chloride-based monomer and pre-polymerizing at a pressure of 8.0 K / G to 8.7 K / G; And post-polymerizing the second vinyl chloride-based monomer and post-polymerization initiator in the presence of the particle nucleus (step 2), wherein the pre-polymerization initiator is 1.3 K / G to 3.5 K / G compared to the pressure during pre-polymerization. It is to be added at a low pressure, and provides a method for producing the vinyl chloride-based polymer as described above in Equation 1 above.
  • the vinyl chloride-based polymer according to the present invention is prepared through the above-described manufacturing method in which the pressure condition during pre-polymerization and the input point of the pre-polymerization initiator are adjusted, so that the particle non-uniformity can be controlled, and can have a high porosity, and thus the compound properties This can be improved and the processability can be excellent.
  • the method for producing a vinyl chloride-based polymer according to the present invention controls the pressure during pre-polymerization in the pre-polymerization step of forming particle nuclei, and lowers the pressure of 1.3 K / G to 3.5 K / G compared to the pressure during pre-polymerization.
  • the surface of the particle nuclei of the initial reaction can be controlled by adding it to participate in the pre-polymerization, whereby a vinyl chloride-based polymer with controlled particle non-uniformity and porosity can be prepared.
  • the method for producing the vinyl chloride-based polymer according to the present invention and the vinyl chloride-based polymer prepared therefrom can be easily applied to industries requiring it, such as vinyl chloride-based resins and molded article related industries.
  • 1 is an SEM image of particles of a vinyl chloride polymer prepared through conventional bulk polymerization.
  • Figure 2 is a SEM image of the particles of the vinyl chloride polymer prepared through conventional suspension polymerization.
  • first vinyl chloride-based monomer' and 'second vinyl chloride-based monomer' used in the present invention are for distinguishing the order of participation in the reaction, and the material itself may mean the same vinyl chloride-based monomer.
  • the term 'particle non-uniformity' used in the present invention refers to the surface non-uniformity of the particles, or the roughness of the particle surface, to obtain a standard deviation between the diameters of 50 particles in the polymer in multiple directions, and the standard deviation of the diameter of each particle It is defined as the average value of, and the smaller the value, the smaller the standard deviation between the diameters of each particle, that is, the diameters in the multiple directions of the particles have similar values, indicating that the particles are close to spherical, and thus the particle surface has a low roughness. Or it could mean smooth.
  • K / G (kgf / cm 2 ) used in the present invention is a unit representing pressure, and 1 K / G may be equal to 0.968 atm.
  • the present invention provides a vinyl chloride-based polymer having excellent processability by improving the blendability by controlling the particle non-uniformity.
  • the vinyl chloride-based polymer according to an embodiment of the present invention can be adjusted by the manufacturing method described below, so that the surface roughness of the particles constituting the polymer can be controlled, and thus the compounding properties can be improved to improve processability.
  • the vinyl chloride-based polymer is characterized in that the particle non-uniformity defined by Equation 1 below is 10 or more. More specifically, the vinyl chloride-based polymer may have a particle non-uniformity of 11 or more and 16 or less.
  • Equation 1 X i is the standard deviation of the i-th particle, and is a value defined by Equation 2 below,
  • a n is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
  • D n is the n-th measurement diameter of the i-th particle
  • D 0 is the longest diameter in the i-th particle
  • n is an integer from 1 to 50.
  • the vinyl chloride-based polymer according to an embodiment of the present invention may have a gelation rate of 50 seconds or more and 80 seconds or less.
  • the vinyl chloride-based polymer according to the present invention can exhibit the gelation rate in the above-described range by having the above-described particle surface non-uniformity, and thus excellent processability.
  • the gelation rate was 50 g of a dry mixture prepared by mixing 2 parts by weight of a heat stabilizer and 2 parts by weight of an epoxidized soybean oil in 100 parts by weight of a vinyl chloride-based polymer, and melted at 30 rpm at 165 ° C at 30 rpm. It was measured by recording the mechanical load that appeared.
  • the vinyl chloride polymer according to the present invention may have a porosity of 59% or more, specifically 59 to 65% or 60% to 63%, and deterioration of mechanical properties within this range Without increasing the plasticizer absorption rate may be excellent workability.
  • the porosity was calculated from the amount of mercury penetrating into each vinyl chloride polymer particle using a mercury porosity analyzer (AutoPore IV 9520, Micromeritics).
  • the vinyl chloride-based polymer according to an embodiment of the present invention may be a bulk polymer.
  • the present invention provides a method for producing a vinyl chloride-based polymer having a controlled particle surface non-uniformity.
  • vinyl chloride-based polymers are manufactured through a method of bulk polymerization, suspension polymerization or emulsion polymerization, and, unlike suspension polymerization or emulsion polymerization, only a monomer, a polymerization initiator, and additives as necessary are added without using a medium. It is widely used in that it can be polymerized and does not require a post-polymerization process such as a drying process, so that production cost is low and mass production is easy.
  • the polymer particle surface has a smooth and angular shape, and thus, when compared with a polymer prepared by suspension polymerization or emulsion polymerization, the bonding strength with the auxiliary raw material is poor, resulting in poor processability.
  • the present invention provides a method for producing a vinyl chloride-based polymer having a vinyl chloride-based polymer prepared through bulk polymerization, but controlling the particle surface morphology by adjusting the input time of the polymerization initiator.
  • the method for preparing the vinyl chloride-based polymer comprises adding a pre-polymerization initiator to the first vinyl chloride-based monomer and pre-polymerizing it at a pressure of 8.0 K / G to 8.7 K / G to form particle nuclei. (Step 1); And post-polymerizing the second vinyl chloride-based monomer and post-polymerization initiator in the presence of the particle nucleus (step 2), wherein the pre-polymerization initiator is 1.3 K / G to 3.5 K / G lower than the pressure during pre-polymerization. It is characterized by adding at pressure.
  • the step A is a pre-polymerization step for forming a particle nucleus, and may be performed by adding a pre-polymerization initiator to the first vinyl chloride monomer and pre-polymerizing the pre-polymerization of 8.0 K / G to 8.7 K / G. It may be performed at a pressure, and the pre-polymerization initiator may be added at a pressure of 1.3 K / G to 3.5 K / G lower than the pressure during the pre-polymerization, specifically, the pre-polymerization initiator is the pressure during the pre-polymerization. Contrast may be to be added at a pressure of 1.5 K / G to 3.0 K / G lower.
  • reaction rate control is required at the beginning of the reaction in order to control the surface shape of the final polymer particles.
  • Polymerization is carried out at a pressure adjusted to the above-mentioned specific range, and when the pre-polymerization initiator reaches a pressure of 1.3 K / G to 3.5 K / G lower than the pressure during pre-polymerization, it is introduced into the first vinyl chloride-based monomer to thereby The non-uniformity and porosity can be adjusted to an appropriate level as described above.
  • step A the first vinyl chloride-based monomer is introduced into the reactor, and the pressure in the reactor is increased to a pressure determined from 8.0 K / G to 8.7 K / G to perform pre-polymerization. It may be that the pre-polymerization initiator is added when a pressure of 1.3 K / G to 3.5 K / G lower than the pre-polymerization performing pressure during the pressure rise, specifically, 1.5 K / G to 3.0 K / G, is reached.
  • the pre-polymerization initiator may be added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the first vinyl chloride-based monomer, and specifically, added in an amount of 0.03 to 0.1 parts by weight. If the prepolymerization initiator is added in the above range, the prepolymerization reaction can be smoothly initiated and the reaction time can be appropriately adjusted. In addition, since the reactant heat can be maintained at an appropriate value, stability deterioration due to the reaction heat can be prevented, and problems such as deterioration of thermal stability by the residual initiator can be minimized.
  • the pre-polymerization initiator is not particularly limited, for example, a peroxy ester or a compound of peroxydicarbonate or the like can be used, and specifically, di-2-ethylhexyl peroxysicarbonate, t-butylperoxyneode Canoate, t-butylperoxy ester, cumylperoxy ester, cumylperoxy neodecanoate, 1,1,3,3-tetramethyl butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate , t-hexyl peroxy pivalate, t-butyl peroxy pivalate, di-sec-butyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, isobutyryl peroxide, 3,5,5 -Trimethylhexanoyl peroxide, lauryl peroxide, and octyl peroxy dicarbonate
  • the first vinyl chloride monomer may be a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a vinyl monomer having copolymerization with the vinyl chloride monomer, wherein the first vinyl chloride monomer is a vinyl chloride monomer and In the case of a mixture of vinyl-based monomers, it may be used by appropriately adjusting so that vinyl chloride in the vinyl chloride-based polymer prepared therefrom is contained in 50% by weight or more.
  • the vinyl-based monomer is not particularly limited, for example, olefin compounds such as ethylene, propylene, and butene; Vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; Unsaturated nitriles such as acrylonitrile; Vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether, and vinyl lauryl ether; Vinylidene halides such as vinylidene chloride; Unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride and anhydrides of these fatty acids; Unsaturated fatty acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; Cross-linkable monomers such as diallyl phthalate, and the vinyl monomers
  • the pre-polymerization of step A may be carried out to 10% to 15% of the polymerization conversion rate.
  • the polymerization conversion rate of the pre-polymerization of the step A is not particularly limited, but the pre-polymerization is a step for preparing the particle nuclei, and if the pre-polymerization is excessively carried out and the particle nuclei are excessively formed, the physical properties of the polymer finally produced are It can be denatured differently than the purpose, so there is a need to control the degree of polymerization of the prepolymerization.
  • a vinyl chloride-based polymer having a desired degree of heterogeneity can be produced without excessively forming particle nuclei, but the polymerization degree and other physical properties may not be affected.
  • the polymerization conversion rate indicates the conversion rate of the first vinyl chloride monomer to the polymer, and may be measured using a butane tracer equipped with gas chromatography. Specifically, under certain polymerization conditions, a polymerization conversion rate curve according to a ratio of a vinyl chloride-based monomer over time with butane may be prepared for each polymerization condition, and based on this, a polymerization conversion rate according to polymerization conditions may be measured. Further, the polymerization conversion rate may include up to an error range according to measurement.
  • the pre-polymerization may be performed in a temperature range condition of 30 °C to 70 °C.
  • the step B is a step for producing a vinyl chloride-based polymer by growing the interior of the particle nucleus prepared by the pre-polymerization, a second vinyl chloride-based monomer and a post polymerization initiator in the presence of the particle nuclei prepared in the pre-polymerization step Can be post-polymerized.
  • the post-polymerization may be performed at a pressure of 6 K / G to 13 K / G.
  • the second vinyl chloride-based monomer may be the same as the first vinyl chloride-based monomer.
  • the post-polymerization initiator may be used in 0.05 parts by weight to 2 parts by weight based on 100 parts by weight of the second vinyl chloride monomer, specifically, 0.1 parts by weight to 0.5 parts by weight.
  • the post-polymerization initiator is not particularly limited, such as di-2-ethylhexyl peroxycarbonate, t-butyl peroxy neodecanoate, t-butyl peroxy ester, cumyl peroxy ester, cumyl peroxy neo Decanoate, 1,1,3,3-tetramethyl butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, di- sec-butyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauryl peroxide and octyl peroxy dicarbonate It may be one or more. Meanwhile, the post-polymerization initiator may be the same or different material from the pre-polymer
  • the post-polymerization may be performed in a temperature range of 30 °C to 70 °C.
