WO2017006185A1 - 염화비닐계 공중합체의 제조방법 및 이로부터 제조된 염화비닐계 공중합체 - Google Patents

염화비닐계 공중합체의 제조방법 및 이로부터 제조된 염화비닐계 공중합체 Download PDF

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Publication number
WO2017006185A1
WO2017006185A1 PCT/IB2016/001074 IB2016001074W WO2017006185A1 WO 2017006185 A1 WO2017006185 A1 WO 2017006185A1 IB 2016001074 W IB2016001074 W IB 2016001074W WO 2017006185 A1 WO2017006185 A1 WO 2017006185A1
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Prior art keywords
vinyl chloride
monomer
maleimide
weight
copolymer
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PCT/IB2016/001074
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English (en)
French (fr)
Inventor
주진혁
하현규
임중철
전양준
강민정
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LG Chem Ltd
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LG Chem Ltd
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Priority to CN201680002905.XA priority Critical patent/CN108055849B/zh
Priority to EP16820907.0A priority patent/EP3243852B1/en
Publication of WO2017006185A1 publication Critical patent/WO2017006185A1/ko
Anticipated expiration legal-status Critical
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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
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—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
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors

Definitions

  • the present invention relates to a method for producing a vinyl chloride copolymer having excellent heat resistance and to a vinyl chloride copolymer prepared therefrom.
  • Conventional fire-resisting synthetic resins are generally vinyl chloride based for the manufacture of sewage pipes.
  • the above-mentioned vinyl chloride resin is a polymer containing 50% or more of vinyl chloride, which is low in price, easy to control hardness, and can be applied to most processing equipment. Due to its excellent properties such as mechanical strength, weather resistance and chemical resistance, it is widely used in various fields such as building materials, household goods, automobile interior materials and decoration materials.
  • the fire-resistant synthetic resin material has excellent heat resistance and flame retardancy according to the installation maintenance and safety management of indoor fire hydrant equipment, and has excellent heat resistance and flame retardancy which does not occur deformation due to heat within 24 hours at 80 ° C.
  • the fire-fighting equipment method has been strengthened for use, the application of vinyl chloride resins as fire-fighting synthetic resin materials has been restricted.
  • the vinyl chloride resin is poor in heat resistance and flame retardancy, so that when exposed to fire or exposed to high heat such as hot water pipes or hot water pipes, the pressure resistance, mechanical strength, and chemical performance drop sharply.
  • Vinyl Chloride Chloride which improves heat resistance, flame retardancy and durability
  • a resin (CPVC, chlorinated polyvinyl chloride) was developed.
  • the chlorinated vinyl chloride resin (CPVC) is more conventional than the vinyl chloride resin.
  • the market and domestic market share is high (Global market growth rate of 7.2% / year, Domestic market growth rate of 10% / year).
  • British Patent No. 1,293,542 discloses a copolymer of an N-arylmaleimide compound and a methacrylic acid ester-based monomer containing at least 50% by weight of methyl methacrylate.
  • a thermoplastic resin composition combining a copolymer of a N-aryl maleimide compound and another monomer capable of copolymerization with the monomer and a vinyl chloride-based polymer is proposed, but the composition is the chlorinated chloride chloride-based resin (CPVC).
  • CPVC chlorinated chloride chloride-based resin
  • N-substituted maleimide monomer is initially added to the vinyl chloride monomer.
  • the present invention has been made to solve the above problems of the prior art, and an object thereof is to provide a method for producing a vinyl chloride copolymer having excellent heat resistance.
  • Another object of the present invention is a vinyl chloride-based compound prepared from the above production method.
  • the present invention provides a prepolymerization step (step 1) of polymerizing a vinyl chloride monomer and a first copolymerizable monomer to form a particle nucleus; and a second copolymer monomer on the particle nucleus.
  • a method of preparing a pore polymer is provided.
  • the present invention also relates to a vinyl chloride copolymer prepared from the above production method.
  • the N-substituted maleimide compound which is used as a comonomer, is not added to the vinyl chloride monomer in a prepolymerization step, but is divided into N-substituted maleimide at a specific ratio.
  • Compounds and vinyl chloride monomers can form copolymers easily with a uniform distribution.
  • the vinyl chloride copolymer according to the present invention is prepared according to the above-mentioned manufacturing method.
  • Copolymers can be easily applied to industries requiring them, especially those using vinyl chloride resins, as well as those requiring resins having excellent heat resistance.
  • the present invention provides a method for producing a vinyl chloride copolymer with excellent heat resistance.
  • the manufacturing method includes a vinyl chloride monomer and a first compound.
  • a prepolymerization step (step 1) of polymerizing a copolymerizable monomer to form particle nuclei; and a post-polymerization step (step 2) of adding and polymerizing a second copolymerizable monomer to the particle nucleus, wherein the first co-synthesis The monomer and second copolymerizable monomer total amount
  • Step 1 is a prepolymerization step for forming a mip nucleus by polymerizing a vinyl chloride monomer and a first copolymer monomer, and injecting the vinyl chloride monomer and the first copolymerizable monomer into a bulk polymerization reactor, Can be combined.
  • the vinyl chloride monomer may be a pure vinyl chloride monomer alone or a combination of a vinyl chloride monomer and a vinyl monomer copolymerizable with the vinyl chloride monomer.
  • the vinyl chloride monomer is a vinyl chloride monomer and a vinyl copolymer capable of copolymerization with the vinyl chloride monomer. In the case of the monomer mixture, the ratio of the mixture may be adjusted so that 50% or more of the vinyl chloride in the final vinyl chloride resin may be contained.
  • the vinyl chloride monomer capable of copolymerization with the vinyl chloride monomer is not particularly limited, but vinyl esters such as olefin compounds such as propylene and butene, vinyl acetate, vinyl propionate and vinyl stearate.
  • Unsaturated nitriles such as acrylonitrile, vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether, vinyl alkyl ethers such as vinyl lauryl ether, and vinylidene halides such as vinylidene chloride, acrylic acid and methacryl Unsaturated fatty acids such as acids, itaconic acid, maleic acid, fumaric acid, maleic anhydride, and anhydrous itaconic acid, and anhydrides of these fatty acids, methyl acrylate, ethyl acrylate, monomethyl maleate, dimethyl maleate, and butylbenzyl maleate. ), Crosslinkable monomers such as diaryl phthalate, and the like, and the vinyl monomers alone or in combination of two or more. And it can be used.
  • Unsaturated nitriles such as acrylonitrile, vinyl methyl ether, vinyl ethyl ether, vinyl octyl ether, vinyl alky
  • the first copolymerizable monomer may be the same material as the second copolymerizable monomer introduced in Step 2 described later.
  • both the first and second copolymerizable monomers may be N-substituted maleimide monomers. That is, the "first" in the first copolymer and the second copolymer monomer and "Second" may be indicative of the difference in time of injection.
  • the first copolymerizable monomer may be an N-substituted maleimide monomer introduced in the prepolymerization stage
  • the second copolymerizable monomer may be an N-substituted maleimide monomer introduced in the postpolymerization stage.
