KR20130090222A - Menufacturing method of chlorinated polyvinyl chloride resin and chlorinated polyvinyl chloride resin using the thereof - Google Patents
Menufacturing method of chlorinated polyvinyl chloride resin and chlorinated polyvinyl chloride resin using the thereof Download PDFInfo
- Publication number
- KR20130090222A KR20130090222A KR1020120011376A KR20120011376A KR20130090222A KR 20130090222 A KR20130090222 A KR 20130090222A KR 1020120011376 A KR1020120011376 A KR 1020120011376A KR 20120011376 A KR20120011376 A KR 20120011376A KR 20130090222 A KR20130090222 A KR 20130090222A
- Authority
- KR
- South Korea
- Prior art keywords
- polyvinyl chloride
- chloride resin
- chlorinated polyvinyl
- chlorinated
- weight
- Prior art date
Links
- 239000011347 resin Substances 0.000 title claims abstract description 146
- 229920005989 resin Polymers 0.000 title claims abstract description 146
- 239000004801 Chlorinated PVC Substances 0.000 title claims abstract description 62
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims description 20
- 229920000915 polyvinyl chloride Polymers 0.000 claims abstract description 83
- 239000004800 polyvinyl chloride Substances 0.000 claims abstract description 83
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 31
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 30
- 239000000460 chlorine Substances 0.000 claims abstract description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000002455 scale inhibitor Substances 0.000 claims description 20
- -1 sodium fatty acid Chemical class 0.000 claims description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 9
- 239000000194 fatty acid Substances 0.000 claims description 9
- 229930195729 fatty acid Natural products 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 150000004665 fatty acids Chemical class 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 235000011167 hydrochloric acid Nutrition 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000000704 physical effect Effects 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 11
- 238000005259 measurement Methods 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000006872 improvement Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- YMOSUBJHLKNJIU-UHFFFAOYSA-N 1,1-dichloroethene Chemical group ClC(Cl)=C.ClC(Cl)=C YMOSUBJHLKNJIU-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- NTXKBEUECOMNMM-UHFFFAOYSA-N 1,2-dichloroethene Chemical group ClC=CCl.ClC=CCl NTXKBEUECOMNMM-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- TVWBTVJBDFTVOW-UHFFFAOYSA-N 2-methyl-1-(2-methylpropylperoxy)propane Chemical compound CC(C)COOCC(C)C TVWBTVJBDFTVOW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005157 alkyl carboxy group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
- E04B2/74—Removable non-load-bearing partitions; Partitions with a free upper edge
- E04B2/7407—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts
- E04B2/7416—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts with free upper edge, e.g. for use as office space dividers
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
- E04B2/74—Removable non-load-bearing partitions; Partitions with a free upper edge
- E04B2/76—Removable non-load-bearing partitions; Partitions with a free upper edge with framework or posts of metal
- E04B2/78—Removable non-load-bearing partitions; Partitions with a free upper edge with framework or posts of metal characterised by special cross-section of the frame members as far as important for securing wall panels to a framework with or without the help of cover-strips
- E04B2/7809—Removable non-load-bearing partitions; Partitions with a free upper edge with framework or posts of metal characterised by special cross-section of the frame members as far as important for securing wall panels to a framework with or without the help of cover-strips of single or multiple tubular form
- E04B2/7818—Removable non-load-bearing partitions; Partitions with a free upper edge with framework or posts of metal characterised by special cross-section of the frame members as far as important for securing wall panels to a framework with or without the help of cover-strips of single or multiple tubular form of substantially rectangular form
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
- E04B2/74—Removable non-load-bearing partitions; Partitions with a free upper edge
- E04B2/7407—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts
- E04B2/7416—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts with free upper edge, e.g. for use as office space dividers
- E04B2002/7418—Accessories supported on the free upper edge, e.g. auxiliary panels, noise abatement devices
-
- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B2/00—Walls, e.g. partitions, for buildings; Wall construction with regard to insulation; Connections specially adapted to walls
- E04B2/74—Removable non-load-bearing partitions; Partitions with a free upper edge
- E04B2/7407—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts
- E04B2/7416—Removable non-load-bearing partitions; Partitions with a free upper edge assembled using frames with infill panels or coverings only; made-up of panels and a support structure incorporating posts with free upper edge, e.g. for use as office space dividers
- E04B2002/742—Details of panel top cap
Landscapes
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
본 발명은 염소화된 폴리염화비닐수지의 제조방법 및 이로 제조된 염소화된 폴리염화비닐수지에 관한 것으로, 보다 구체적으로는 특정 분자량 분포를 가지는 2종의 폴리염화비닐수지 및 스케일방지제를 포함하여 염소화된 폴리염화비닐수지를 제조함으로써, 성형가공성, 내열성 및 내충격성이 현저히 향상되고, 반응기 내부 벽면에 스케일이 생성되지 않는 염소화된 폴리염화비닐수지의 제조방법 및 이로 제조된 염소화된 폴리염화비닐수지에 관한 것이다.