  • the manufacturing method according to an embodiment of the present invention can remove the reactivity of the remaining post polymerization initiator by adding a polymerization inhibitor at the end of post polymerization, wherein the polymerization inhibitor is not particularly limited, for example, hydro Quinone, butylated hydroxy toluene, monomethyl ether hydroquinone, quaternary butyl catechol, diphenylamine, triisopropanol amine, triethanol amine, and the like can be used.
  • the polymerization inhibitor is not particularly limited, for example, hydro Quinone, butylated hydroxy toluene, monomethyl ether hydroquinone, quaternary butyl catechol, diphenylamine, triisopropanol amine, triethanol amine, and the like can be used.
  • the amount of the polymerization inhibitor may be appropriately adjusted depending on the amount of the post-polymerization initiator remaining, but is usually 0.001 part by weight to 0, based on 100 parts by weight of the total amount of vinyl chloride-based monomers used for pre-polymerization and post-polymerization. Can be used as 1 part by weight.
  • the manufacturing method may use a reaction medium as necessary, and further additives such as molecular weight modifiers may be used.
  • the reaction medium is not particularly limited, and a conventional organic solvent can be used.
  • aromatic compounds such as benzene, toluene, and xylene and methyl ethyl ketone, acetone, n-hexane, chloroform, cyclohexane, and the like can be used.
  • the molecular weight modifier is not particularly limited, for example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and the like can be used.
  • a vinyl chloride monomer was added to a 0.5 m 3 post-polymerization reactor, and the prepared particle nuclei were transferred, and then 1,1,3,3-tetramethyl butyl peroxy when the reactor internal pressure was 4 K / G.
  • 95 g of neodicarbonate (OND) was added, and the mixture was stirred and stirred, and polymerized at a pressure of 8 K / G for 180 minutes. After the polymerization was completed, unreacted vinyl chloride monomer remaining in vacuum for 30 minutes while stirring was collected to prepare a vinyl chloride polymer.
  • Example 1 a vinyl chloride polymer was prepared in the same manner as in Example 1, except that di-2-ethyl hexyl peroxydicarbonate was added at a time when 5 K / G was reached.
  • Example 1 the prepolymerization was carried out at 8.7 K / G, and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 6.7 K / G, and the same method as in Example 1 was used. A vinyl chloride polymer was prepared.
  • Example 1 the same method as in Example 1 except that 95 g of 1,1,3,3-tetramethyl butyl peroxy neodicarbonate (OND) was added together with the vinyl chloride monomer during post-polymerization. Through this, a vinyl chloride polymer was prepared.
  • OND 1,1,3,3-tetramethyl butyl peroxy neodicarbonate
  • Example 1 a vinyl chloride polymer was prepared in the same manner as in Example 1, except that pre-polymerization was performed at 12 K / G.
  • Example 1 a vinyl chloride polymer was prepared in the same manner as in Example 1, except that di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 7 K / G, but normal particle nuclei were obtained. The polymer was not produced because it was not produced. This is a result which means that di-2-ethylhexyl peroxydicarbonate is late and the dispersion is insufficient.
  • Example 1 a vinyl chloride polymer was prepared in the same manner as in Example 1, except that di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 4 K / G.
  • Example 1 except that the prepolymerization was carried out at 10 K / G and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 8.5 K / G, the same method as in Example 1 was used. A vinyl chloride polymer was prepared.
  • Example 1 except that the prepolymerization was carried out at 7 K / G and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 5.5 K / G, the same method as in Example 1 was carried out. A vinyl chloride polymer was prepared, but the polymer was not produced because normal particle nuclei were not produced. This is a result which means that the polymerization was not normally performed because the pressure was too low during pre-polymerization.
  • Example 1 the prepolymerization was carried out at 10 K / G, and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 6.5 K / G.
  • a vinyl chloride polymer was prepared.
  • Example 1 the prepolymerization was carried out at 9.5 K / G, and di-2-ethyl hexyl peroxydicarbonate was added at the time when 8 K / G was reached, and the same method as in Example 1 was used. A vinyl chloride polymer was prepared.
  • Example 1 a vinyl chloride polymer was prepared in the same manner as in Example 1, except that pre-polymerization was performed at 9.5 K / G.
  • Comparative Example 1 a vinyl chloride polymer was prepared through the same method as Comparative Example 1, except that post polymerization was performed at 7 K / G.
  • the particle non-uniformity is measured by measuring the longest diameter of each particle for a total of 50 particles observed using an optical microscope for each polymer surface, and measuring the 50 diameters passing through the center thereof. It was calculated through Equation 3. That is, the standard deviation of the diameter of each particle is calculated through Equations 2 and 3 using the longest diameter for each 50 particles and 50 diameters passing through the center thereof, and the average for the calculated 50 diameter standard deviation is calculated. It is represented by non-uniformity.
  • Equation 1 Xi is a standard deviation of the i-th particle, and is a value defined by Equation 2 below,
  • Equation 2 An is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
  • D n is the n-th measurement diameter of the i-th particle
  • D 0 is the longest diameter in the i-th particle
  • n is an integer from 1 to 50.
  • the polymerization degree was measured according to ASTM D1 243-49.
  • the porosity was calculated from the amount of mercury that penetrated into each vinyl chloride polymer particle using a mercury porosity analyzer (AutoPore IV 9520, Micromeritics).
  • Comparative Examples 9 and 10 in order to confirm the change in particle non-uniformity according to the conditions during post-polymerization, pre-polymerization proceeds in the same manner as in Comparative Example 1, and the post-polymerization initiator input time and post-polymerization pressure are changed during post-polymerization.
  • the post-polymerization initiator was added at a time of -2.5 K / G than that of post-polymerization, but the particle non-uniformity was not controlled, and in Comparative Example 10, the particle non-uniformity was not controlled and the polymerization degree was large. Rose.
  • the surface non-uniformity of the finally produced polymer particles can be controlled by adjusting the pre-polymerization pressure during pre-polymerization and adjusting the input time of the pre-polymerization initiator, and adjusting the pressure during post-polymerization and the control of the post-polymerization initiator input time. Through the above, it was confirmed that it may act as an obstacle to the production of the desired polymer.
  • Comparative Example 2 and Comparative Example 5 a polymer was not prepared, and thus the physical properties were not measured.
  • each vinyl chloride polymer of Examples and Comparative Examples was mixed with DOP (dioctyl phthalate), and calculated by the following Equation 4 to measure plasticizer absorption.
  • Plasticizer absorption rate (% by weight) [(B-A) / A] X100
  • Equation 4 A is the weight of the vinyl chloride polymer, and B is the weight of the vinyl chloride polymer absorbed by the plasticizer after mixing with the plasticizer.
  • the vinyl chloride polymers of Examples 1 to 4 according to an embodiment of the present invention have excellent blendability more than twice as compared to the vinyl chloride polymer of the comparative example, while the gelation rate is reduced by more than half, and the plasticizer Absorption rate was significantly increased and protrusions were significantly reduced.
  • the gelation rate is reduced and the plasticizer absorption rate is controlled by controlling the particle non-uniformity and porosity. It can be increased, and thus it was confirmed that the compoundability is excellent, and thus it is possible to show greatly improved processability.

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Abstract

The present invention relates to a method for producing a vinyl chloride-based polymer having improved processability by exhibiting excellent blending properties, and a vinyl chloride-based polymer produced thereby, and provides a vinyl chloride-based polymer having a particle non-uniformity, defined by mathematical equation 1, of at least 10, and a method for producing same.

Description

염화비닐계 중합체 및 이의 제조방법Vinyl chloride-based polymer and manufacturing method thereof
[관련출원과의 상호인용][Mutual citations with related applications]
본 출원은 2018. 09. 21.자 한국 특허 출원 제10-2018-0113823 및 2019. 08. 02.자 한국 특허 출원 제10-2019-0094160호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application Nos. 10-2018-0113823 on September 21, 2018 and Korean Patent Application Nos. 10-2019-0094160 on August 02, 2019, and claims the relevant Korean patent All content disclosed in the documents of is included as part of the present specification.
[기술분야][Technical field]
본 발명은 입자의 표면 불균일도가 조절되어 배합물성이 우수하고, 가공성이 개선된 염화비닐계 중합체 및 이의 제조방법에 관한 것이다.The present invention relates to a vinyl chloride-based polymer having an excellent blendability and processability improved by controlling the surface non-uniformity of particles.
염화비닐계 중합체는 염화비닐을 50% 이상 함유하는 중합체로서, 가격이 저렴하고 경도 조절이 용이하며 대부분의 가공기기에 적용 가능하여 응용분야가 다양하다. 게다가, 물리적·화학적 성질, 예컨대 기계적 강도, 내후성, 내약품성 등이 우수한 성형품을 제공할 수 있어 여러 분야에서 광범위하게 사용되고 있다. The vinyl chloride-based polymer is a polymer containing 50% or more of vinyl chloride, and is inexpensive, easy to control hardness, and can be applied to most processing equipment, and has various application fields. In addition, it is widely used in various fields because it can provide molded articles excellent in physical and chemical properties, such as mechanical strength, weather resistance, and chemical resistance.
한편, 염화비닐계 중합체는 부원료들과 배합되어 여러 분야에 적용되는데, 이때 염화비닐계 중합체 입자의 표면이 매끈한 경우 부원료와의 결합력이 좋지 못하여 결과적으로 배합물성이 저하되고 가공성이 좋지 못할 수 있다.On the other hand, the vinyl chloride-based polymer is blended with the auxiliary materials and applied to various fields. In this case, when the surface of the vinyl chloride-based polymer particles is smooth, the bonding strength with the auxiliary material is poor, and as a result, the compounding property may be deteriorated and the processability may not be good.
이러한, 염화비닐계 중합체는 목적하는 바에 따라 괴상중합, 현탁중합 또는 유화중합 등을 통하여 제조되어 사용되고 있다. 이 중, 괴상중합을 통한 제조는 현탁중합 또는 유화중합과는 달리 물과 같은 매체를 사용하지 않고 염화비닐계 단량체와 개시제 그리고 기타의 반응 첨가제를 이용하여 중합하기 때문에 건조 공정이 필요하지 않아 생산비용이 상대적으로 저렴하여 산업에서 널리 적용되고 있다. The vinyl chloride-based polymer is manufactured and used through bulk polymerization, suspension polymerization, or emulsion polymerization as desired. Among these, the production through bulk polymerization is not necessary because a polymerization process is performed without using a medium such as water and using a vinyl chloride monomer, an initiator, and other reaction additives, unlike suspension polymerization or emulsion polymerization, so a drying process is not necessary and thus the production cost It is relatively inexpensive and widely used in industry.
그러나, 대부분의 괴상중합으로 제조된 염화비닐계 중합체 입자는 표면이 매끈하고 각진 형태를 지니며(도 1 참고), 이에 표면이 불균일한 현탁중합으로 제조된 염화비닐계 중합체(도 2 참고) 대비 배합 가공시 부원료와의 결합력이 낮아 배합물이 뭉치게 되어 가공성이 좋지 못한 것으로 알려져 있다. However, most of the vinyl chloride-based polymer particles produced by bulk polymerization have a smooth surface and an angular shape (see FIG. 1), and thus a vinyl chloride-based polymer prepared by suspension polymerization with a non-uniform surface (see FIG. 2). It is known that the processability is poor because the binding power with the auxiliary raw material is low when the compounding process is performed.