  • the N-substituted maleimide monomer is N-methyl maleimide, N-ethyl maleimide, Nn-propyl maleimide, N-isopropyl maleimide, Nn-butyl maleimide, N-phenyl maleimide, N It may be one or more selected from the group consisting of -hydroxyphenyl maleimide, N-carboxyphenyl maleimide, N-nitrophenyl maleimide and N-methylphenyl maleimide. Specifically, the N-substituted maleimide monomer May be N-phenylmaleimide.
  • the N-substituted maleimide monomer may be used in an amount of 5 to 30 parts by weight based on 100 parts by weight of the vinyl chloride monomer, i.e., the first copolymerizable monomer introduced in the prepolymerization step and the postpolymerization step.
  • the total amount of the second copolymerizable monomer may be 30 parts by weight of the quinine ring: part relative to 100 parts by weight of the vinyl chloride monomer.
  • the first copolymer monomer is introduced in the prepolymerization stage.
  • the amount of the second copolymer may be relatively small compared to the amount of the second copolymerizable monomer, and specifically, the first copolymer and the second copolymer may have a weight ratio of 3: 7 to 4: 6.
  • the first copolymerizable monomer may be 3 parts by weight to 4 parts by weight
  • the second copolymerizable monomer may be 6 parts by weight to 7 parts by weight.
  • the particle nucleus may not be stably formed. As a result, the effect of improving heat resistance may be reduced.
  • the particle nucleus is formed by binding vinyl chloride monomers to each other.
  • Primary particles formed by condensing particles and primary copolymer monomers may represent secondary particles formed by condensing with each other, wherein the particle nucleus is relatively larger than the voids in the final copolymer. May have voids.
  • the prepolymerization of step 1 may be carried out in the presence of a prepolymerization initiator, if necessary.
  • a prepolymerization initiator is not particularly limited, for example, 0.01 parts by weight to 1 part by weight based on 100 parts by weight of the vinyl chloride monomer. It may be by weight.
  • the type of prepolymerization initiator is not particularly limited, and for example, a peroxy ester or a compound of peroxydicarbonate can be used. Specifically, di-2-ethylnuclear siloxy dicarbonate, t-butyl peroxy
  • Neodecanoate diisopropyl peroxydicarbonate, methyl ethyl ketone peroxide, di-3-methoxybutyl peroxydicarbonate, t-butylperoxy
  • Pivalate t-amylperoxypivalate, t-nuxylperoxypivalate, or a combination thereof.
  • the prepolymerization is not particularly limited, but may be performed, for example, at a reaction pressure of 8.5 K / G to 13 K / G and a temperature range of 30 ° C to 70 ° C.
  • Step 2 is a post-polymerization step for producing a vinyl chloride-based copolymer by growing the particle nucleus produced in the pre-polymerization step, the low 12 copolymer monomer is introduced into the particle nucleus produced in the pre-polymerization step.
  • vinyl chloride monomer can be used, if necessary, and the amount can be properly adjusted according to the purpose.
  • the vinyl chloride monomer can be filled in the inside.
  • the "straightening" may be indicative of input or existence.
  • the second co-polymerizable monomer may be the same material as the first copolymer-polymerized monomer, and the amount of the second copolymer-polymerized monomer may be used within the same ratio range as described above.
  • one or more of the second copolymerizable monomers may be added at a time point within the whole polymerization process immediately after the start of polymerization, immediately after the start, or after the start of the postpolymerization. Post-polymerization starts after the start of post-polymerization.
  • the time point within 1/4 may be within 25 minutes immediately after the start of post-polymerization.
  • the second copolymerizable monomer may react with the second copolymerizable monomers to form separate particles rather than reacting with the particle nucleus, resulting in a vinyl chloride coefficient. The heat resistance of the paper can be reduced.
  • the post-polymerization of step 2 may be carried out in the presence of a post-polymerization initiator, if necessary.
  • the use of the post-polymerization initiator is not particularly limited, for example, 0.01 parts by weight to 2 parts by weight of vinyl chloride monomer is added. It may be by weight.
  • the postpolymerization initiator may be introduced into the postpolymerization reactor together with the particle nucleus, or may be introduced at any point at which the transfer of the particle nucleus is completed or at any point during postpolymerization, and specifically, after the transfer of the particle nucleus is completed, the transfer may be performed.
  • 1/4 of the entire polymerization process may be introduced at a time point, wherein the post-polymerization initiator is added at one time or divided into several points, or It may be continuous feeding.
  • the postpolymerization initiator is not particularly limited but may be, for example, a peroxy ester or a compound of peroxydicarbonate. Specifically, the postpolymerization initiator may be cumyl peroxy ester or t-butyl peroxide. Oxyester, octylperoxy dicarbonate, 1,1,3,3-tetramethyl . Butyl oxyneodicarbonate,.
  • the post-polymerization is not particularly limited, but may be performed at a reaction pressure of 7.5 K / G to 11 K / G and a silver range of 30 ° C to 70 ° C.
  • the manufacturing method according to an embodiment of the present invention can eliminate the reaction of the post-polymerization initiator remaining by adding a polymerization inhibitor at the end of the post-polymerization . have.
  • the polymerization inhibitor is not particularly limited, for example, hydroquinone, butylated hydroxy the toluene, monomethyl ether hydroquinone, quaternary butyl catechol, diphenyl amine, tri isopropanol play min, triethanolamine
  • the amount of the polymerization inhibitor may be appropriately adjusted according to the amount of residual polymerization initiator, but may be used in an amount of 0.001 parts by weight to 0.1 parts by weight with respect to 100 parts by weight of the vinyl chloride monomer.
  • the manufacturing method according to the embodiment of the present invention is combined with a vinyl chloride monomer.
  • the reaction medium may be used in combination, and in addition to the active ingredients described above, it may further include additives such as molecular weight regulators and antioxidants.
  • the reaction medium is not particularly limited, but aromatic compounds such as benzene, roluene, and xylene, and methyl ethyl ketone, acetone, n-nucleic acid, chloroform, and cyclonucleic acid may be used.
  • the molecular weight regulator is not particularly limited, but may be, for example, n-butyl mercaptan, n-octyl mercaptan, ⁇ -dodecyl mercaptan, t-dodecyl mercaptan and the like.
  • the antioxidant is not particularly limited.
  • BHT 2,5-di-t-butyl-P-cresol
  • the manufacturing method according to an embodiment of the present invention may further include a devolatilization step after the post-polymerization step.
  • the above-mentioned manufacturing method is performed by splitting and injecting N-substituted maleimide compounds used as comonomers at a predetermined ratio without collectively adding them together with the vinyl chloride monomer in the prepolymerization step.
  • the N-substituted maleimide compound can be easily integrated with the vinyl chloride monomer to exhibit a uniform distribution, and the heat resistance of the vinyl chloride copolymer prepared therein can be easily improved.
  • the present invention provides a vinyl chloride copolymer produced from the above production method.
  • the vinyl chloride copolymer according to one embodiment of the present invention is N-substituted
  • the N-substituted maleimide monomer may be as described above.
  • the N-substituted maleimide monomer-derived portion indicates a portion derived from the N-substituted maleimide monomer in the vinyl chloride copolymer.
  • the vinyl chloride copolymer is in the temperature range of 1.00 ° C to 120 ° C
  • the vinyl chloride copolymer may also have a heat deflection temperature (HDT) in the temperature range of 92 ° C to 110 ° C.