The present invention relates to a method for producing a chlorinated polyvinyl chloride resin and a chlorinated polyvinyl chloride resin prepared therefrom, and more specifically, to a chlorinated compound including two polyvinyl chloride resins having a specific molecular weight distribution and a scale inhibitor. By producing a polyvinyl chloride resin, a process for producing a chlorinated polyvinyl chloride resin which significantly improves molding processability, heat resistance and impact resistance, and does not generate scale on the inner wall of the reactor, and a chlorinated polyvinyl chloride resin prepared therefrom will be.
폴리염화비닐수지(Polyvinyl Chloride, PVC)는 기계적 강도, 내후성, 내약품성, 난연성 등의 여러 가지 장점이 있는 우수한 재로로써 많은 분야에 이용되고 있다. 그러나 내열성 및 내충격성이 부족하여 다양한 적용에 한계가 있었다. 부족한 내열성 및 내충격성을 개선하기 위한 방법으로 폴리염화비닐수지를 염소화함으로써 물성을 향상시키는 연구가 진행되어 왔다. Polyvinyl chloride resin (PVC) has been used in many fields as an excellent material having various advantages such as mechanical strength, weather resistance, chemical resistance, and flame retardancy. However, there is a limit to various applications due to the lack of heat resistance and impact resistance. In order to improve heat resistance and impact resistance, studies have been conducted to improve physical properties by chlorinating polyvinyl chloride resin.
종래의 폴리염화비닐수지(PVC)의 열변형온도(HDT, Heat Distortion Temperature)가 60~70℃ 부근이기 때문에 60℃ 이상인 열수에 대해서 사용할 수 없는 문제가 있었으나 염소화된 폴리염화비닐수지(CPVC)는 열변형온도(HDT, Heat Distortion Temperature)가 종래의 폴리염화비닐수지(PVC)보다 20 내지 40℃ 가량 높기 때문에 60℃ 이상되는 열수에 대하여 사용이 가능하게 되었으며, 기존 열수에 사용되어 왔던 금속관 및 금속연결부 등에서 발생하는 부식문제를 해결할 수 있었다. Since the heat distortion temperature (HDT) of conventional polyvinyl chloride resin (PVC) is around 60 to 70 ° C, there is a problem that cannot be used for hot water above 60 ° C, but chlorinated polyvinyl chloride resin (CPVC) Since heat distortion temperature (HDT) is about 20 to 40 ° C higher than that of conventional polyvinyl chloride resin (PVC), it can be used for hot water of 60 ° C or more. Corrosion problems at the joints were solved.
그러나 염소화된 폴리염화비닐수지(CPVC)는 열변형온도가 높기 때문에, 용융 및 가공 성형시에 높은 온도와 강한 전단력이 요구되고, 이로 인하여 수지의 열화가 쉽게 발생하는 문제가 발생함으로써, 염소화된 폴리염화비닐수지는 성형 가공폭이 좁고, 충분히 용융되지 못한 상태에서 성형 및 가공이 되는 경우가 많이 발생하였다. However, since chlorinated polyvinyl chloride resin (CPVC) has a high heat deformation temperature, high temperature and strong shear force are required at the time of melting and processing molding, thereby causing a problem of easily deterioration of the resin. Vinyl chloride resins have a narrow molding process width, and many cases are formed and processed in a state in which they are not sufficiently melted.