따라서, 생산비용 측면에서 이점이 있는 괴상중합을 통해 제조된 염화비닐계 중합체의 산업 적용성을 더 높이기 위해서는 괴상중합을 통해 제조하되 제조되는 염화비닐계 중합체의 입자 표면을 거칠게 할 수 있는 방법이 필요한 실정이다.Therefore, in order to further increase the industrial applicability of the vinyl chloride polymer produced through bulk polymerization, which has an advantage in terms of production cost, a method capable of roughening the particle surface of the vinyl chloride polymer produced through mass polymerization is required. This is true.
본 발명은 상기 종래 기술의 문제점을 해결하기 위하여 안출된 것으로, 입자의 표면 불균일도가 조절된 가공성이 우수한 염화비닐계 중합체를 제공하는 것을 목적으로 한다. The present invention was devised to solve the problems of the prior art, and an object of the present invention is to provide a vinyl chloride-based polymer having excellent processability with a controlled surface non-uniformity of particles.
또한, 본 발명은 상기 염화비닐계 중합체의 제조방법을 제공하는 것을 목적으로 한다.In addition, an object of the present invention is to provide a method for producing the vinyl chloride-based polymer.
상기의 과제를 해결하기 위하여, 본 발명은 하기 수학식 1로 정의되는 입자 불균일도가 10 이상인 염화비닐계 중합체를 제공한다.In order to solve the above problems, the present invention provides a vinyl chloride-based polymer having a particle non-uniformity of 10 or more defined by the following equation (1).
[수학식 1][Equation 1]
Figure PCTKR2019009907-appb-I000001
Figure PCTKR2019009907-appb-I000001
상기 수학식 1에서, Xi는 i번째 입자의 표준편차로, 하기 수학식 2로 정의되는 값이고, In Equation 1, X i is the standard deviation of the i-th particle, and is a value defined by Equation 2 below,
[수학식 2][Equation 2]
Figure PCTKR2019009907-appb-I000002
Figure PCTKR2019009907-appb-I000002
상기 수학식 2에서, An은 i번째 입자의 n번째 측정 지름의 보정값이고, 여기에서 보정값은 하기 수학식 3으로 정의되는 값이며,In Equation 2, A n is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
[수학식 3][Equation 3]
Figure PCTKR2019009907-appb-I000003
Figure PCTKR2019009907-appb-I000003
상기 수학식 3에서, Dn은 i번째 입자의 n번째 측정 지름이고, D0은 i번째 입자에서 가장 긴 지름이며, n은 1 내지 50의 정수이다.In Equation 3, D n is the n-th measurement diameter of the i-th particle, D 0 is the longest diameter in the i-th particle, and n is an integer from 1 to 50.
또한, 본 발명은 제1 염화비닐계 단량체에 전중합 개시제를 첨가하고 8.0 K/G 내지 8.7 K/G의 압력에서 전중합하여 입자핵을 형성시키는 단계(단계 1); 및 상기 입자핵의 존재 하에 제2 염화비닐계 단량체 및 후중합 개시제를 후중합하는 단계(단계 2)를 포함하고, 상기 전중합 개시제는 전중합 시 압력 대비 1.3 K/G 내지 3.5 K/G으로 낮은 압력에서 첨가하는 것이며, 상기 수학식 1로 정의되는 입자 불균일도가 10 이상인 상기의 염화비닐계 중합체의 제조방법을 제공한다.In addition, the present invention is a step of forming a particle nucleus by adding a pre-polymerization initiator to the first vinyl chloride-based monomer and pre-polymerizing at a pressure of 8.0 K / G to 8.7 K / G; And post-polymerizing the second vinyl chloride-based monomer and post-polymerization initiator in the presence of the particle nucleus (step 2), wherein the pre-polymerization initiator is 1.3 K / G to 3.5 K / G compared to the pressure during pre-polymerization. It is to be added at a low pressure, and provides a method for producing the vinyl chloride-based polymer as described above in Equation 1 above.
본 발명의 따른 염화비닐계 중합체는 전중합 시 압력조건 및 전중합 개시제 투입시점이 조절된 상기의 제조방법을 통하여 제조됨으로써 입자 불균일도가 조절될 수 있고, 높은 기공률을 가질 수 있으며, 이에 배합물성이 향상되어 가공성이 우수할 수 있다.The vinyl chloride-based polymer according to the present invention is prepared through the above-described manufacturing method in which the pressure condition during pre-polymerization and the input point of the pre-polymerization initiator are adjusted, so that the particle non-uniformity can be controlled, and can have a high porosity, and thus the compound properties This can be improved and the processability can be excellent.
또한, 본 발명에 따른 염화비닐계 중합체의 제조방법은 입자핵을 형성시키는 전중합 단계에서 전중합 시 압력을 조절하고 전중합 개시제를 전중합 시 압력 대비 1.3 K/G 내지 3.5 K/G 낮은 압력일 때 첨가하여 전중합에 참여시킴으로써 반응 초기 입자핵의 표면을 조절할 수 있고, 이에 입자 불균일도 및 기공률이 조절된 염화비닐계 중합체를 제조할 수 있다. In addition, the method for producing a vinyl chloride-based polymer according to the present invention controls the pressure during pre-polymerization in the pre-polymerization step of forming particle nuclei, and lowers the pressure of 1.3 K / G to 3.5 K / G compared to the pressure during pre-polymerization. When it is added, the surface of the particle nuclei of the initial reaction can be controlled by adding it to participate in the pre-polymerization, whereby a vinyl chloride-based polymer with controlled particle non-uniformity and porosity can be prepared.
따라서, 본 발명에 따른 염화비닐계 중합체의 제조방법 및 이로부터 제조된 염화비닐계 중합체는 이를 필요로 하는 산업, 예컨대 염화비닐계 수지 및 성형품 관련 산업에 용이하게 적용할 수 있다.Therefore, the method for producing the vinyl chloride-based polymer according to the present invention and the vinyl chloride-based polymer prepared therefrom can be easily applied to industries requiring it, such as vinyl chloride-based resins and molded article related industries.
본 명세서에 첨부되는 다음의 도면은 본 발명의 구체적인 실시예를 예시하는 것이며, 전술한 발명의 내용과 함께 본 발명의 기술 사상을 더욱 이해시키는 역할을 하는 것이므로, 본 발명은 그러한 도면에 기재된 사항에만 한정되어 해석되어서는 안된다.The following drawings attached to the present specification illustrate specific embodiments of the present invention, and serve to further understand the technical spirit of the present invention together with the contents of the above-described invention, and therefore the present invention is limited to those described in those drawings. It should not be interpreted limitedly.
도 1은, 통상적인 괴상중합을 통하여 제조된 염화비닐 중합체의 입자를 관찰한 SEM 이미지이다. 1 is an SEM image of particles of a vinyl chloride polymer prepared through conventional bulk polymerization.
도 2는, 통상적인 현탁중합을 통하여 제조된 염화비닐 중합체의 입자를 관찰한 SEM 이미지이다.Figure 2 is a SEM image of the particles of the vinyl chloride polymer prepared through conventional suspension polymerization.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다. Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
본 명세서 및 청구범위에서 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the present specification and claims should not be interpreted as being limited to ordinary or lexical meanings, and the inventor can appropriately define the concept of terms in order to best describe his or her invention. Based on the principle that it should be interpreted as meanings and concepts consistent with the technical spirit of the present invention.
본 발명에서 사용되는 용어 '제1 염화비닐계 단량체' 및 '제2 염화비닐계 단량체'는 반응에 참여시키는 순서를 구별하기 위한 것으로, 물질 자체는 동일한 염화비닐계 단량체를 의미할 수 있다. The terms 'first vinyl chloride-based monomer' and 'second vinyl chloride-based monomer' used in the present invention are for distinguishing the order of participation in the reaction, and the material itself may mean the same vinyl chloride-based monomer.
본 발명에서 사용되는 용어 '입자 불균일도'는 입자의 표면 불균일성, 또는 입자 표면의 거칠기를 나타내는 것으로, 중합체 내 50개 입자에 대한 다수방향의 지름간 표준편차를 얻고, 이들 각 입자의 지름 표준편차의 평균값으로 정의하였으며, 수치가 작을수록 각 입자의 지름간 표준편차가 작은 것, 즉 입자의 다수방향의 지름들이 유사한 값을 갖는 것으로 입자가 구형에 가까움을 나타내는 것이며, 따라서 입자 표면의 거칠기가 낮다 혹은 매끈하다는 것을 의미할 수 있다. The term 'particle non-uniformity' used in the present invention refers to the surface non-uniformity of the particles, or the roughness of the particle surface, to obtain a standard deviation between the diameters of 50 particles in the polymer in multiple directions, and the standard deviation of the diameter of each particle It is defined as the average value of, and the smaller the value, the smaller the standard deviation between the diameters of each particle, that is, the diameters in the multiple directions of the particles have similar values, indicating that the particles are close to spherical, and thus the particle surface has a low roughness. Or it could mean smooth.
본 발명에서 사용되는 단위 "K/G(kgf/cm2)"는 압력을 나타내는 단위로, 1 K/G는 0.968 atm과 같을 수 있다.The unit “K / G (kgf / cm 2 )” used in the present invention is a unit representing pressure, and 1 K / G may be equal to 0.968 atm.
본 발명은 입자 불균일도가 조절되어 배합성이 개선됨으로써 가공성이 우수한 염화비닐계 중합체를 제공한다. The present invention provides a vinyl chloride-based polymer having excellent processability by improving the blendability by controlling the particle non-uniformity.
본 발명의 일 실시예에 따른 염화비닐계 중합체는 후술하는 제조방법으로 제조됨으로써 중합체를 이루는 입자의 표면의 거칠기가 조절될 수 있고, 이에 배합물성이 향상되어 가공성이 우수할 수 있다. The vinyl chloride-based polymer according to an embodiment of the present invention can be adjusted by the manufacturing method described below, so that the surface roughness of the particles constituting the polymer can be controlled, and thus the compounding properties can be improved to improve processability.
구체적으로, 상기 염화비닐계 중합체는 하기 수학식 1로 정의되는 입자 불균일도가 10 이상인 것을 특징으로 한다. 더 구체적으로, 상기 염화비닐계 중합체는 입자 불균일도가 11 이상 16 이하인 것일 수 있다.Specifically, the vinyl chloride-based polymer is characterized in that the particle non-uniformity defined by Equation 1 below is 10 or more. More specifically, the vinyl chloride-based polymer may have a particle non-uniformity of 11 or more and 16 or less.
[수학식 1][Equation 1]
Figure PCTKR2019009907-appb-I000004
Figure PCTKR2019009907-appb-I000004
상기 수학식 1에서, Xi는 i번째 입자의 표준편차로, 하기 수학식 2로 정의되는 값이고, In Equation 1, X i is the standard deviation of the i-th particle, and is a value defined by Equation 2 below,
[수학식 2][Equation 2]
Figure PCTKR2019009907-appb-I000005
Figure PCTKR2019009907-appb-I000005
상기 수학식 2에서, An은 i번째 입자의 n번째 측정 지름의 보정값이고, 여기에서 보정값은 하기 수학식 3으로 정의되는 값이며,In Equation 2, A n is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
[수학식 3][Equation 3]
Figure PCTKR2019009907-appb-I000006
Figure PCTKR2019009907-appb-I000006
상기 수학식 3에서, Dn은 i번째 입자의 n번째 측정 지름이고, D0은 i번째 입자에서 가장 긴 지름이며, n은 1 내지 50의 정수이다.In Equation 3, D n is the n-th measurement diameter of the i-th particle, D 0 is the longest diameter in the i-th particle, and n is an integer from 1 to 50.