  • HDT heat deflection temperature
  • the glass transition temperature Using a differential scanning calorimetry (DSC) Ta instrument Q 10, the temperature was raised to 10 0 C / min from room temperature to 200 ° C, and then reduced to 20 o C / min until -80 ° C. Is the measurement of the highest variation point of the incremental heat flow during which phase change occurs.
  • the temperature (HDT) is 100 parts by weight of vinyl chloride copolymer 3 parts by weight of tin stabilizer, 0.5 parts by weight of stearic acid in a roll shaker of 190 ° C. for 3 minutes and then the temperature of 190 ° C. and 80 kg / cm 2 Press-molded for 10 minutes to produce a 3 mm thick plate-shaped specimen, and preheat each sample to 4 minutes by immersing it in oil according to ASTM D648, heating it at 120 0 C / hour It is a measurement of the temperature when mm is dropped.
  • the vinyl chloride-based copolymer according to an embodiment of the present invention is manufactured through the manufacturing method of the above being can have an elevated glass transition temperature and heat distortion temperature.
  • neodecanoate BND
  • the inner core was degassed with a vacuum pump while stirring and prepolymerization reaction was carried out for 20 minutes while maintaining the prepolymerization pressure at 12 K / G to prepare a particle nucleus.
  • the prepared particle nucleus was transferred to an internal volume 1 m 3 post-stained polymerization reactor equipped with a stirrer, and when the transfer was completed, 3 parts of N-phenylmaleimide, 2,6-di-t-butyl-P-cresol (BHT) 0.0001 parts by weight, Polyvinylacetate-co-crotonic acid (CT-5) 0.00009 parts by weight,
  • a vinyl chloride copolymer was obtained in the same manner as in Example 1, except that 8 parts by weight of N-phenylmaleimide was added in the prepolymerization step and 12 parts by weight were added in the postpolymerization step.
  • a vinyl chloride copolymer was obtained through the same method as in Example 1, except that 18 parts by weight was added in the step.
  • a vinyl chloride copolymer was obtained in the same manner as in Example 1, except that 6 parts by weight of N-phenylmaleimide was added in the prepolymerization step and 14 parts by weight were added in the postpolymerization step.
  • a vinyl chloride-based polymer was obtained in the same manner as in Example 1 except that N-phenylmaleimide was not used.
  • a vinyl chloride-based polymer was obtained in the same manner as in Example 1, except that the step was not added. ;
  • Comparative Example 3 A vinyl chloride polymer was obtained in the same manner as in Example 1, except that 5 parts by weight of N-phenylmaleimide was not added in the pre-polymerization step but only in the post-polymerization step.
  • a vinyl chloride polymer was obtained in the same manner as in Example 1, except that 2 parts by weight of N-phenylmaleimide was added in the prepolymerization step and 18 parts by weight in the postpolymerization step.
  • a vinyl chloride-based polymer was obtained in the same manner as in Example 1, except that 4 parts by weight of N-phenylmaleimide was added in the prepolymerization step and 16 parts by weight in the postpolymerization step.
  • a vinyl chloride polymer was obtained in the same manner as in Example 1, except that 12 parts by weight of N-phenylmaleimide was added in the prepolymerization step and 8 parts by weight in the postpolymerization step.
  • Neodycanonate (BND) was added 0.088 parts by weight, degassed with a vacuum pump while stirring, and 100 parts by weight of vinyl chloride monomer and 5 parts by weight of N-phenylmaleimide were added at once.
  • the temperature in the reactor was 62 ° C. during the reaction process. the reaction was conducted while maintaining. the polymerization reaction at a time when the jeunghap if the pressure is 1.0 kg / cm 2 changes Stop and triethylene
  • a vinyl chloride copolymer was obtained in the same manner as in Comparative Example 9 except that 20 parts by weight of N-phenylmaleimide was used.
  • the glass transition temperature was measured using a differential scanning calorimetry (DSC) Ta instrument Q10. Specifically, the vinyl chloride copolymer and the vinyl chloride copolymer were used at room temperature up to 200 ° C. After the temperature was raised to 0 C / min, the temperature was reduced to 20 ° C / min to -80 ° C, and the highest variation point of the period change heat flow where the phase change occurred when the temperature was raised for the second time was measured.
  • DSC differential scanning calorimetry
  • the heat deflection temperature was increased while the vinyl chloride copolymers of Examples 1 to 5 exhibited high overall glass transition temperatures in comparison with the vinyl chloride polymers of Comparative Example 1 and the vinyl chloride copolymers of Comparative Examples 2 to 10. Shown.
  • the vinyl chloride copolymer of Example 1 (using 5 parts by weight of N-phenylmaleimide) was compared with the vinyl chloride polymer (vinyl chloride monomer alone polymerization) of Comparative Example 1, The glass transition temperature of the vinyl chloride copolymer was compared with that of Comparative Example 1 .
  • N-phenylmaleimide is prepared according to a manufacturing method according to an embodiment of the present invention.
  • the vinyl chloride copolymer and the N-phenylmaleimide of Example 4 prepared in Example 1 were prepared by split injection at a ratio of 3: 7 to 4: 6. Beyond the input ratio suggested by the As a result of comparing the vinyl chloride copolymers of Comparative Examples 2 to 6 prepared by comparison, the vinyl chloride copolymers of Examples 2 to 4 were compared with those of the vinyl chloride copolymers of Comparative Examples 2 to 6.
  • the vinyl chloride copolymers of Examples 2 to 4 were generally compared with those of Comparative Examples 2 to 6. It was confirmed that the heat distortion temperature was increased by about 6% to 12% compared to the vinyl copolymer.
  • the polyvinyl chloride copolymer of Example 5 prepared by injecting at a point within 1/4 after the start of the polymerization is removed from the quarter.
  • the glass transition temperature was increased by about 3% or 9%, and at the same time, the heat deformation temperature was increased by about 5% or 11%.
  • N-phenyl according to a manufacturing method according to an embodiment of the present invention.
  • N-phenylmaleimide and vinyl chloride monomer can be easily formed into a homogeneous distribution so that the heat resistance can be further improved.
  • Comparative Example 9 and Comparative Example 10 prepared by conventionally known suspension polymerization, and not by the method of mass polymerization according to one embodiment of the present invention.
  • the vinyl chloride copolymer exhibited a reduced glass transition temperature as compared to the vinyl chloride copolymers of Examples 1 (compared to Comparative Example 9) and Examples 2 (compared to Comparative Example 10) as well as a thermal deformation temperature of about 89%. Level (comparative example 9 compared to example 1) and about 93% . It was reduced to the level (Comparative Example 10 compared to Example 2). This means that the production method through bulk polymerization according to the present invention produces a vinyl chloride copolymer having excellent heat resistance compared to the production method through conventional suspension polymerization. This means that you can do it.