또한, 종래 기술에는 내열성 및 내충격성 향상을 위하여, 충진제 또는 염화비닐과 공중합 가능한 비닐계 수지를 사용하는 기술도 공지되어 있으나, 내열성 향상이 미미해지는 문제가 있으며, 성형 가공시 용융성능이 향상되는 정도가 미약하고, 중합시 다량의 스케일이 발생하여 반응기 벽면에 부착되어 스케일 제거작업이 함께 수행되어야하는 문제점이 있었다. In addition, in the prior art, a technique using a vinyl resin copolymerizable with a filler or vinyl chloride is also known to improve heat resistance and impact resistance, but there is a problem that the heat resistance improvement is insignificant, and the degree of improvement in melt performance during molding processing. It was weak and there was a problem that a large amount of scale was generated during polymerization and attached to the wall of the reactor so that descaling work should be performed together.
일본공개특허 제2005-126519호(특허문헌 1)에는 클로로포름과 같은 팽창액의 사용 없이 수상에서 폴리염화비닐수지의 광염소화 반응을 개시하여 제조되는 방법을 언급하고 있으며, 대한민국등록특허 제0452391호(특허문헌 2)에는 염소화된 폴리에틸렌 및 충격 변형제를 포함하여 2단계의 염소화반응이 진행된 염소화된 폴리염화비닐화합물을 개시하고 있다. Japanese Laid-Open Patent Publication No. 2005-126519 (Patent Document 1) refers to a method for preparing a photochlorination reaction of a polyvinyl chloride resin in an aqueous phase without using an expansion liquid such as chloroform, and Korean Patent No. 0452391 ( Patent Document 2) discloses a chlorinated polyvinyl chloride compound in which a two-step chlorination reaction is performed, including a chlorinated polyethylene and an impact modifier.
이상에서 살핀 바와 같이, 종래기술을 통해서는 폴리염화비닐수지의 염소화가 충분히 되면 용융성 및 성형가공성이 저하되고, 용융성 및 성형가공성이 향상되면, 내열성이 저하되는 문제를 발생하는 등, 용융특성 및 성형가공성이 우수하면서 내충격성 및 내열성이 우수한 염소화 폴리염화비닐수지의 제조가 어려운 문제가 있다. As described above, according to the prior art, when the chlorination of the polyvinyl chloride resin is sufficient, the meltability and the moldability decrease, and when the meltability and the moldability improve, the problem of heat resistance decreases. And it is difficult to manufacture a chlorinated polyvinyl chloride resin having excellent molding processability and excellent impact resistance and heat resistance.
특히, 염소화과정에서 스케일이 발생하여, 반응기 내벽을 오염시키게 되며, 이로 인해 염소화반응이 잘 진행되지 않으며, 특히, 발생되는 스케일에 의하여 자외선 조사가 원활하게 이루어지지 않아, 반응시간이 길어지며, 염소화반응이 균일하게 이루어지지 않는 단점이 있다.
In particular, the scale is generated during the chlorination process, which contaminates the inner wall of the reactor, and thus the chlorination reaction does not proceed well, and in particular, the irradiation time is not long due to the generated scale, so that the reaction time is long, and the chlorination There is a disadvantage that the reaction is not uniform.