또한, 본 발명의 일 실시예에 따른 상기 염화비닐계 중합체는 겔화 속도가 50초 이상 80초 이하인 것일 수 있다. 본 발명에 따른 상기 염화비닐계 중합체는 상기의 입자 표면 불균일도를 가짐으로써 전술한 범위의 겔화 속도를 나타낼 수 있고, 이에 가공성이 우수할 수 있다.In addition, the vinyl chloride-based polymer according to an embodiment of the present invention may have a gelation rate of 50 seconds or more and 80 seconds or less. The vinyl chloride-based polymer according to the present invention can exhibit the gelation rate in the above-described range by having the above-described particle surface non-uniformity, and thus excellent processability.
여기에서, 상기 겔화 속도는 염화비닐계 중합체 100 중량부에 열안정제 2 중량부, 에폭시화 대두유 2 중량부를 혼합하여 제조한 건조 혼합물 50 g을 Brabender Torque Rhomixer에 투입하고 165℃에서 30 rpm으로 용융시키면서 나타나는 기계적 부하를 기록하여 측정한 것이다.Here, the gelation rate was 50 g of a dry mixture prepared by mixing 2 parts by weight of a heat stabilizer and 2 parts by weight of an epoxidized soybean oil in 100 parts by weight of a vinyl chloride-based polymer, and melted at 30 rpm at 165 ° C at 30 rpm. It was measured by recording the mechanical load that appeared.
또한, 본 발명이 일 실시예에 따른 상기 염화비닐계 중합체는 기공률이 59% 이상인 것일 수 있고, 구체적으로는 59 내지 65% 또는 60% 내지 63%일 수 있으며, 이 범위 내에서 기계적 물성의 저하 없이 가소제 흡수율이 증가하여 가공성이 우수할 수 있다.Further, the vinyl chloride polymer according to the present invention may have a porosity of 59% or more, specifically 59 to 65% or 60% to 63%, and deterioration of mechanical properties within this range Without increasing the plasticizer absorption rate may be excellent workability.
여기에서, 상기 기공률은 수은 기공률 분석기(AutoPore IV 9520, Micromeritics 社)를 이용하여 각 염화비닐 중합체 입자 내로 침투한 수은의 양으로부터 계산하였다.Here, the porosity was calculated from the amount of mercury penetrating into each vinyl chloride polymer particle using a mercury porosity analyzer (AutoPore IV 9520, Micromeritics).
한편, 본 발명의 일 실시예에 따른 상기 염화비닐계 중합체는 괴상중합체일 수 있다. Meanwhile, the vinyl chloride-based polymer according to an embodiment of the present invention may be a bulk polymer.
또한, 본 발명은 입자 표면의 불균일도가 조절된 염화비닐계 중합체의 제조방법을 제공한다. In addition, the present invention provides a method for producing a vinyl chloride-based polymer having a controlled particle surface non-uniformity.
일반적으로 염화비닐계 중합체는 괴상중합, 현탁중합 또는 유화중합의 방법을 통하여 제조되고 있으며, 이중 괴상중합은 현탁중합 또는 유화중합과 달리 매질을 사용하지 않고 단량체와 중합 개시제 그리고 필요에 따른 첨가제 만을 투입하여 중합할 수 있어서 건조공정 등 중합 후의 공정이 필요하지 않아 생산원가가 저렴하고 대량생산이 용이한 점에서 널리 이용되고 있다. 그러나, 괴상중합으로 제조된 중합체의 경우 중합체 입자 표면이 매끄럽고 각진 형태를 가지고 있어 입자 표면이 거친 현탁중합이나 유화중합으로 제조된 중합체 대비 배합시 부원료와의 결합력이 떨어져 가공성이 좋지 못한 문제가 있다. In general, vinyl chloride-based polymers are manufactured through a method of bulk polymerization, suspension polymerization or emulsion polymerization, and, unlike suspension polymerization or emulsion polymerization, only a monomer, a polymerization initiator, and additives as necessary are added without using a medium. It is widely used in that it can be polymerized and does not require a post-polymerization process such as a drying process, so that production cost is low and mass production is easy. However, in the case of a polymer prepared by bulk polymerization, the polymer particle surface has a smooth and angular shape, and thus, when compared with a polymer prepared by suspension polymerization or emulsion polymerization, the bonding strength with the auxiliary raw material is poor, resulting in poor processability.
이에, 본 발명은 괴상중합을 통하여 염화비닐계 중합체를 제조하되, 중합 초기 중합 개시제의 투입 시점을 조절하여 입자 표면 형태를 조절한 염화비닐계 중합체의 제조방법을 제공한다. Thus, the present invention provides a method for producing a vinyl chloride-based polymer having a vinyl chloride-based polymer prepared through bulk polymerization, but controlling the particle surface morphology by adjusting the input time of the polymerization initiator.
본 발명의 일 실시예에 따른 상기 염화비닐계 중합체의 제조방법은 제1 염화비닐계 단량체에 전중합 개시제를 첨가하고 8.0 K/G 내지 8.7 K/G의 압력에서 전중합하여 입자핵을 형성시키는 단계(단계 1); 및 상기 입자핵의 존재 하에 제2 염화비닐계 단량체 및 후중합 개시제를 후중합하는 단계(단계 2)를 포함하고, 상기 전중합 개시제는 전중합 시 압력 대비 1.3 K/G 내지 3.5 K/G 낮은 압력에서 첨가하는 것을 특징으로 한다.The method for preparing the vinyl chloride-based polymer according to an embodiment of the present invention comprises adding a pre-polymerization initiator to the first vinyl chloride-based monomer and pre-polymerizing it at a pressure of 8.0 K / G to 8.7 K / G to form particle nuclei. (Step 1); And post-polymerizing the second vinyl chloride-based monomer and post-polymerization initiator in the presence of the particle nucleus (step 2), wherein the pre-polymerization initiator is 1.3 K / G to 3.5 K / G lower than the pressure during pre-polymerization. It is characterized by adding at pressure.
상기 단계 A는 입자핵을 형성시키기 위한 전중합 단계로, 제1 염화비닐계 단량체에 전중합 개시제를 첨가하고 전중합하여 수행할 수 있으며, 이때 상기 전중합은 8.0 K/G 내지 8.7 K/G의 압력에서 수행하는 것일 수 있고, 상기 전중합 개시제는 상기 전중합 시 압력 대비 1.3 K/G 내지 3.5 K/G 낮은 압력에서 첨가하는 것일 수 있으며, 구체적으로는 상기 전중합 개시제는 상기 전중합 시 압력 대비 1.5 K/G 내지 3.0 K/G 낮은 압력에서 첨가하는 것일 수 있다. The step A is a pre-polymerization step for forming a particle nucleus, and may be performed by adding a pre-polymerization initiator to the first vinyl chloride monomer and pre-polymerizing the pre-polymerization of 8.0 K / G to 8.7 K / G. It may be performed at a pressure, and the pre-polymerization initiator may be added at a pressure of 1.3 K / G to 3.5 K / G lower than the pressure during the pre-polymerization, specifically, the pre-polymerization initiator is the pressure during the pre-polymerization. Contrast may be to be added at a pressure of 1.5 K / G to 3.0 K / G lower.
괴상중합의 경우 반응 초기에 중합체 입자의 외벽을 생성하고, 그 안을 채우는 방식으로 중합이 진행되기 때문에 최종 중합체 입자의 표면 형태를 조절하기 위해서는 반응 초기에 반응속도 제어가 필요하며, 본 발명은 상기 전중합을 상기의 특정범위로 조절된 압력에서 수행하고 전중합 개시제를 전중합 시 압력 대비 1.3 K/G 내지 3.5 K/G 낮은 압력에 도달했을 때 제1 염화비닐계 단량체에 투입함으로써 중합체 입자 표면의 불균일도와 기공률을 전술한 바와 같은 적정수준으로 조절되도록 할 수 있다. In the case of bulk polymerization, since the outer wall of the polymer particles is generated at the beginning of the reaction and polymerization proceeds by filling the inside, the reaction rate control is required at the beginning of the reaction in order to control the surface shape of the final polymer particles. Polymerization is carried out at a pressure adjusted to the above-mentioned specific range, and when the pre-polymerization initiator reaches a pressure of 1.3 K / G to 3.5 K / G lower than the pressure during pre-polymerization, it is introduced into the first vinyl chloride-based monomer to thereby The non-uniformity and porosity can be adjusted to an appropriate level as described above.
구체적으로, 본 발명에 따른 상기 단계 A는 반응기에 제1 염화비닐계 단량체를 투입하고 반응기 내 압력을 8.0 K/G 내지 8.7 K/G 중 정해놓은 압력이 되도록 승압시켜 전중합을 수행하며, 상기 승압 중 전중합 수행 압력보다 1.3 K/G 내지 3.5 K/G 낮은 압력, 구체적으로는 1.5 K/G 내지 3.0 K/G 낮은 압력에 도달했을 때 전중합 개시제를 첨가하는 것일 수 있다. Specifically, in step A according to the present invention, the first vinyl chloride-based monomer is introduced into the reactor, and the pressure in the reactor is increased to a pressure determined from 8.0 K / G to 8.7 K / G to perform pre-polymerization. It may be that the pre-polymerization initiator is added when a pressure of 1.3 K / G to 3.5 K / G lower than the pre-polymerization performing pressure during the pressure rise, specifically, 1.5 K / G to 3.0 K / G, is reached.
또한, 상기 전중합 개시제는 제1 염화비닐계 단량체 100 중량부에 대하여 0.01 중량부 내지 1 중량부로 첨가하는 것일 수 있고, 구체적으로는 0.03 내지 0.1의 중량부로 첨가하는 것일 수 있다. 만약, 상기 전중합 개시제를 상기의 범위로 첨가하는 경우에는 전중합 반응을 원활하게 개시할 수 있으면서 반응시간을 적절하게 조절할 수 있다. 또한, 반응제열이 적정치로 유지될 수 있어 반응열에 의한 안정성 저하를 방지할 수 있으면서 잔류 개시제에 의한 열안정성 저하 등의 문제가 최소화될 수 있다.Further, the pre-polymerization initiator may be added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the first vinyl chloride-based monomer, and specifically, added in an amount of 0.03 to 0.1 parts by weight. If the prepolymerization initiator is added in the above range, the prepolymerization reaction can be smoothly initiated and the reaction time can be appropriately adjusted. In addition, since the reactant heat can be maintained at an appropriate value, stability deterioration due to the reaction heat can be prevented, and problems such as deterioration of thermal stability by the residual initiator can be minimized.
또한, 상기 전중합 개시제는 특별히 제한되는 것은 아니나, 예컨대 퍼옥시에스터 또는 퍼옥시디카보네이트의 화합물 등을 사용할 수 있으며, 구체적으로는 디-2-에틸헥실 퍼옥시시카보네이트, t-부틸퍼옥시네오데카노에이트, t-부틸퍼옥시 에스터, 큐밀퍼옥시 에스터, 큐밀퍼옥시 네오데카노에이트, 1,1,3,3-테트라메틸 부틸 퍼옥시 네오데카노에이트, t-헥실 퍼옥시 네오데카노에이트, t-헥실 퍼옥시 피발레이트, t-부틸 퍼옥시 피발레이트, 디-sec-부틸 퍼옥시 디카보네이트, 디-2-에톡시에틸 퍼옥시 디카보네이트, 이소부티릴 퍼옥사이드, 3,5,5-트리메틸헥사노일 퍼옥사이드, 라우릴 퍼옥사이드 및 옥틸퍼옥시 디카보네이트 중에서 선택된 1종 이상일 수 있다. In addition, the pre-polymerization initiator is not particularly limited, for example, a peroxy ester or a compound of peroxydicarbonate or the like can be used, and specifically, di-2-ethylhexyl peroxysicarbonate, t-butylperoxyneode Canoate, t-butylperoxy ester, cumylperoxy ester, cumylperoxy neodecanoate, 1,1,3,3-tetramethyl butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate , t-hexyl peroxy pivalate, t-butyl peroxy pivalate, di-sec-butyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, isobutyryl peroxide, 3,5,5 -Trimethylhexanoyl peroxide, lauryl peroxide, and octyl peroxy dicarbonate.