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Abstract

본 발명은 우수한 내열성을 갖는 염화비닐계 공중합체의 제조방법 및 이로부터 제조된 염화비닐계 공중합체에 관한 것이다. 이에 따른 제조방법은 공단량체로 사용되는 N-치환 말레이미드 화합물을 전중합 단계에서 염화비닐계 단량체와 함께 일괄적으로 투입하지 않고, 특정 비율로 분할 투입함으로써 Ν-치환 말레이미드 화합물과 염화비닐계 단량체가 균일한 분포로 용이하게 공중합체를 형성할 수 있으며, 이에 제조된 염화비닐계 공중합체는 우수한 내열성을 나타낼 수 있다. 따라서, 본 발명에 따른 염화비닐계 공중합체의 제조방법 및 염화비닐계 공중합체는 이를 필요로 하는 산업, 특히 염화비닐계 수지를 이용하는 산업뿐 아니라 우수한 내열성을 갖는 수지를 필요로 하는 산업에 용이하게 적용될 수 있다.

Description

명세서
발명의명칭:염화비닐계공중합체의제조방법및이로부터제조된 염화비닐계공중합체
기술분야
[1] 본발명은우수한내열성을갖는염화비닐계공중합체의제조방법및이로부터 제조된염화비닐계공중합체에관한것이다.
[2]
배경기술
[3] 종래의소방용합성수지재는일반적으로하수관을제조하는염화비닐계
수지를사용하였다.상기염화비닐계수지는염화비닐을 50%이상함유하는 중합체로서,가격이저렴하고경도조절이용이하며，대부분의가공기기에적용 가능하여웅용분야가다양하다.게다가，물리적 ·화학적성질，예컨대기계적 강도,내후성，내약품성등이우수하여건축자재,생활용품，자동차내장재， 장식재등여러분야에서광범위하게사용되고있다.
[4]
[5] 그러나，옥내소화전설비의설치유지및안전관리에따라상기소방용합성 수지재는내열성및난연성이우수한것으로서 80°C에서 24시간이내에열로 인한변형이생기지않는내열성및난연성이우수한특성을갖는것을 사용하도록소방설비법이강화되면서，염화비닐계수지의소방용합성 수지재로서의적용이제한되고있다.
[6]
[7] 상기염화비닐계수지는내열성및난연성이좋지못하여화재에노출되거나 온수배관용이나온천수배관용등고열에노출되는경우내압성과기계적강도 및화학적성능이급격히저하되는문제가있다.이에，염화비닐계수지의 최대약점인내열성,난연성및내구성을향상시킨염소화염화비닐계
수지 (CPVC, chlorinated polyvinyl chloride)가개발되었다.
[8] 상기염소화염화비닐계수지 (CPVC)는통상적인염화비닐계수지보다
염소화물을 20%더높인염소화수지로，유리전이온도및열변형온도가
증가하여 120°C까지의열에견딜수있는내열성，황산,염산,질산등부식에 강한특성,자기소화성및가공성이우수하여소방용은물론내약품성이뛰어나 고온의화학약품배관용으로도용이하게적용되고있으며,시계시장및국내 시장의높은점유율 (세계시장성장율약 7.2%/년,국내시장성장율약 10%/년)을 보이고있다.
[9]
[1이 따라서 ,상기의시장의변화에부응하기위하여염소화염화비닐계수지를 대체할수있는수지의개발이요구되고있으며，특히국내의경우염소화 염화비닐계수지 (CPVC)를전량수입에의존하고있어이를대체할수있는 수지의개발이절실히요구되고있다.
[11]
[12] 이에，다양한방안들이제안되고있으며，일례로영국특허제 1,293,542호에는 N-아릴말레이미드화합물과메타크릴산메틸을적어도 50중량 ·¾이상 함유하는메타크릴산에스테르계단량체와의공중합체，또는 N-아릴 말레이미드화합물과상기단량체에다시공중합가능한다른단량체를 조합시킨공중합체와염화비닐계중합체를흔합한열가소성수지조성물을 제안하고있으나,상기조성물은상기염소화염화비닐계수지 (CPVC)를 대체하기에는내열성이충분하지못한문제가있다.
[13] 또한,염화비닐계단량체에 N-치환말레이미드계단량체를초기
일괄투입하거나분할투입하는현탁중합을통하여내열성을높인염화비닐계 수지를제조하는방안이제안된바있다.그러나,상기현탁중합을통한 제조방법은 N-치환말레이미드계단량체를투입하면반응시간이지연되고 N-치환말레이미드계단량체의공명구조형성으로인하여반웅성이감소하는 단점이있다.뿐만아니라중합시염화비닐계단량체와 N-치환말레이미드계 단량체의블균일로인하여제조된공중합체가두점의유리전이온도를가지게 되고，결과적으로내열성향상은미미한문제가있디-.
[14]
[15] .따라서,염소화염화비닐계수지를대체할수있는，내열성및난연성특성이 우수한수지의개발이여전히필요한실정이다.
[16]
발명의상세한설명
기술적과제
[17] 본발명은상기의종래기술의문제를해결하기위하여안출된것으로，우수한 내열성을갖는염화비닐계공중합체의제조방법을제공하는것을목적으로 한다.
[18] 본발명의다른목적은상기의제조방법으로부터제조된염화비닐계
공중합체를제공하는것이다.
[19]
과제해결수단
[20] 상기의과제를해결하기위하여，본발명은염화비닐계단량체와제 1공중합성 단량체를중합하여입자핵을형성시키는전중합단계 (단계 1);및상기입자핵에 제 2공중합성단량체를첨가하고중합하는후중합단계 (단계 2)를포함하고， 상기제 1공증합성단량체및제 2공중합성단량체합계량이염화비닐계단량체 100중량부를기준으로 5증량부내지 30증량부인것인염화비닐계공중합체의 제조방법을제공한다. [21]
[22] 또한,본발명은상기의제조방법으로부터제조된염화비닐계공중합체를
제공한다.
[23]
발명의효과
[24] 본발명에따른제조방법은공단량체로사용되는 N-치환말레이미드화합물을 전중합단계에서염화비닐계단량체와함께일괄적으로투입하지않고，특정 비율로분할투입함으로써 N-치환말레이미드화합물과염화비닐계단량체가 균일한분포로용이하게공중합체를형성할수있다.
[25] 또한，본발명에따른염화비닐계공증합체는상기의제조방법으로
제조됨으로써단일의상승된유리전이온도를나타낼수있으며，이와동시에 열변형온도가높아질수있어우수한내열성을나타낼수있다.
[26] 따라서，본발명에따른염화비닐계공중합체의제조방법및염화비닐계
공중합체는이를필요로하는산업,특히염화비닐계수지를이용하는산업뿐 아니라우수한내열성을갖는수지를필요로하는산업에용이하게적용될수 있다.
[27]
발명의실시를위한최선의 형태
[28] 이하，본발명에대한이해를돕기위하여본발명을더욱상세하게설명한다.
[29] 본명세서및청구범위에사용된용어나단어는통상적이거나사전적인의미로 한정해서해석되어서는아니되며，발명자는그자신의발명을가장최선의 방법으로설명하기위해용어의개념을적절하게정의할수있다는원칙에 입각하여본발명의기술적사상에부합하는의미와개념으로해석되어야만 한다.
[30]
[31] 본발명은우수한내열성을갖는염화비닐계공증합체의제조방법을제공한다.
[32] 본발명의일실시예에따른상기제조방법은염화비닐계단량체와제 1
공중합성단량체를중합하여입자핵을형성시키는전중합단계 (단계 1);및상기 입자핵에제 2공중합성단량체를첨가하고중합하는후중합단계 (단계 2)를 포함하고,상기제 1공증합성단량체및제 2공중합성단량체합계량이
염화비닐계단량체 100증량부를기준으로 5증량부내지 30중량부인것을 특징으로한다.