본 발명은 종래의 문제점을 해결하기 위한 것으로, 특정 분자량 분포를 가지는 2종의 폴리염화비닐 수지 및 스케일방지제를 포함하는 조성물을 이용하여, 염소화된 폴리염화비닐수지를 제조했을 때, 성형가공성, 내열성 및 내충격성이 현저히 향상되고, 특히, 반응기 내부 벽면에 스케일이 생성되지 않는 염소화된 폴리염화비닐수지의 제조방법을 제공하는 것을 목적으로 한다. The present invention has been made to solve the conventional problems, and when forming a chlorinated polyvinyl chloride resin using a composition comprising two kinds of polyvinyl chloride resin having a specific molecular weight distribution and an anti-scaling agent, molding processability, heat resistance And to provide a method for producing a chlorinated polyvinyl chloride resin in which impact resistance is remarkably improved, and in particular, no scale is formed on the inner wall of the reactor.
또한, 상기 제조방법으로 제조된 염소화된 폴리염화비닐 수지를 제공하는 것을 목적으로 한다.
It is also an object of the present invention to provide a chlorinated polyvinyl chloride resin prepared by the above method.
본 발명은 상기와 같은 목적을 달성하기 위하여, According to an aspect of the present invention,
(a) 중합도가 400 내지 800이고, K값이 40 내지 62인 제1폴리염화비닐수지, 중합도가 900 내지 1800이고, K값이 64 내지 81인 제2폴리염화비닐수지 및 스케일방지제를 물과 혼합하여 수성 슬러리를 제조하는 단계; (b) 상기 수성 슬러리에 염소를 투입하고 가압하여 염소화하는 단계; 및 (c) 과량의 염산과 염소화폴리염화비닐수지를 분리하는 단계;를 포함하며, (a)단계에서 슬러리에 포함되는 산소의 농도가 100ppm 미만이 되도록 제어하고, (b)단계에서 염소화단계는 10 내지 100psig의 압력에서 5 내지 50분간 진행하는 염소화폴리염화비닐수지의 제조방법을 제공한다. (a) a first polyvinyl chloride resin having a polymerization degree of 400 to 800, a K value of 40 to 62, a second polyvinyl chloride resin having a polymerization degree of 900 to 1800 and a K value of 64 to 81, and a scale inhibitor; Mixing to prepare an aqueous slurry; (b) chlorination by adding chlorine to the aqueous slurry and pressing; And (c) separating the excess hydrochloric acid and chlorinated polyvinyl chloride resin, and (c) controlling the concentration of oxygen contained in the slurry to be less than 100 ppm, and in the (b) chlorination step. It provides a method for producing chlorinated polyvinyl chloride resin proceeding for 5 to 50 minutes at a pressure of 10 to 100 psig.
또한, 상기 (a)단계에서 제1폴리염화비닐수지 및 제2폴리염화비닐수지의 혼합비는 95~5중량% : 95~5중량%이며, 상기 스케일방지제는 상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지 혼합물 100중량부에 대하여 0.01 내지 10중량부인 염소화폴리염화비닐수지의 제조방법을 제공한다.
In addition, the mixing ratio of the first polyvinyl chloride resin and the second polyvinyl chloride resin in step (a) is 95 to 5% by weight: 95 to 5% by weight, the scale inhibitor is the first polyvinyl chloride resin and agent Provided is a method for producing a chlorinated polyvinyl chloride resin that is 0.01 to 10 parts by weight with respect to 100 parts by weight of the dipolyvinyl chloride resin mixture.
또한, 본 발명은 상기와 같은 목적을 달성하기 위하여, 상기 제조방법으로 제조되는 염소 함유율이 65 내지 75%인 염소화폴리염화비닐수지를 제공한다. In addition, the present invention provides a chlorinated polyvinyl chloride resin having a chlorine content of 65 to 75% prepared by the above production method in order to achieve the above object.
상기 염소화폴리염화비닐수지는 중합도가 400 내지 800이고 K값이 40 내지 62인 제1폴리염화비닐수지, 중합도가 900 내지 1800이고 K값이 64 내지 81인 제2폴리염화비닐수지 및 스케일방지제를 포함하는 염소화폴리염화비닐수지를 제공한다. The chlorinated polyvinyl chloride resin has a polymerization degree of 400 to 800 and a first polyvinyl chloride resin having a K value of 40 to 62, a second polyvinyl chloride resin having a polymerization degree of 900 to 1800 and a K value of 64 to 81 and a scale inhibitor. It provides a chlorinated polyvinyl chloride resin containing.