또한, 상기 제1 염화비닐계 단량체는 염화비닐 단량체 또는 염화비닐 단량체 및 상기 염화비닐 단량체와의 공중합성을 갖는 비닐계 단량체의 혼합인 것일 수 있으며, 상기 제1 염화비닐계 단량체가 염화비닐 단량체와 비닐계 단량체의 혼합인 경우에는 이를 통하여 제조된 염화비닐계 중합체 내 염화비닐이 50 중량% 이상으로 포함되도록 적절히 조절하여 사용하는 것일 수 있다. Further, the first vinyl chloride monomer may be a vinyl chloride monomer or a mixture of a vinyl chloride monomer and a vinyl monomer having copolymerization with the vinyl chloride monomer, wherein the first vinyl chloride monomer is a vinyl chloride monomer and In the case of a mixture of vinyl-based monomers, it may be used by appropriately adjusting so that vinyl chloride in the vinyl chloride-based polymer prepared therefrom is contained in 50% by weight or more.
상기 비닐계 단량체는 특별히 제한하는 것은 아니나, 예컨대 에틸렌, 프로필렌, 부틴 등의 올레핀(olefin) 화합물; 초산비닐, 프로피온산 비닐, 스테아린산 비닐 등의 비닐 에스테르(vinyl ester)류; 아크릴로니트릴 등의 불포화 니트릴류; 비닐메틸 에테르, 비닐에틸 에테르, 비닐옥틸 에테르, 비닐라우릴 에테르 등의 비닐알킬 에테르류; 염화비닐리덴 등의 할로겐화 비닐리덴(vinylidene)류; 아크릴산, 메타크릴산, 이타콘산, 말레인산, 푸마르산, 무수말레산, 무수이타콘산 등의 불포화 지방산 및 이들 지방산의 무수물; 아크릴산 메틸, 아크릴산 에틸, 말레인산 모노 메틸, 말레인산 디메틸, 말레인산 부틸벤질 등의 불포화 지방산 에스테르(ester)류; 디알릴프탈레이트 등의 가교성 단량체 등일 수 있으며, 상기 비닐계 단량체는 단독 또는 2종 이상을 혼합하여 사용할 수 있다.The vinyl-based monomer is not particularly limited, for example, olefin compounds such as ethylene, propylene, and butene; Vinyl esters such as vinyl acetate, vinyl propionate, and vinyl stearate; Unsaturated nitriles such as acrylonitrile; Vinyl alkyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether, and vinyl lauryl ether; Vinylidene halides such as vinylidene chloride; Unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, and itaconic anhydride and anhydrides of these fatty acids; Unsaturated fatty acid esters such as methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate; Cross-linkable monomers such as diallyl phthalate, and the vinyl monomers may be used alone or in combination of two or more.
한편, 상기 단계 A의 전중합은 중합 전환율 10% 내지 15%까지 수행하는 것일 수 있다. 상기 단계 A의 전중합의 중합 전환율이 특별히 제한되지는 않으나, 상기 전중합은 입자핵을 제조하기 위한 단계로 전중합이 과도하게 진행되어 입자핵이 과하게 형성되는 경우 최종적으로 제조되는 중합체의 물성을 목적과 다르게 변성시킬 수 있으며, 따라서 전중합의 중합 정도가 조절되어야 할 필요성이 있다. 만약, 상기 전중합을 상기의 중합 전환율까지 수행하는 경우에는 입자핵을 과도하게 형성시키지 않으면서 목적하는 불균일도을 갖는 염화비닐계 중합체를 제조할 수 있으면서 중합도 및 다른 물성에는 영향을 미치지 않을 수 있다. On the other hand, the pre-polymerization of step A may be carried out to 10% to 15% of the polymerization conversion rate. The polymerization conversion rate of the pre-polymerization of the step A is not particularly limited, but the pre-polymerization is a step for preparing the particle nuclei, and if the pre-polymerization is excessively carried out and the particle nuclei are excessively formed, the physical properties of the polymer finally produced are It can be denatured differently than the purpose, so there is a need to control the degree of polymerization of the prepolymerization. If the prepolymerization is performed up to the above polymerization conversion rate, a vinyl chloride-based polymer having a desired degree of heterogeneity can be produced without excessively forming particle nuclei, but the polymerization degree and other physical properties may not be affected.
이때, 상기 중합 전환율은 제1 염화비닐계 단량체의 중합체로의 전환율을 나타내는 것으로, 가스 크로마토그래피를 장착한 부탄 트레이서(butane tracer)를 이용하여 측정한 것일 수 있다. 구체적으로, 일정 중합 조건에서 시간에 따른 염화비닐계 단량체의 부탄과의 비율에 따른 중합 전환율 곡선을 중합 조건 때마다 작성해 두고, 이를 근거로 하여 중합 조건에 따른 중합 전환율을 측정한 것일 수 있다. 또한, 상기 중합 전환율은 측정에 따른 오차범위까지 포함하는 것일 수 있다. At this time, the polymerization conversion rate indicates the conversion rate of the first vinyl chloride monomer to the polymer, and may be measured using a butane tracer equipped with gas chromatography. Specifically, under certain polymerization conditions, a polymerization conversion rate curve according to a ratio of a vinyl chloride-based monomer over time with butane may be prepared for each polymerization condition, and based on this, a polymerization conversion rate according to polymerization conditions may be measured. Further, the polymerization conversion rate may include up to an error range according to measurement.
또한, 상기 전중합은 30℃ 내지 70℃의 온도 범위 조건에서 수행하는 것일 수 있다.In addition, the pre-polymerization may be performed in a temperature range condition of 30 ℃ to 70 ℃.
상기 단계 B는 상기 전중합에 의해서 제조된 입자핵의 내부를 성장시켜 염화비닐계 중합체를 제조하기 위한 단계로, 전중합 단계에서 제조된 입자핵의 존재 하에 제2 염화비닐계 단량체 및 후중합 개시제를 후중합하여 수행할 수 있다. The step B is a step for producing a vinyl chloride-based polymer by growing the interior of the particle nucleus prepared by the pre-polymerization, a second vinyl chloride-based monomer and a post polymerization initiator in the presence of the particle nuclei prepared in the pre-polymerization step Can be post-polymerized.
여기에서, 상기 후중합은 6 K/G 내지 13 K/G의 압력에서 수행하는 것일 수 있다. Here, the post-polymerization may be performed at a pressure of 6 K / G to 13 K / G.
상기 제2 염화비닐계 단량체는 제1 염화비닐계 단량체와 동일한 것일 수 있다. The second vinyl chloride-based monomer may be the same as the first vinyl chloride-based monomer.
상기 후중합 개시제는 제2 염화비닐게 단량체 100 중량부에 대하여 0.05 중량부 내지 2 중량부로 사용하는 것일 수 있고, 구체적으로는 0.1 중량부 내지 0.5 중량보로 사용하는 것일 수 있다. The post-polymerization initiator may be used in 0.05 parts by weight to 2 parts by weight based on 100 parts by weight of the second vinyl chloride monomer, specifically, 0.1 parts by weight to 0.5 parts by weight.
또한, 상기 후중합 개시제는 특별히 제한하는 것은 아니나 예컨대 디-2-에틸헥실 퍼옥시시카보네이트, t-부틸퍼옥시네오데카노에이트, t-부틸퍼옥시 에스터, 큐밀퍼옥시 에스터, 큐밀퍼옥시 네오데카노에이트, 1,1,3,3-테트라메틸 부틸 퍼옥시 네오데카노에이트, t-헥실 퍼옥시 네오데카노에이트, t-헥실 퍼옥시 피발레이트, t-부틸 퍼옥시 피발레이트, 디-sec-부틸 퍼옥시 디카보네이트, 디-2-에톡시에틸 퍼옥시 디카보네이트, 이소부티릴 퍼옥사이드, 3,5,5-트리메틸헥사노일 퍼옥사이드, 라우릴 퍼옥사이드 및 옥틸 퍼옥시 디카보네이트 중에서 선택된 1종 이상인 것 일 수 있다. 한편, 상기 후중합 개시제는 상기 전중합 개시제와 동일하거나 상이한 물질일 수 있다. In addition, the post-polymerization initiator is not particularly limited, such as di-2-ethylhexyl peroxycarbonate, t-butyl peroxy neodecanoate, t-butyl peroxy ester, cumyl peroxy ester, cumyl peroxy neo Decanoate, 1,1,3,3-tetramethyl butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, di- sec-butyl peroxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauryl peroxide and octyl peroxy dicarbonate It may be one or more. Meanwhile, the post-polymerization initiator may be the same or different material from the pre-polymerization initiator.
또한, 상기 후중합은 30℃ 내지 70℃의 온도범위에서 수행하는 것일 수 있다. In addition, the post-polymerization may be performed in a temperature range of 30 ℃ to 70 ℃.
한편, 본 발명의 일 실시예에 따른 상기 제조방법은 후중합 말기에 중합억제제를 투입하여 잔류하는 상기 후중합 개시제의 반응성을 제거할 수 있으며, 이때 상기 중합억제제는 특별히 제한하는 것은 아니나, 예컨대 하이드로퀴논, 부틸레이티드 하이드록시 톨루엔, 모노메틸 에테르 하이드로퀴논, 4차 부틸 카테콜, 디페닐아민, 트리이소프로파놀 아민, 트리에탄올 아민 등을 사용할 수 있다. 또한, 상기 중합억제제의 사용량은 잔류하는 후중합 개시제의 양에 따라 적절히 조절하여 사용할 수 있으나, 통상 전중합 및 후중합에 사용된 전체 염화비닐계 단량체 총 100 중량부에 대하여 0.001 중량부 내지 0,1 중량부로 사용할 수 있다. On the other hand, the manufacturing method according to an embodiment of the present invention can remove the reactivity of the remaining post polymerization initiator by adding a polymerization inhibitor at the end of post polymerization, wherein the polymerization inhibitor is not particularly limited, for example, hydro Quinone, butylated hydroxy toluene, monomethyl ether hydroquinone, quaternary butyl catechol, diphenylamine, triisopropanol amine, triethanol amine, and the like can be used. In addition, the amount of the polymerization inhibitor may be appropriately adjusted depending on the amount of the post-polymerization initiator remaining, but is usually 0.001 part by weight to 0, based on 100 parts by weight of the total amount of vinyl chloride-based monomers used for pre-polymerization and post-polymerization. Can be used as 1 part by weight.
또한, 상기 제조방법은 필요에 따라 반응매질을 사용할 수 있으며, 분자량 조절제와 같은 첨가제를 더 사용할 수 있다. In addition, the manufacturing method may use a reaction medium as necessary, and further additives such as molecular weight modifiers may be used.