[33]
[34] 상기단계 1은염화비닐계단량체와제 1공중합성단량체를중합하여밉자핵을 형성시키기위한전중합단계로，전중합반웅기에염화비닐계단량체및제 1 공중합성단량체를투입하고괴상중합하여수행할수있다. [36] 상기염화비닐계단량체는순수한염화비닐단량체단독또는염화비닐 단량체와상기염화비닐단량체와공중합가능한비닐계단량체의흔합물일수 있다.상기염화비닐계단량체가염화비닐단량체와이와공중합가능한비닐계 단량체의흔합물일경우에는최종제조된염화비닐계수지내염화비닐이 50% 이상포함될수있도록상기흔합물의비율을조절하여사용하는것일수있다.
[37] 상기염화비닐단량체와공중합이가능한비닐계단량체로는특별히제한되는 것은아니나，예컨대프로필렌，부텐등의올레핀 (olefin)화합물,초산비닐， 프로피온산비닐，스테아린산비닐등의비닐에스테르 (vinyl ester)류， 아크릴로니트릴등의불포화니트릴류，비닐메틸에테르，비닐에틸에테르， 비닐옥틸에테르，비닐라우릴에테르등의비닐알킬에테르류,염화비닐리덴 등의할로겐화비닐리덴 (vinylidene)류，아크릴산，메타크릴산,이타콘산， 말레인산，푸마르산，무수말레산，무수이타콘산등의불포화지방산및이들 지방산의무수물，아크릴산메틸,아크릴산에틸，말레인산모노메틸，말레인산 디메틸,말레인산부틸벤질등의불포화지방산에스테르 (ester)류，디아릴 프탈레이트등의가교성단량체등일수있으며，상기비닐계단량체는단독 또는 2종이상을흔합하여사용할수있다.
[38]
[39] 본발명의일실시예에따른상기제 1공중합성단량체는후술하는단계 2에서 투입되는제 2공중합성단량체와서로동일한물질인것일수있다.
[40] 구체적으로，상기제 1공중합성단량체및제 2공중합성단량체는둘다 N-치환 말레이미드계단량체일수있다.즉,상기제 1공중합성단량체와제 2공증합체 단량체에서 "제 1"및 "제 2"는투입시점의차이를나타내는것일수있다.
예컨대,제 1공중합성단량체는전중합단계에서투입되는 N-치환말레이미드계 단량체를나타내는것이고，제 2공중합성단량체는후중합단계에서투입되는 N-치환말레이미드계단량체를나타내는것일수있다.
[41]
[42] 상기 N-치환말레이미드계단량체는 N-메틸말레이미드， N-에틸말레이미드， N-n-프로필말레이미드， N-이소프로필말레이미드 , N-n-부틸말레이미드, N-페닐말레이미드, N-히드록시페닐말레이미드 , N-카르복시페닐말레이미드, N-니트로페닐말레이미드및 N-메틸페닐말레이미드로이루어진군으로부터 선택된 1종이상인것일수있다.구체적으로는,상기 N-치환말레이미드계 단량체는 N-페닐말레이미드일수있다.
[43]
[44] 상기 N-치환말레이미드계단량체는상기염화비닐계단량체 100중량부대비 5중량부내지 30증량부로사용될수있다.즉，전중합단계에서투입되는제 1 공중합성단량체와후중합단계에서투입되는제 2공중합성단량체합계량이 상기염화비닐계단량체 100중량부대비 5중링:부대비 30중량부일수있다. 이때，전중합단계에서투입되는게 1공중합성단량체가후중합단계에서 투입되는제 2공중합성단량체에비하여상대적으로적은양일수있으며, 구체적으로는게 1공중합성단량체와제 2공중합성단량체가 3:7내지 4:6의 중량비를가지는것일수있다.예컨대，사용되는제 1공중합성단량체및저 12 공중합성단량체의총량이 10증량부일경우제 1공증합성단량체는 3중량부 내지 4중량부이고，제 2공중합성단량체는 6중량부내지 7중량부일수있다. 만약,상기제 1공중합성단량체가거 12공중합성단량체보다다량일경우，즉 상기제 1공중합성단량체와제 2공중합성단량체의비율이상기의범위를 벗어날경우에는입자핵을안정적으로형성하지못할수있으며，결과적으로 내열성향상효과가감소될수있다.
[45] 여기에서，상기입자핵은염화비닐계단량체끼리결합하여형성된기초
입자들이웅집되어형성된 1차입자와제 1공중합성단량체입자가서로 웅집되어형성된 1차입자핵들이서로응집하여형성된 2차입자를나타내는 것일수있다.이때，입자핵은최종제조된공중합체내공극보다상대적으로큰 공극을가질수있다.
[46]
[47] 상기단계 1의전중합은필요에따라전중합개시제의존재하에수행될수 있다.상기전증합개시제의사용량은특별히제한되는것은아니나，예컨대 염화비닐계단량체 100중량부에대하여 0.01중량부내지 1중량부일수있다. 또한，상기전중합개시제의종류로는특별히제한되는것은아니나，예컨대 퍼옥시에스터또는퍼옥시디카보네이트의화합물등을사용할수있다. 구체적으로는,디 -2-에틸핵실퍼옥시디카보네이트, t-부틸퍼옥시
네오데카노에이트，디이소프로필퍼옥시디카보네이트,메틸에틸케톤 퍼옥사이드,디 -3-메톡시부틸퍼옥시디카보네이트, t-부틸퍼옥시
피발레이트 (pivalate), t-아밀퍼옥시피발레이트, t-핵실퍼옥시피발레이트또는 이들을흔합하여사용하는것일수있다.
[48]
[49] 또한，상기전중합은특별히제한되는것은아니나，예컨대 8.5 K/G내지 13 K/G의반웅압및 30°C내지 70°C의온도범위조건에서수행하는것일수있다.
[50]
[51] 상기단계 2는，상기전증합단계에서제조된입자핵을성장시켜염화비닐계 공중합체를제조하기위한후중합단계로,전증합단계에서제조된입자핵에 저 12공중합성단량체를투입하고괴상증합하여수행할수있다.이때,필요에 따라염화비닐계단량체를추가로사용할수있으며，사용량은목적하는바에 따라적절히조절하여사용할수있다.
[52] 구체적으로，후중합반응기에상기전중합단계에서제조된입자핵을
이송시키고제 2공중합성단량체를투입한후반웅압과반웅기온도를조절한 후괴상중합을진행시켜수행할수있다.이때,후중합단계에서염화비닐계 • 단량체를추가로사용할경우에는상기입자핵을이송시키기전후중합반웅기 내에상기염화비닐계단량체를충진시켜놓을수있다.
[53] 여거에서，상기 "층진"은투입또는존재함을나타내는것일수있다.
[54]
[55] 상기제 2공증합성단량체는전술한바와같이제 1공중합성단량체와동일한 물질일수있으며，상기제 2공중합성단량체의사용량은전술한바와같은비율 범위내에서사용하는것일수있다.