상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지의 혼합비는 95~5중량% : 5~95중량%이고, 상기 스케일방지제는 상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지 혼합물 100중량부에 대하여 0.01 내지 10중량부 포함하는 염소화폴리염화비닐수지를 제공한다.The mixing ratio of the first polyvinyl chloride resin and the second polyvinyl chloride resin is 95 to 5% by weight: 5 to 95% by weight, the scale inhibitor is the mixture of the first polyvinyl chloride resin and the second polyvinyl chloride resin 100 It provides a chlorinated polyvinyl chloride resin containing 0.01 to 10 parts by weight based on parts by weight.
스케일방지제는 비누(지방산 나트륨), 모노알킬 황산염, 알킬폴리옥시에틸렌 황산염, 알킬벤젠술폰산염, 모노알킬인산염, 모노알킬트리메틸암모늄염, 디알킬디메틸암모늄염, 알킬벤질메틸암모늄염, 알킬설포베타인, 알킬카르복시베타인, 폴리옥시에틸렌알킬에테르, 지방산 솔비탄에스테르, 지방산 디에탄올아민, 알킬모노글리세릴에테르 중에서 선택되는 1종 또는 2종 이상인 염소화폴리염화비닐수지를 제공한다.Antiscalants include soap (sodium fatty acid), monoalkyl sulfates, alkylpolyoxyethylene sulfates, alkylbenzenesulfonates, monoalkylphosphates, monoalkyltrimethylammonium salts, dialkyldimethylammonium salts, alkylbenzylmethylammonium salts, alkylsulfobetaines, alkylcarboxy Provided is one or two or more chlorinated polyvinyl chloride resins selected from betaine, polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, and alkyl monoglyceryl ether.
또한, 염소화폴리염화비닐수지는 인장강도가 500~600kg/㎠이고, 굴곡강도가 700~800kg/㎠이며, 충격강도가 20 내지 60kgcm/cm이고, 비커트 연화점이 100 내지 140℃인 염소화폴리염화비닐수지를 제공한다. In addition, the chlorinated polyvinyl chloride resin has a tensile strength of 500 to 600 kg / cm 2, a flexural strength of 700 to 800 kg / cm 2, an impact strength of 20 to 60 kgcm / cm, and a non-cut softening point of 100 to 140 ° C. Provide vinyl resin.
본 발명의 염소화된 폴리염화비닐수지의 제조방법 및 이로 제조된 염소화된 폴리염화비닐수지에 따르면, 특정 분자량 분포를 가지는 2종의 폴리염화비닐 수지, 염소 및 스케일방지제를 포함하여 염소화된 폴리염화비닐수지를 제조했을 때, 성형가공성과 고내열성 및 내충격성이 현저히 향상되었으며, 특정의 스케일방지제를 포함함으로써 반응기 내부 벽면에 스케일이 생성되지 않아, 제조공정에서 획기적으로 반응시간을 단축시킬 수 있으며, 생산성의 향상을 이룬다.
According to the production method of chlorinated polyvinyl chloride resin of the present invention and the chlorinated polyvinyl chloride resin prepared therefrom, chlorinated polyvinyl chloride including two polyvinyl chloride resins having a specific molecular weight distribution, chlorine and scale inhibitors When the resin is manufactured, the molding processability, high heat resistance and impact resistance are remarkably improved, and by including a specific anti-scaling agent, no scale is generated on the inner wall of the reactor, which dramatically shortens the reaction time in the manufacturing process, and productivity Achieves an improvement.
이하, 본 발명의 염소화된 폴리염화비닐수지의 제조방법 및 이로 제조된 염소화된 폴리염화비닐 수지에 대하여 바람직한 실시형태 및 물성측정 방법을 상세히 설명한다. 본 발명은 하기의 실시예에 의하여 보다 더 잘 이해될 수 있으며, 하기의 실시예는 본 발명의 예시 목적을 위한 것이고, 첨부된 특허 청구범위에 의하여 한정되는 보호범위를 제한하고자 하는 것은 아니다.