상기 반응매질은 특별이 제한하지 않고 통상의 유기용매가 사용될 수 있으며, 예컨대 벤젠, 톨루엔, 자일렌 등의 방향족 화합물과 메틸에틸케톤, 아세톤, n-헥산, 클로로포름, 시클로헥산 등이 사용될 수 있다. The reaction medium is not particularly limited, and a conventional organic solvent can be used. For example, aromatic compounds such as benzene, toluene, and xylene and methyl ethyl ketone, acetone, n-hexane, chloroform, cyclohexane, and the like can be used.
상기 분자량 조절제는 특별히 제한하는 것은 아니나, 예컨대 n-부틸머캅탄, n-옥틸머캅탄, n-도데실머캅탄, t-도데실머캅탄 등이 사용될 수 있다. The molecular weight modifier is not particularly limited, for example, n-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and the like can be used.
이하, 실시예 및 실험예에 의하여 본 발명을 더욱 상세하게 설명한다. 그러나, 하기 실시예 및 실험예는 본 발명을 예시하기 위한 것으로 이들 만으로 본 발명의 범위가 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail by examples and experimental examples. However, the following examples and experimental examples are intended to illustrate the present invention, but the scope of the present invention is not limited thereto.
실시예 1Example 1
고진공으로 탈기한 부피 0.2 m3의 전중합 반응기에 염화비닐 단량체 135 kg을 투입하고, 교반하면서 8 K/G까지 승압하여 중합 전환율 10%까지 중합하여 입자핵을 제조하였다. 이때, 승압 중 반응기 내부 압력이 6.5 K/G에 도달했을 때 디-2-에틸 헥실 퍼옥시디카보네이트(OPP) 40 g을 투입하여 반응에 참여시켰다. Into a pre-polymerization reactor having a volume of 0.2 m 3 degassed with high vacuum, 135 kg of vinyl chloride monomer was added, and the mixture was raised to 8 K / G while stirring to polymerize to a polymerization conversion rate of 10% to prepare particle nuclei. At this time, when the pressure inside the reactor reached 6.5 K / G during the boost, 40 g of di-2-ethyl hexyl peroxydicarbonate (OPP) was added to participate in the reaction.
이후, 0.5 m3의 후중합 반응기에 염화비닐 단량체 75 kg을 투입하고 상기 제조된 입자핵을 이송시킨 후 반응기 내부 압력이 4 K/G일 때 1,1,3,3-테트라메틸 부틸 퍼옥시 네오디카보네이트(OND) 95 g을 투입하고 교반하면서 승압하여 8 K/G의 압력에서 180분 동안 중합하였다. 중합이 완료된 후 교반하면서 30분간 진공으로 잔류하는 미반응 염화비닐 단량체를 회수하고 염화비닐 중합체를 제조하였다.Subsequently, 75 kg of a vinyl chloride monomer was added to a 0.5 m 3 post-polymerization reactor, and the prepared particle nuclei were transferred, and then 1,1,3,3-tetramethyl butyl peroxy when the reactor internal pressure was 4 K / G. 95 g of neodicarbonate (OND) was added, and the mixture was stirred and stirred, and polymerized at a pressure of 8 K / G for 180 minutes. After the polymerization was completed, unreacted vinyl chloride monomer remaining in vacuum for 30 minutes while stirring was collected to prepare a vinyl chloride polymer.
실시예 2Example 2
실시예 1에 있어서, 디-2-에틸 헥실 퍼옥시디카보네이트를 5 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, a vinyl chloride polymer was prepared in the same manner as in Example 1, except that di-2-ethyl hexyl peroxydicarbonate was added at a time when 5 K / G was reached.
실시예 3Example 3
실시예 1에 있어서, 전중합을 8.7 K/G에서 실시하고, 디-2-에틸 헥실 퍼옥시디카보네이트를 6.7 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, the prepolymerization was carried out at 8.7 K / G, and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 6.7 K / G, and the same method as in Example 1 was used. A vinyl chloride polymer was prepared.
실시예 4Example 4
실시예 1에 있어서, 후중합 시 1,1,3,3-테트라메틸 부틸 퍼옥시 네오디카보네이트(OND) 95 g을 염화비닐 단량체와 함께 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, the same method as in Example 1 except that 95 g of 1,1,3,3-tetramethyl butyl peroxy neodicarbonate (OND) was added together with the vinyl chloride monomer during post-polymerization. Through this, a vinyl chloride polymer was prepared.
비교예 1Comparative Example 1
실시예 1에 있어서, 전중합을 12 K/G에서 실시한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, a vinyl chloride polymer was prepared in the same manner as in Example 1, except that pre-polymerization was performed at 12 K / G.
비교예 2Comparative Example 2
실시예 1에 있어서, 디-2-에틸 헥실 퍼옥시디카보네이트를 7 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였으나, 정상적인 입자핵이 생성되지 않아 중합체가 제조되지 못하였다. 이는, 디-2-에틸헥실 퍼옥시디카보네이트가 투입이 늦어 분산이 충분하지 못한것을 의미하는 결과이다. In Example 1, a vinyl chloride polymer was prepared in the same manner as in Example 1, except that di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 7 K / G, but normal particle nuclei were obtained. The polymer was not produced because it was not produced. This is a result which means that di-2-ethylhexyl peroxydicarbonate is late and the dispersion is insufficient.
비교예 3Comparative Example 3
실시예 1에 있어서, 디-2-에틸 헥실 퍼옥시디카보네이트를 4 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, a vinyl chloride polymer was prepared in the same manner as in Example 1, except that di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 4 K / G.
비교예 4Comparative Example 4
실시예 1에 있어서, 전중합을 10 K/G에서 실시하고, 디-2-에틸 헥실 퍼옥시디카보네이트를 8.5 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, except that the prepolymerization was carried out at 10 K / G and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 8.5 K / G, the same method as in Example 1 was used. A vinyl chloride polymer was prepared.
비교예 5Comparative Example 5
실시예 1에 있어서, 전중합을 7 K/G에서 실시하고, 디-2-에틸 헥실 퍼옥시디카보네이트를 5.5 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였으나, 정상적인 입자핵이 생성되지 않아 중합체가 제조되지 못하였다. 이는, 전중합 시 압력이 너무 낮아 중합이 정상적으로 이뤄지지 못한 것을 의미하는 결과이다. In Example 1, except that the prepolymerization was carried out at 7 K / G and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 5.5 K / G, the same method as in Example 1 was carried out. A vinyl chloride polymer was prepared, but the polymer was not produced because normal particle nuclei were not produced. This is a result which means that the polymerization was not normally performed because the pressure was too low during pre-polymerization.
비교예 6Comparative Example 6
실시예 1에 있어서, 전중합을 10 K/G에서 실시하고, 디-2-에틸 헥실 퍼옥시디카보네이트를 6.5 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, the prepolymerization was carried out at 10 K / G, and di-2-ethyl hexyl peroxydicarbonate was added at the time of reaching 6.5 K / G. A vinyl chloride polymer was prepared.
비교예 7Comparative Example 7
실시예 1에 있어서, 전중합을 9.5 K/G에서 실시하고, 디-2-에틸 헥실 퍼옥시디카보네이트를 8 K/G 도달한 시점에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다. In Example 1, the prepolymerization was carried out at 9.5 K / G, and di-2-ethyl hexyl peroxydicarbonate was added at the time when 8 K / G was reached, and the same method as in Example 1 was used. A vinyl chloride polymer was prepared.
비교예 8Comparative Example 8
실시예 1에 있어서, 전중합을 9.5 K/G에서 수행한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Example 1, a vinyl chloride polymer was prepared in the same manner as in Example 1, except that pre-polymerization was performed at 9.5 K / G.
비교예 9Comparative Example 9
비교예 1에 있어서, 후중합 시 1,1,3,3-테트라메틸 부틸 퍼옥시 네오디카보네이트를 5.5 K/G 도달한 시점에 투입한 것을 제외하고는 상기 비교예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Comparative Example 1, after post-polymerization, 1,1,3,3-tetramethyl butyl peroxy neodicarbonate was added through the same method as Comparative Example 1, except that it was added at the time of reaching 5.5 K / G. Vinyl polymer was prepared.
비교예 10Comparative Example 10
비교예 1에 있어서, 후중합을 7 K/G에서 실시한 것을 제외하고는 상기 비교예 1과 동일한 방법을 통하여 염화비닐 중합체를 제조하였다.In Comparative Example 1, a vinyl chloride polymer was prepared through the same method as Comparative Example 1, except that post polymerization was performed at 7 K / G.
실험예 1Experimental Example 1
상기 실시예 1 내지 실시예 4 및 비교예 1 내지 비교예 10에서 제조한 각 염화비닐 중합체 입자 표면의 불균일도, 중합도 및 기공률(%)을 측정하였다. 결과를 하기 표 1에 나타내었다. The non-uniformity, polymerization degree and porosity (%) of each vinyl chloride polymer particle surface prepared in Examples 1 to 4 and Comparative Examples 1 to 10 were measured. The results are shown in Table 1 below.
(1) 입자 불균일도(1) Particle non-uniformity
상기 입자 불균일도는 각 중합체 표면에 대하여 광학 현미경을 이용하여 관찰되는 입자 중 총 50개의 입자에 대해서 각 입자 당 가장 긴 지름을 측정하고, 이의 중심을 지나는 50개의 지름을 측정하여 하기 수학식 1 내지 수학식 3을 통하여 계산하였다. 즉, 각 50개의 입자에 대해 가장 긴 지름과 이의 중심을 지나는 50개의 지름를 이용하여 각 입자의 지름 표준편차를 수학식 2 및 3을 통하여 계산하고, 계산된 50개의 지름 표준편차에 대한 평균을 입자 불균일도로 나타내었다. The particle non-uniformity is measured by measuring the longest diameter of each particle for a total of 50 particles observed using an optical microscope for each polymer surface, and measuring the 50 diameters passing through the center thereof. It was calculated through Equation 3. That is, the standard deviation of the diameter of each particle is calculated through Equations 2 and 3 using the longest diameter for each 50 particles and 50 diameters passing through the center thereof, and the average for the calculated 50 diameter standard deviation is calculated. It is represented by non-uniformity.
[수학식 1] [Equation 1]
Figure PCTKR2019009907-appb-I000007
Figure PCTKR2019009907-appb-I000007
상기 수학식 1에서, Xi는 i번째 입자의 표준편차로, 하기 수학식 2로 정의되는 값이고, In Equation 1, Xi is a standard deviation of the i-th particle, and is a value defined by Equation 2 below,
[수학식 2][Equation 2]
Figure PCTKR2019009907-appb-I000008
Figure PCTKR2019009907-appb-I000008
상기 수학식 2에서, An은 i번째 입자의 n번째 측정 지름의 보정값이고, 여기에서 보정값은 하기 수학식 3으로 정의되는 값이며,In Equation 2, An is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
[수학식 3][Equation 3]
Figure PCTKR2019009907-appb-I000009
Figure PCTKR2019009907-appb-I000009
상기 수학식 3에서, Dn은 i번째 입자의 n번째 측정 지름이고, D0은 i번째 입자에서 가장 긴 지름이며, n은 1 내지 50의 정수이다.In Equation 3, D n is the n-th measurement diameter of the i-th particle, D 0 is the longest diameter in the i-th particle, and n is an integer from 1 to 50.
(2) 중합도(2) degree of polymerization
중합도는 ASTM D1 243-49에 의거하여 측정하였다. The polymerization degree was measured according to ASTM D1 243-49.