[56] 또한，상기제 2공중합성단량체는후중합개시와함께，개시직후，또는후중합 개시후후중합전체공정중 1/4이내시점에첨가하는것일수있다.이때，상기 후중합전체공정중 1/4이내시점은후중합개시직후부터후중합을
수행하는데걸리는총시간중 1/4시간에도달한시점올나타내는것이다. 예컨대，후중합전체공정시간이 100분일경우，상기 1/4이내시점은후중합 개시직후부터 25분이내인시점일수있다.만약,상기제 2공중합성단량체를 후중합개시후후중합전체공정중 1/4이지난시점에서투입할경우에는 투입된상기제 2공중합성단량체가상기입자핵과반웅하여중합되기보다제 2 공중합성단량체끼리반응하여별도의입자를형성하는문제가발생할수 있으며，결과적으로염화비닐계수지의내열성이저하될수있다.
[57]
[58] 상기단계 2의후중합은필요에따라후중합개시제의존재하에수행될수 있다.상기후중합개시제의사용량은특별히제한되는것은아니나，예컨대 염화비닐계단량체 100증량부에대하여 0.01중량부내지 2중량부일수있다. 또한，상기후증합개시제는상기입자핵과함께후중합반응기에투입되거나， 상기입자핵의이송이완료된시점또는후중합중어느시점에나투입할수 있으며,구체적으로는상기입자핵의이송이완료된후바로,이송이완료된후 후중합개시후,또는후증합개시후후중합전체공정중 1/4이내시점에 투입할수있다.이때,상기후중합개시제는한시점에일괄적으로투입하거나， 여러시점으로나누어분할투입또는연속투입하는것일수있다.
[59] 상기후중합개시제의종류로는특별히제한되는것은아니나，예컨대퍼옥시 에스터또는퍼옥시디카보네이트의화합물등을사용할수있다.구체적으로는， 상기후중합개시제는큐밀퍼옥시에스터， t-부틸퍼옥시에스터，옥틸퍼옥시 디카보네이트， 1，1，3,3-테트라메틸.부틸 옥시네오디카보네이트, .
디이소프로필퍼옥시디카보네이트,메틸에틸케톤퍼옥사이드,
디 _3-메특시부틸퍼옥시디카보네이트， t-부틸퍼옥시피발레이트 (pivalate), tᅳ아밀퍼옥시피발레이트， t_핵실퍼옥시피발레이트또는이들조합을포함하는 것일수있다.
[60]
[61] 또한,상기후중합은특별히제한되는것은아니나，예컨대 7.5 K/G내지 11 K/G의반응압및 30oC내지 70°C의은도범위조건에서수행하는것일수있다. [63] 본발명의일실시예에따른상기제조방법은후중합말기에중합억제제를 투입하여잔류하는상기후중합개시제의반웅성을제거할수.있다.
[64] 상기중합억제제는특별히제한되는것은아니나,예컨대하이드로퀴논， 부틸레이티드하이드록시를루엔，모노메틸에테르하이드로퀴논， 4차부틸 카테콜，디페닐아민,트리이소프로파놀아민,트리에탄올아민등일수있다. 상기중합억제제의사용량은잔류하는후중합개시제의양에따라적절히 조절하여사용될수있으나，예컨대염화비닐계단량체 100증량부에대하여 0.001중량부내지 0.1중량부로사용될수있다.
[65]
[66] 또한，본발명의일실시예에따른제조방법은염화비닐계단량체와함께
반응매질을흔합하여사용할수있으며，상기기재한유효성분이외에분자량 조절제，산화방지제와같은첨가제를추가로포함할수있다.
[67]
[68] 상기반웅매질은특별히제한되는것은아니나，예컨대벤젠,롤루엔,자일렌 등의방향족화합물과메틸에틸케톤，아세톤， n-핵산，클로로포름，사이클로핵산 등이사용될수있다.
[69]
[70] 상기분자량조절제는특별히제한되는것은아니나,예컨대 n-부틸머캅탄， n-옥틸머캅탄 , η-도데실머캅탄， t-도데실머캅탄등일수있다.
[71] 또한,상기산화방지제는.특별히제한되는것은아니나，예컨대
2,5-디 -t-부틸 -P-크레솔 (BHT),폴리비닐아세테이트 -co-크로노닉애시드， 트리에틸렌글리콜-비스 -[3-(3-t-부틸 -5-메틸 -4-히드록시페닐)프로피노에이트]일 수있다.
[72]
[73] 아을러，본발명의일실시예에따른상기제조방법은후중합단계이후에 탈휘발단계를추가로포함할수있다.
[74]
[75] 본발명의일실시예에따른상기제조방법은공단량체로사용되는 N-치환 말레이미드화합물을전중합단계에서염화비닐계단량체와함께일괄적으로 투입하지않고，특정비율로분할투입함으로써 N-치환말레이미드화합물이 염화비닐계단량체와용이하게증합하여균일한분포를보일수있으며，이에 제조된염화비닐계공증합체의내열성이용이하게향상될수있다.
[76]
[77] 또한,본발명은상기의제조방법으로부터제조된염화비닐계공중합체를 제공한다.
[78] 본발명의일실시예에따른상기염화비닐계공중합체는 N-치환
말레이미드계단량체유래부분을 5중량 %내지 30중량 %포함하는것을 특징으로한다. 상기 N-치환말레이미드계단량체는전술한바와같을수있다.또한，상기 N-치환말레이미드계단량체유래부분은염화비닐계공증합체내 N-치환 말레이미드계단량체로부터유래된부분을나타내는것으로， N-치환
말레이미드계단량체자체성분이거나상기 N-치환말레이미드계단량체를 주체로하여형성된어떠한입자등을나타내는것일수있다. 상기염화비닐계공증합체는 1.00°C내지 120°C온도범위의
유리전이온도 (Tg)를갖는것일수있다.또한，상기염화비닐계공중합체는 92°C 내지 110°C온도범위의열변형온도 (HDT)를갖는것일수있다.여기에서，상기 유리전이온도는시차주사열량계 (Differential Scanning Calorimetry, DSC) Ta instrument Q 10을이용하여상온에서 200°C까지 10 0C/min으로승온시킨후 -80°C까지 20 oC/min으로감온시키고，다시두번째승온시킬때상변화가일어난 구간증 heat flow의최고변이점을측정한것이다.또한,상기열변형
온도 (HDT)는염화비닐계공중합체 100중량부에주석계안정제 3중량부, 스테아린산 0.5중량부를 190°C의롤흔련기에서 3분동안흔련한후 190°C의 온도및 80 kg/cm2의압력으로 10분동안프레스성형하여두깨 3 mm의판상 시편을제작하고， ASTM D648규격에의거하여각시편을.오일에침적하여 4분 동안예열하고 120 0C/시간승온속도로가열하면서시편이 0.254 mm처질때의 온도를측정한것이다. ' _ 본발명의일실시예에따른상기염화비닐계공중합체는상기의제조방법을 통하여제조됨으로써상승된유리전이온도와열변형온도를가질수있다.이에, 상기의염화비닐계공증합체는종래의염화비닐계증합체에비하여상대적으로 우수한내열성을나타낼수있다. 이하，실시예및실험예에의하여본발명을더욱상세하게설명한다.그러나， 하기실시예및실험예는본발명을예시하기위한것으로이들만으로본 발명의범위가한정되는것은아니다. 실시예 1
교반기가부착된내부용적 1 m3의스테인레스전중합반웅기에염화비닐 단량체 1.00증량부 , Ν-페닐말레이미드 2증량부， t-부틸퍼옥시
네오데카노네이트 (BND) 0.03중량부를투입한후교반하면서내부를진공 펌프로탈기하고전중합반웅기내압력을 12 K/G로유지하면서 20분동안 전중합반웅을진행하여입자핵을제조하였다.제조된입자핵을교반기가 부착된내부용적 1 m3의스테인레스후증합반응기에이송하고이송이완료된 시점에 N—페닐말레이미드 3증량부， 2，6-디 -t-부틸 -P-크레솔 (BHT) 0.0001중량부， 폴리비닐아세테이트 -co-크로토닉애시드 (CT-5) 0.00009증량부，
1,1,3,3-테트라메틸부틸퍼옥시네오디카보네이트 (OND) 0.078중량부를 투입하고내부를진공펌프로탈기하여후중합반웅기내압력을 7.8 K/G로 유지하면서 180분동안후중합반웅을진행하였다.그후
트리에틸렌글리콜-비스 -[3-(3-t-부틸 -5-메틸 -4-히드록시페닐)프로피오네이트]
0.05중량부를첨가하여미반응단량체를회수하고염화비닐계공증합체를 수득하였다.