Hereinafter, preferred embodiments of the chlorinated polyvinyl chloride resin of the present invention and chlorinated polyvinyl chloride resin prepared therefrom will be described in detail. The present invention may be better understood by the following examples, which are for the purpose of illustrating the present invention and are not intended to limit the scope of protection defined by the appended claims.
본 발명은 염소화된 폴리염화비닐수지의 제조방법에 대하여 상세히 설명한다. (a) 중합도가 400 내지 800이고 K값이 40 내지 62인 제1폴리염화비닐수지, 중합도가 900 내지 1800이고 K값이 64 내지 81인 제2폴리염화비닐수지 및 스케일방지제를 물과 혼합하여 수성 슬러리를 제조하는 단계; (b) 상기 수성 슬러리에 염소를 투입하고 가압하여 염소화하는 단계; 및 (c) 과량의 염산과 염소화폴리염화비닐수지를 분리하는 단계를 포함하는 것이 바람직하다.
The present invention will be described in detail for the production method of chlorinated polyvinyl chloride resin. (a) a first polyvinyl chloride resin having a polymerization degree of 400 to 800 and a K value of 40 to 62, a second polyvinyl chloride resin having a polymerization degree of 900 to 1800 and a K value of 64 to 81 and a scale inhibitor with water Preparing an aqueous slurry; (b) chlorination by adding chlorine to the aqueous slurry and pressing; And (c) separating the excess hydrochloric acid and chlorinated polyvinyl chloride resin.
제1폴리염화비닐수지 및 제2폴리염화비닐수지를 포함하는 수성슬러리는 밀폐가 가능한 반응기에서 반응시키는 것이 바람직하며, 상기 (a)단계의 온도는 10 내지 40℃의 온도를 유지하는 것이 효과적이다. 상기 온도 범위에서 반응기에 충진되는 염소가 폴리염화비닐수지에 효과적으로 침투할 수 있는 장점이 있으며, 상기 반응기의 온도가 10℃미만일 경우에는, 염소의 용존량은 증가하나, (b)단계시 승온과정에서 시간이 많이 소요되는 문제가 발생하고, 상기 반응기의 온도가 40℃ 초과일 경우에는, 염소의 용존량이 감소하여 (b)단계의 반응시간이 길어지는 문제가 발생한다. It is preferable to react the aqueous slurry including the first polyvinyl chloride resin and the second polyvinyl chloride resin in a reactor that can be sealed, and the temperature of step (a) is effective to maintain a temperature of 10 to 40 ℃. . In the above temperature range, the chlorine charged in the reactor can effectively penetrate the polyvinyl chloride resin. When the temperature of the reactor is less than 10 ° C., the dissolved amount of chlorine increases, but in step (b), the temperature raising process is performed. In the time-consuming problem occurs, and when the temperature of the reactor is more than 40 ℃, the dissolved amount of chlorine decreases, the problem occurs that the reaction time of step (b) is long.
또한, 반응기 내부에 산소가 많이 존재할 경우, 염소화반응 진행에 방해가 되기 때문에, 질소, 헬륨, 아르곤 등을 포함하는 불활성 기체를 투입하여 산소의 함량을 제어하거나, 반응기 내부를 감압하여 산소의 함량을 제어하는 등 통상적인 방법으로 실시될 수 있으며, 반응기 내부의 산소 농도가 100ppm 미만이 되도록 제어하는 것이 효과적이다. In addition, when there is a lot of oxygen in the reactor, because it interferes with the progress of the chlorination reaction, inert gas containing nitrogen, helium, argon, etc. is added to control the content of oxygen, or to reduce the content of oxygen by reducing the inside of the reactor It can be carried out by a conventional method such as control, it is effective to control so that the oxygen concentration in the reactor is less than 100ppm.