(3) 기공률(%)(3) Porosity (%)
기공률은 수은 기공률 분석기(AutoPore IV 9520, Micromeritics 社)를 이용하여 각 염화비닐 중합체 입자 내로 침투한 수은의 양으로부터 계산하였다.The porosity was calculated from the amount of mercury that penetrated into each vinyl chloride polymer particle using a mercury porosity analyzer (AutoPore IV 9520, Micromeritics).
Figure PCTKR2019009907-appb-T000001
Figure PCTKR2019009907-appb-T000001
상기 표 1에 나타난 바와 같이, 본 발명의 일 실시예에 따른 실시예 1 내지 실시예 4의 염화비닐 중합체는 모두 동등수준의 중합도를 나타내면서 입자 불균일도가 10 이상으로 거친 표면을 가지고 기공률이 증가된 것을 확인하였다. 반면, 비교예 1, 비교예 3, 비교예 4 및 비교예 6 내지 비교예 10은 입자 불균일도가 10 미만으로 매끈한 표면을 가졌으며 기공률도 실시예 1 내지 4 대비 크게 감소하였다. 또한, 비교예 2 및 비교예 5의 경우에는 중합체가 생성되지 못하였다. As shown in Table 1, all of the vinyl chloride polymers of Examples 1 to 4 according to an embodiment of the present invention exhibit a degree of polymerization of the same level, while having a rough surface with a particle non-uniformity of 10 or more and increased porosity. Was confirmed. On the other hand, Comparative Example 1, Comparative Example 3, Comparative Example 4 and Comparative Example 6 to Comparative Example 10 had a smooth surface with a particle non-uniformity of less than 10, and porosity was also significantly reduced compared to Examples 1 to 4. In addition, in Comparative Examples 2 and 5, no polymer was produced.
구체적으로, 전중합 시 8.7 K/G 보다 높은 압력에서 중합을 실시한 비교예 1, 비교예 4, 비교예 6 내지 비교예 10의 경우 실시예 1 내지 4 대비 불균일도가 현저히 낮았으며, 특히 비교예 4, 비교예 7 및 비교예 8의 경우에는 전중합 개시제가 중합시 압력 대비 1.5 K/G 또는 3.0 K/G 낮은 시점에 투입했음에도 불구하고 입자 표면이 매끄러운 중합체가 생성되었다. 이는, 전중합 시 압력이 너무 높을 경우 초반 입자 외형이 빠르고 매끄럽게 형성되어 입자 표면의 불균일도를 일정 범위 이상으로 조절할 수 없음을 나타내는 결과이다. Specifically, in the case of Comparative Example 1, Comparative Example 4, and Comparative Examples 6 to 10 in which polymerization was carried out at a pressure higher than 8.7 K / G during pre-polymerization, the degree of non-uniformity was significantly lower than Examples 1 to 4, especially Comparative Example 4, in the case of Comparative Examples 7 and 8, a polymer having a smooth particle surface was produced even though the pre-polymerization initiator was added at a point of 1.5 K / G or 3.0 K / G lower than the pressure during polymerization. This is a result indicating that the initial particle appearance is quickly and smoothly formed when the pressure is too high during pre-polymerization, so that the degree of non-uniformity of the particle surface cannot be controlled beyond a certain range.
또한, 전중합 개시제를 전중합시 압력 대비 -4 K/G인 시점에 투입한 비교예 3의 경우에도 실시예 1 내지 4 대비 입자의 표면 불균일도가 낮았으며, 이는, 전중합 개시제의 투입이 너무 빠를 경우 전중합 개시제의 분산 및 활성 시간이 길어져 초반 입자 외형의 빠르고 매끄럽게 형성될 수 있고, 결과적으로 입자 표면의 불균일도가 일정 범위 이상으로 조절될 수 없음을 나타내는 결과이다. In addition, in the case of Comparative Example 3 in which the prepolymerization initiator was added at a point of -4 K / G compared to the pressure during prepolymerization, the surface nonuniformity of the particles was lower than in Examples 1 to 4, which means that the prepolymerization initiator was introduced. If it is too fast, the dispersion and activation time of the pre-polymerization initiator is prolonged, and thus it can be formed quickly and smoothly of the appearance of the early particles, and as a result, the non-uniformity of the particle surface cannot be controlled beyond a certain range.
또한, 비교예 1, 3 내지 4, 7 및 8은 실시예 1 내지 4 대비 입자의 기공율도 약 4% 내지 8% 크게 감소되었으며, 이를 통하여 전중합 시 압력 및 전중합 개시제의 투입시점이 조절된 본 발명의 제조방법의 경우 입자 내 기공을 발달시킬 수 있고, 이에 기공특성이 우수한 염화비닐계 중합체를 제조할 수 있음을 확인하였다. In addition, in Comparative Examples 1, 3 to 4, 7 and 8, the porosity of the particles was also significantly reduced by about 4% to 8% compared to Examples 1 to 4, thereby controlling the pressure during the pre-polymerization and the input point of the pre-polymerization initiator. In the case of the manufacturing method of the present invention, it was confirmed that the pores in the particles can be developed, and thus a vinyl chloride-based polymer having excellent pore characteristics can be produced.
한편, 비교예 9 및 비교예 10은 후중합 시 조건에 따른 입자 불균일도 변화를 확인하기 위하여 전중합은 비교예 1과 동일하게 진행하고 후중합 시 후중합 개시제 투입시점 및 후중합 압력을 변화시킨 것으로, 비교예 9의 경우 후중합 개시제를 후중합 시보다 -2.5 K/G인 시점에 투입하였으나 입자 불균일도는 조절되지 않았으며, 비교예 10의 경우에는 입자 불균일도는 조절하지 못하고 중합도가 크게 상승하였다. 이를 통하여 최종 생성되는 중합체 입자의 표면 불균일도는 전중합 시에 전중합 압력 조절 및 전중합 개시제의 투입시점을 조절함으로써 조절할 수 있는 것임을 확인하였으며, 후중합시 압력 조절 및 후중합 개시제 투입시점 조절을 통해서는 오히려 목적하는 중합체 제조의 방해요인으로 작용할 수 있음을 확인하였다. On the other hand, in Comparative Examples 9 and 10, in order to confirm the change in particle non-uniformity according to the conditions during post-polymerization, pre-polymerization proceeds in the same manner as in Comparative Example 1, and the post-polymerization initiator input time and post-polymerization pressure are changed during post-polymerization. In the case of Comparative Example 9, the post-polymerization initiator was added at a time of -2.5 K / G than that of post-polymerization, but the particle non-uniformity was not controlled, and in Comparative Example 10, the particle non-uniformity was not controlled and the polymerization degree was large. Rose. Through this, it was confirmed that the surface non-uniformity of the finally produced polymer particles can be controlled by adjusting the pre-polymerization pressure during pre-polymerization and adjusting the input time of the pre-polymerization initiator, and adjusting the pressure during post-polymerization and the control of the post-polymerization initiator input time. Through the above, it was confirmed that it may act as an obstacle to the production of the desired polymer.
실험예 2Experimental Example 2
상기 실시예 및 비교예의 염화비닐계 중합체의 배합성, 가소제 흡수율, 돌기특성 및 겔화 속도를 측정하였다. 결과를 하기 표 2에 나타내었다. The blendability, plasticizer absorption rate, projection properties and gelation rate of the vinyl chloride polymers of Examples and Comparative Examples were measured. The results are shown in Table 2 below.
한편, 비교예 2 및 비교예 5는 중합체가 제조되지 못하였으며, 이에 상기 물성을 측정하지 못하였다. On the other hand, in Comparative Example 2 and Comparative Example 5, a polymer was not prepared, and thus the physical properties were not measured.
(1) 배합성 (1) Blendability
실시예 및 비교예의 각 염화비닐 중합체 100 g, Ca-Zn 열안정제 6 g, 아크릴계 충격보강제 7 g, 지당(이산화티타늄) 4 g, 탄산칼슘 30 g을 Brabender Planetary Mixer에 투입한 후 120℃에서 12분간 배합하여 각 분말을 얻고, 이를 35 mesh 채를 통과시켜 미통과된 잔량을 측정하고, 총 분말 100 중량%에 대한 잔량의 비율(중량%)을 배합물성 값으로 나타내었다. 이때, 잔량의 비율이 낮을수록 배합물성이 우수함을 나타낸다. Each vinyl chloride polymer of Examples and Comparative Examples 100 g, Ca-Zn heat stabilizer 6 g, acrylic impact modifier 7 g, sugar (titanium dioxide) 4 g, calcium carbonate 30 g was added to the Brabender Planetary Mixer and then at 120 ° C. 12 Each powder was obtained by blending for a minute, and the unreceived residual amount was measured by passing through a 35 mesh wire, and the ratio (% by weight) of the residual amount to 100% by weight of the total powder was expressed as a blending property value. At this time, the lower the proportion of the remaining amount, the better the compoundability.
(2) 겔화 속도(2) Gelation rate
실시예 및 비교예의 각 염화비닐 중합체 100 중량부, Ca-Zn 열안정제 3 중량부, 에폭시화 대두유 2 중량부를 혼합한 혼합 분말 50 g을 Brabender Planetary Mixer에 투입한 후 165℃에서 30 rpm으로 용융시키면서 나타나는 기계적 부하를 기록하여 겔화 속도로 나타내었다. 이때, 겔화 속도가 적은 값일수록 가공성이 우수함을 나타낸다. 50 g of mixed powder of 100 parts by weight of each vinyl chloride polymer of Examples and Comparative Examples, 3 parts by weight of Ca-Zn heat stabilizer, and 2 parts by weight of epoxidized soybean oil was added to a Brabender Planetary Mixer and melted at 30 rpm at 165 ° C. The resulting mechanical load was recorded and expressed as the gelation rate. At this time, the smaller the gelation rate, the better the workability.
(3) 가소제 흡수율(CPA, 중량%)(3) Plasticizer absorption rate (CPA, weight%)
ASTM D3367-98에 의거하여, 실시예 및 비교예의 각 염화비닐 중합체를 DOP(디옥틸 프탈레이트)와 혼합시키고, 하기 수학식 4로 계산하여 가소제 흡수율을 측정하였다. According to ASTM D3367-98, each vinyl chloride polymer of Examples and Comparative Examples was mixed with DOP (dioctyl phthalate), and calculated by the following Equation 4 to measure plasticizer absorption.
[수학식 4][Equation 4]
가소제 흡수율(중량%)=[(B-A)/A]X100Plasticizer absorption rate (% by weight) = [(B-A) / A] X100
상기 수학식 4에서 A는 염화비닐 중합체의 무게이고, B는 가소제와 혼합 후, 가소제가 흡수된 염화비닐 중합체의 무게이다. In Equation 4, A is the weight of the vinyl chloride polymer, and B is the weight of the vinyl chloride polymer absorbed by the plasticizer after mixing with the plasticizer.
(4) 돌기특성(4) Protrusion characteristics
실시예 및 비교예의 각 염화비닐 중합체 100 중량부, DOP 45 중량부, 스테아린산 바륨 0.1 중량부, 주석계 안정제 0.2 중량부, 카본블랙 0.1 중량부를 145℃의 6인치 롤을 이용하여 4분간 혼합 및 혼련한 후 두께 0.3 mm의 시트를 만들고, 육안으로 관찰하여 시트의 400 cm2 중의 백색 투명입자를 세고, 이를 돌기특성으로 나타내었다. 백색 투명입자 수가 작을수록 돌기특성이 우수함을 나타내고, 결과적으로 표면특성이 우수함을 나타낸다.100 parts by weight of each vinyl chloride polymer of Examples and Comparative Examples, 45 parts by weight of DOP, 0.1 parts by weight of barium stearate, 0.2 parts by weight of tin-based stabilizer, and 0.1 parts by weight of carbon black were mixed and kneaded for 4 minutes using a 6-inch roll at 145 ° C. After that, a sheet having a thickness of 0.3 mm was made, and observed with the naked eye to count white transparent particles in 400 cm 2 of the sheet, and this was indicated as a projection characteristic. The smaller the number of white transparent particles, the better the protruding characteristics, and the better the surface characteristics.