[90]
[91] 실시예 2
[92] N-페닐말레이미드를전중합단계에서 8중량부를투입하고，후증합단계에서 12증량부를투입한것을제외하고는상기실시예 1과동일한방법을통하여 염화비닐계공중합체를수득하였다.
[93]
[94] 실시예 3
[95] N—페닐말레이미드를전중합단계에서 12중량부를투입하고,후중합
단계에서 18중량부를투입한것을제외하고는상기실시예 1과동일한방법을 통하여염화비닐계공중합체를수득하였다.
[96]
[97] 실시예 4
[98] N-페닐말레이미드를전중합단계에서 6중량부를투입하고，후중합단계에서 14증량부를투입한것을제외하고는상기실시예 1과동일한방법을통하여 염화비닐계공중합체를수득하였다.
[99]
[100] 실시예 5
[101] N-페닐말레이미드를전증합단계에서 8중량부를투입하고，후증합단계에서 후중합개시후 30분이된시점에 12중량부를투입한것을제외하고는상기 실시예 1과동일한방법을통하여염화비닐계공중합체를수득하였다.
[102]
[103] 비교예 1
[104] N—페닐말레이미드를사용하지않은것을제외하고는상기실시예 1과동일한 방법을통하여염화비닐계중합체를수득하였다.
[105]
[106] 비교예 2
[107] N-페닐말레이미드를전중합단계에서만 5중량부를투입하고후중합
단계에서는투입하지않은것을제외하고는상기.실시예 1과동일한방법을 통하여염화비닐계중합체를수득하였다. ；
[108]
[109] 비교예 3 [110] N-페닐말레이미드를전중합단계에서는투입하지않고후중합단계에서만 5 중량부를투입한것을제외하고는상기실시예 1과동일한방법을통하여 염화비닐계중합체를수득하였다.
[11 1]
[112] 비교예 4
[113] N-페닐말레이미드를전중합단계에서 2중량부투입하고，후중합단계에서 18 중량부를투입한것을제외하고는상기실시예 1과동일한방법을통하여 염화비닐계증합체를수득하였다.
[114]
[115] 비교예 5
[116] N-페닐말레이미드를전중합단계에서 4중량부투입하고,후중합단계에서 16 중량부를투입한것을제외하고는상기실시예 1과동일한방법을통하여 염화비닐계증합체를수득하였다.
[117]
[118] 비교예 6
[119] N-페닐말레이미드를전증합단계에서 12중량부투입하고，후중합단계에서 8 중량부를투입한것을제외하고는상기실시예 1과동일한방법을통하여 염화비닐계중합체를수득하였다.
[120]
[121] 비교예 7
[122] N-페닐말레이미드를전중합단계에서 8중량부를투입하고,후중합단계에서 후중합개시후 60분이된시점에 12중량부를투입한것을제외하고는상기 실시예 1과동일한방법을통하여염화비닐계공중합체를수득하였다.
[123]
[124] 비교예 8
[125] N-페닐말레이미드를전중합단계에서 8중량부를투입하고，후중합단계에서 후증합개시후 90분이된시점에 12증량부를투입한것을제외하고는상기 실시예 1과동일한방법을통하여염화비닐계공중합체를수록하였다. '
[126]
[127] 비교예 9
[128] 환류웅축기및교반기가부착된내부용적 1 m3의스테인레스중합반웅기에 증합수 140증량부，수화도가 88%인폴리비닐알코올 0.05증량부，수화도가 72%인폴리비닐알코올 0.02증량부，수화도가 55%인폴리비닐알코올 0.015 중량부,히드록시프로필메틸샐롤로오스 0.005중량부， t-부틸퍼옥시
네오디카노네이트 (BND) 0.088중량부를투입하고교반하면서진공펌프로 탈기하고염화비닐단량체 100중량부와 N-페닐말레이미드 5중량부를 일괄투입하였다.반웅전과정동안증합반응기내온도를 62°C로유지하면서 반응을진행하였다.증합반응지압력이 1.0 kg/cm2변화가있는시점에중합을 정지시키고트리에틸렌
글리콜-비스 -p[(3-t-부틸 -5-메틸 -4-히드록시페닐)프로피오네이트]를 0.088 중량부를첨가한후미반응단량체를회수하고형성된공중합체슬러리를 회수하였다.얻어진슬러리를유동층건조기에서건조하여염화비닐계 공중합체를수득하였다.
[129]
[130] 비교예 10
[131] N-페닐말레이미드를 20중량부로사용한것을제외하고는상기비교예 9와 동일한방법을통하여염화비닐계공증합체를수득하였디-.
[132]
[133] 실험예
[134] 상기실시예 1내지실시예 5에서제조된염화비닐계공중합체，비교예 1의 염화비닐계중합체및비교예 2내지비교예 10에서제조된염화비닐계 공중합체의물성을비교분석하기위하여，상기각염화비닐계공증합체및 염화비닐계중합체의유리전이온도및열변형온도를측정하였다.결과를하기 표 1에나타내었다.
[135] 1)유리전이온도 (Tg, °C)
[136] 유리전이온도는시차주사열량계 (Differential Scanning Calorimetry, DSC) Ta instrument Q10을이용하여측정하였다.구체적으로는,상기각염화비닐계 공중합체및염화비닐계증합체를상온에서 200°C까지 10 0C/min으로승온시킨 후 -80°C까지 20 °C/min으로감은시키고，다시두번째승온시킬때상변화가 일어난구간증 heat flow의최고변이점을측정하였다.
[137] 2)열변형온도 (HDT)
[138] 상기각염화비닐계공증합체및염화비닐계중합체 100증량부에주석계 안정제 3증량부，스테아린산 0.5중량부를 190°C의를흔련기에서 3분동안 흔련한후 190°C의온도및 80 kg/cm2의압력으로 10분동안프레스성형하여 두께 3 mm의판상시편을제작하였다.제작한각시편을 ASTM D648규격에 의거하여정교하게절단하여내열시험시편을만들고，만들어진시편의크기에 따라하중을계산하여결정된하중을시편에가하였다.그후,각시편을오일에 침적하여 4분동안예열하고 120 °C/시간승온속도로가열하면서시편이 0.254 mm처질때의온도를측정하였다. [139] [표 1]
Figure imgf000013_0001
[140]
[141] 상기표 1에 나타난바와같이，본발명에따른제조방법에 의하여 제조된
실시예 1내지실시예 5의 염화비닐계공증합체가비교예 1의 염화비닐계 중합체및비교예 2내지 10의 염화비닐계공중합체와비교하여 전반적으로 높은유리전이온도를나타내면서상승된열변형온도를나타내었다.
[142] 구체적으로,실시예 1의 염화비닐계공중합체 (N-페닐말레이미드 5중량부 사용)와비교예 1의 염화비닐계중합체 (염화비닐단량체단독중합)를비교한 결과,실시예 1의 염화비닐계공중합체의유리전이온도가비교예 1의 .
염화비닐계중합체보다약 10%상승하였으며，열변형온도는약 16% ' 상승하였다.이는，본발명의 일실시예에 따라제조된상기 ¾시예 1의 염화비닐계공중합체가종래의 염화비닐계중합체대비 현저히우수한 내열성을가질수있음을나타내는결과이다.
[143] 또한，본발명의 일실시예에따른제조방법에따라 N-페닐말레이미드를
전증합과후중합에서 3:7내지 4:6의 비율로분할투입하여제조된실시예 1내 실시예 4의 염화비닐계공중합체와 N-페닐말레이미드를사용하였으나본 발명의 일실시예에따른제조방법에서제시하는투입 비율을벗어나게 투입하여제조된비교예 2내지비교예 6의염화비닐계공중합체를비교한결과 실시예 2내지실시예 4의염화비닐계공중합체가비교예 2내지비교예 6의 염화비닐계공중합체대비전반적으로다소향상된유리전이온도를
나타내었으며,동일한함량의 N-페닐말레이미드를사용하여제조된각 염화비닐계공중합체와비교한결과전반적으로실시예 2내지실시예 4의 염화비닐계공중합체가비교예 2내지비교예 6의염화비닐계공증합체에 비하여열변형온도가약 6%~12%상승된것을확인하였다.
[144] 아을러， N-페닐말레이미드를후증합단계에서투입시후증합개시후 1/4 내인시점에투입하여제조된실시예 5의염화비닐계공중합체가 1/4이내인 시점을벗어나투입하여제조된비교예 7및비교예 8의염화비닐계공중합체에 비하여를비교한결과유리전이온도가약 3%또는 9%상승하였고，이와동시에 열변형온도가약 5%또는 11%상승하였다.
[145] 상기의결과는,본발명의일실시예에따른제조방법에따라 N-페닐
말레이미드를전중합과후중합에특정비율및시점에분할투입함으로써 N-페닐말레이미드와염화비닐단량체가균일한분포로용이하게공중합체를 형성함으로써내열성이더크게향상될수.있음을나타낸결과이다.
[146] 한편，본발명의일실시예에따른괴상중합을통한제조방법이아닌종래의 통상적으로알려진현탁중합을통해제조한비교예 9및비교예 10의
염화비닐계공중합체는실시예 1(비교예 9대비)및실시예 2(비교예 10대비)의 염화비닐계공중합체에비하여감소된유리전이온도를나타낼뿐아니라 열변형온도도각각약 89%수준 (실시예 1대비비교예 9)및약 93% .수준 (실시예 2대비비교예 10)으로감소되었디-.이는，본발명에따른괴상중합을통한 제조방법이종래의현탁중합을통한제조방법에비하여현저히우수한 내열성을갖는염화비닐계공중합체를제조할수있음을의미하는결과이다.

Claims

청구범위
[청구항 1] 염화비닐계단량체와제 1공중합성단량체를중합하여 입자핵을
형성시키는전중합단계;및
상기 입자핵에제 2공중합성 단량체를첨가하고중합하는후증합단계를 포함하고,
상기 제 1공중합성단량체및거 12공중합성 단량체합계량이 염화비닐계 단량체 100중량부를기준으로 5증량부내지 30중량부인것인
염화비닐계공증합체의제조방법 .
[청구항 2] 청구항 1에 있어서，
상기제 1공중합성단량체와제 2공중합성 단량체는 3:7내지 4:6의 중량비로사용되는것인염화비닐계공중합체의 제조방법 .
[청구항 3] 청구항 1에 있어서,
상기 제 2공중합성 단량체는후중합개시 후후중합전체공정중의 1/4 이내시점에 첨가하는것인염화비닐계공중합체의 제조방법.
[청구항 4] 청구항 1에 있어서,
상기제 1공중합성 단량체및제 2공중합성 단량체는서로동일한물질인 것인염화비닐계공중합체의제조방법 .
[청구항 5] 청구항 1에 있어서,
상기 제 1공중합성 단량체및제 2공중합성 단량체는 N-치환 말레이미드계단량체인것인염화비닐계공증합체의 제조방법.
[청구항 6] 청구항 5에 있어서， .
상기 N-치환말레이미드계단량체는 N-메틸말레이미드， N-에틸 말레이미드, N-n-프로필말레이미드， N-이소프로필말레이미드, N-n-부틸 말레이미드, N-페닐말레이미드, N-히드록시페닐말레이미드，
N-카르복시페닐말레이미드 , Ν-니트로페닐말레이미드및 Ν-메틸페닐 말레이미드로이루어진군으로부터선택된 1종이상인것인염화비닐계 공중합체의 제조방법.
[청구항 7] 청구항 5에 있어서，
상기 Ν-치환말레이미드계,단량체는 Ν-페닐말레이미드인것인 염화비닐계공중합체의 제조방법.
[청구항 8] 청구항 1에 있어서，
상기 전중합은 8.5 K/G내지 13 K/G의 반응압및 30oC내지 70oC의 온도에서괴상중합하여수행하는것인염화비닐계공중합체의제조방법 .
[청구항 9] 청구항 1에 있어서,
상기후중합은 7.5 K/G내지 11 K/G의 반웅압및 30°C내지 70°C의 온도에서괴상중합하여수행하는것인염화비닐계공중합체의제조방법 .
[청구항 10] 청구항 1의 제조방법으로부터 제조된염화비닐계공중합체 .
[청구항 11] 청구항 10에 있어서，
상기 염화비닐계공중합체는 N-치환말레이미드계단량체유래부분을 5 중량 %내지 30증량 %포함하는것인염화비닐계공중합체.
[청구항 12] 청구항 11에 있어서，
상기 N-치환말레이미드계단량체는 N-페닐말레이미드인것인 염화비닐계공중합체.
[청구항 13] 청구항 10에 있어서,
상기 염화비닐계공중합체는 100°C내지 120oC온도범위의 유리전이온도 (Tg)를갖는것인염화비닐계공중합체 .
[청구항 14] 청구항 10에 있어서，
상기 염화비닐계공중합체는 92°C내지 110°C은도범위의 열변형온도 (HDT)를갖는것인염화비닐계공중합체.
PCT/IB2016/001074 2015-07-03 2016-07-29 염화비닐계 공중합체의 제조방법 및 이로부터 제조된 염화비닐계 공중합체 Ceased WO2017006185A1 (ko)

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