Figure PCTKR2019009907-appb-T000002
Figure PCTKR2019009907-appb-T000002
상기 표 2를 통해 확인할 수 있듯이, 본 발명의 일 실시예에 따른 실시예 1 내지 4의 염화비닐 중합체는 배합성이 비교예의 염화비닐 중합체 대비 2배 이상 우수하면서도 겔화 속도가 절반이상 감소하였으며, 가소제 흡수율이 크게 증가하고 돌기발생이 크게 감소하였다. 이를 통하여, 본 발명에 따른 전중합 단계의 압력조건 및 전중합 개시제의 투입시점이 조절된 제조방법으로 제조된 염화비닐계 중합체의 경우 입자 불균일도 및 기공률이 조절됨으로써 겔화속도가 감소하고 가소제 흡수율이 증가될 수 있으며, 이에 배합물성이 우수하여 크게 개선된 가공성을 나타낼 수 있음을 확인하였다.As can be seen through Table 2, the vinyl chloride polymers of Examples 1 to 4 according to an embodiment of the present invention have excellent blendability more than twice as compared to the vinyl chloride polymer of the comparative example, while the gelation rate is reduced by more than half, and the plasticizer Absorption rate was significantly increased and protrusions were significantly reduced. Through this, in the case of a vinyl chloride-based polymer prepared by a manufacturing method in which the pressure conditions of the pre-polymerization step and the input point of the pre-polymerization initiator are controlled, the gelation rate is reduced and the plasticizer absorption rate is controlled by controlling the particle non-uniformity and porosity. It can be increased, and thus it was confirmed that the compoundability is excellent, and thus it is possible to show greatly improved processability.

Claims (11)

  1. 하기 수학식 1로 정의되는 입자 불균일도가 10 이상인 염화비닐계 중합체:Vinyl chloride-based polymer having a particle non-uniformity of 10 or more defined by the following Equation 1:
    [수학식 1][Equation 1]
    Figure PCTKR2019009907-appb-I000010
    Figure PCTKR2019009907-appb-I000010
    상기 수학식 1에서, Xi는 i번째 입자의 표준편차로, 하기 수학식 2로 정의되는 값이고, In Equation 1, X i is the standard deviation of the i-th particle, and is a value defined by Equation 2 below,
    [수학식 2][Equation 2]
    Figure PCTKR2019009907-appb-I000011
    Figure PCTKR2019009907-appb-I000011
    상기 수학식 2에서, An은 i번째 입자의 n번째 측정 지름의 보정값이고, 여기에서 보정값은 하기 수학식 3으로 정의되는 값이며,In Equation 2, A n is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
    [수학식 3][Equation 3]
    Figure PCTKR2019009907-appb-I000012
    Figure PCTKR2019009907-appb-I000012
    상기 수학식 3에서, Dn은 i번째 입자의 n번째 측정 지름이고, D0은 i번째 입자에서 가장 긴 지름이며, n은 1 내지 50의 정수이다.In Equation 3, D n is the n-th measurement diameter of the i-th particle, D 0 is the longest diameter in the i-th particle, and n is an integer from 1 to 50.
  2. 청구항 1에 있어서, The method according to claim 1,
    상기 염화비닐계 중합체는 입자 불균일도가 11 이상 16 이하인 것인 염화비닐계 중합체. The vinyl chloride-based polymer is a vinyl chloride-based polymer having a particle non-uniformity of 11 or more and 16 or less.
  3. 청구항 1에 있어서, The method according to claim 1,
    상기 염화비닐계 중합체는 괴상중합체인 것인 염화비닐계 중합체.The vinyl chloride-based polymer is a vinyl chloride-based polymer.
  4. 청구항 1에 있어서, The method according to claim 1,
    상기 염화비닐계 중합체는 기공률이 59% 이상인 것인 염화비닐계 중합체.The vinyl chloride-based polymer is a vinyl chloride-based polymer having a porosity of 59% or more.
  5. 제1 염화비닐계 단량체에 전중합 개시제를 첨가하고 8.0 K/G 내지 8.7 K/G의 압력에서 전중합하여 입자핵을 형성시키는 단계; 및Adding a prepolymerization initiator to the first vinyl chloride monomer and prepolymerizing it at a pressure of 8.0 K / G to 8.7 K / G to form particle nuclei; And
    상기 입자핵의 존재 하에 제2 염화비닐계 단량체 및 후중합 개시제를 후중합하는 단계를 포함하고, Post-polymerizing a second vinyl chloride-based monomer and a post-polymerization initiator in the presence of the particle nucleus,
    상기 전중합 개시제는 전중합 시 압력 대비 1.3 K/G 내지 3.5 K/G으로 낮은 압력에서 첨가하는 것이며,The pre-polymerization initiator is to be added at a low pressure of 1.3 K / G to 3.5 K / G compared to the pressure during pre-polymerization,
    하기 수학식 1로 정의되는 입자 불균일도가 10 이상인 청구항 1의 염화비닐계 중합체의 제조방법:Method for producing a vinyl chloride-based polymer of claim 1 having a particle non-uniformity of 10 or more defined by the following equation:
    [수학식 1][Equation 1]
    Figure PCTKR2019009907-appb-I000013
    Figure PCTKR2019009907-appb-I000013
    상기 수학식 1에서, Xi는 i번째 입자의 표준편차로, 하기 수학식 2로 정의되는 값이고, In Equation 1, X i is the standard deviation of the i-th particle, and is a value defined by Equation 2 below,
    [수학식 2][Equation 2]
    Figure PCTKR2019009907-appb-I000014
    Figure PCTKR2019009907-appb-I000014
    상기 수학식 2에서, An은 i번째 입자의 n번째 측정 지름의 보정값이고, 여기에서 보정값은 하기 수학식 3으로 정의되는 값이며,In Equation 2, A n is a correction value of the n-th measurement diameter of the i-th particle, where the correction value is a value defined by Equation 3 below,
    [수학식 3][Equation 3]
    Figure PCTKR2019009907-appb-I000015
    Figure PCTKR2019009907-appb-I000015
    상기 수학식 3에서, Dn은 i번째 입자의 n번째 측정 지름이고, D0은 i번째 입자에서 가장 긴 지름이며, n은 1 내지 50의 정수이다.In Equation 3, D n is the n-th measurement diameter of the i-th particle, D 0 is the longest diameter in the i-th particle, and n is an integer from 1 to 50.
  6. 청구항 5에 있어서, The method according to claim 5,
    상기 전중합 개시제는 전중합 시 압력 대비 1.5 K/G 내지 3.0 K/G 낮은 압력에서 첨가하는 것인 염화비닐계 중합체의 제조방법. The prepolymerization initiator is a method for producing a vinyl chloride-based polymer that is added at a pressure of 1.5 K / G to 3.0 K / G lower than the pressure during prepolymerization.
  7. 청구항 5에 있어서,The method according to claim 5,
    상기 전중합 개시제는 제1 염화비닐계 단량체 100 중량부에 대하여 0.01 중량부 내지 1 중량부로 첨가하는 것인 염화비닐계 중합체의 제조방법. The prepolymerization initiator is a method for producing a vinyl chloride-based polymer that is added in an amount of 0.01 to 1 part by weight based on 100 parts by weight of the first vinyl chloride-based monomer.
  8. 청구항 5에 있어서, The method according to claim 5,
    상기 전중합은 중합 전환율 10% 내지 15%까지 수행하는 것인 염화비닐계 중합체의 제조방법. The prepolymerization is a method for producing a vinyl chloride-based polymer that is carried out up to 10% to 15% polymerization conversion.
  9. 청구항 5에 있어서,The method according to claim 5,
    상기 후중합은 6 K/G 내지 13 K/G의 압력에서 수행하는 것인 염화비닐계 중합체의 제조방법. The post-polymerization is a method of producing a vinyl chloride-based polymer that is performed at a pressure of 6 K / G to 13 K / G.
  10. 청구항 5에 있어서,The method according to claim 5,
    상기 후중합 개시제는 제2 염화비닐계 단량체 100 중량부 대비 0.05 중량부내지 2 중량부로 사용하는 것인 염화비닐계 중합체의 제조방법. The post-polymerization initiator is a method for producing a vinyl chloride-based polymer that is used in an amount of 0.05 to 2 parts by weight compared to 100 parts by weight of the second vinyl chloride-based monomer.
  11. 청구항 5에 있어서,The method according to claim 5,
    상기 전중합 개시제 및 후중합 개시제는 각각 디-2-에틸헥실 퍼옥시디카보네이트, t-부틸퍼옥시 네오데카노에이트, t-부틸퍼옥시 에스터, 큐밀퍼옥시 에스터, 큐밀퍼옥시 네오데카노에이트, 1,1,3,3-테트라메틸 부틸 퍼옥시 네오데카노에이트, t-헥실 퍼옥시 네오데카노에이트, t-헥실 퍼옥시 피발레이트, t-부틸 퍼옥시 피발레이트, 디-sec-부틸 퍼옥시 디카보네이트, 디-2-에톡시에틸 퍼옥시 디카보네이트, 이소부티릴 퍼옥사이드, 3,5,5-트리메틸헥사노일 퍼옥사이드, 라우릴 퍼옥사이드 및 옥틸퍼옥시 디카보네이트 중에서 선택된 1종 이상인 것인 염화비닐계 중합체의 제조방법.The pre-polymerization initiator and post-polymerization initiator are di-2-ethylhexyl peroxydicarbonate, t-butylperoxy neodecanoate, t-butylperoxy ester, cumylperoxy ester, cumylperoxy neodecanoate, respectively. 1,1,3,3-tetramethyl butyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, di-sec-butyl per One or more selected from oxy dicarbonate, di-2-ethoxyethyl peroxy dicarbonate, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, lauryl peroxide and octylperoxy dicarbonate Method for producing phosphorus vinyl chloride polymer.
PCT/KR2019/009907 2018-09-21 2019-08-07 Vinyl chloride-based polymer and method for producing same WO2020060028A1 (en)

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KR20090039117A (en) * 2007-10-17 2009-04-22 주식회사 엘지화학 Mass polymerization method of vinyl chloride resin with low fine particle content
KR20100023340A (en) * 2008-08-21 2010-03-04 주식회사 엘지화학 Method of manufacturing of well dispersible vinyl chloride-based resins
KR20110006223A (en) * 2009-07-13 2011-01-20 주식회사 엘지화학 Manufacturing method of bulk polymerization of pvc polymer and pvc copolymer using organic base material as ph control agent
KR20160061126A (en) * 2014-11-21 2016-05-31 주식회사 엘지화학 Vinyl chloride polymer and preparing method thereof
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KR20100023340A (en) * 2008-08-21 2010-03-04 주식회사 엘지화학 Method of manufacturing of well dispersible vinyl chloride-based resins
KR20110006223A (en) * 2009-07-13 2011-01-20 주식회사 엘지화학 Manufacturing method of bulk polymerization of pvc polymer and pvc copolymer using organic base material as ph control agent
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