상기 b) 단계는 수성 슬러리에 염소를 투입하고 가압하여 염소화하는 단계이다. 염소화 반응을 효과적으로 수행하기 위하여 수성 슬러리가 포함된 반응기 내부로 과량의 염소(Cl)를 기체 또는 액체 상태로 투입하여 수성 슬러리 상에 염소가 충분히 용존되도록 교반시키는 침잠단계가 선행되는 것이 바람직하고, 상기 침잠단계는 10 내지 100psig의 압력에서 5 내지 50분간 수행하는 것이 효과적이다. 반응기의 압력이 10psig 미만일 경우에는, 수성슬러리에 염소가 충분히 용존되지 못하여 염소화 반응시간이 지나치게 길어지고, 충분한 내열성 및 내충격성의 물성향상이 어려운 문제가 발생하고, 반응기의 압력이 100psig 초과일 경우에는, 반응시간은 다소 짧아지나, 균일한 염소화가 어려워 내열성 및 내충격성의 물성향상 효과를 미미하게 하는 문제가 발생한다. Step b) is a step of chlorination by adding chlorine to the aqueous slurry and pressurization. In order to effectively perform the chlorination reaction, it is preferable that a immersion step of injecting excess chlorine (Cl) into a gas or liquid state into the reactor containing the aqueous slurry and agitating so that chlorine is sufficiently dissolved in the aqueous slurry is performed. The submerging step is effective for 5 to 50 minutes at a pressure of 10 to 100 psig. When the pressure of the reactor is less than 10 psig, chlorine is not sufficiently dissolved in the aqueous slurry, so the chlorination reaction time becomes too long, and it is difficult to improve the physical properties of sufficient heat resistance and impact resistance, and when the pressure of the reactor is more than 100 psig, Although the reaction time is rather short, there is a problem that it is difficult to uniform chlorination, so that the effect of improving the physical properties of heat resistance and impact resistance is insignificant.
상기 침잠시간이 5분 미만일 경우에는 1,1-디클로로에틸렌(1,1-dichloroethylene)구조가 많이 형성되어, 내열성 및 내충격성의 물성이 저하되는 문제가 발생하며, 침잠시간이 50분 초과이면, 반응시간이 지나치게 길어져, 상업적 측면에서 봤을 때, 공정비용이 상승하는 문제가 발생한다. 5 내지 50분의 최적의 시간으로 침잠시킬 경우, 1,2-디클로로에틸렌(1,2-dichloroethylene)구조가 많이 형성되어, 안정한 염소화 반응이 진행될 수 있으며, 이로 인하여 내열성 및 내충격성이 현저히 향상되는 장점이 있다. 상기 침잠단계를 수행하지 않고 바로 염소화단계를 진행할 수 있으나, 이는 염소화 반응 효율을 감소시켜 반응시간이 길어지고, 내열성 및 내충격성 등의 물성 향상을 미미하게 하는 문제가 발생한다. When the submersion time is less than 5 minutes, a lot of 1,1-dichloroethylene (1,1-dichloroethylene) structure is formed, the problem of deterioration of heat resistance and impact resistance properties occurs, if the submersion time is more than 50 minutes, reaction The time is too long, and from a commercial point of view, there is a problem that the process cost increases. When immersed in an optimal time of 5 to 50 minutes, a lot of 1,2-dichloroethylene (1,2-dichloroethylene) structure is formed, a stable chlorination reaction can proceed, thereby significantly improving heat resistance and impact resistance There is an advantage. The chlorination step may proceed directly without performing the submersion step, but this decreases the chlorination reaction efficiency, resulting in a long reaction time, and a problem of insignificant improvement in physical properties such as heat resistance and impact resistance.
상기 침잠단계 후, 광조사나 화학반응개시제를 사용하여 염소화 반응을 진행하는 것이 효과적이다. 반응개시광원으로는 통상적으로 사용되는 광경화반응용 광원이면 제한되지 않으며, 예를 들면, Neon Glow Tube, Fluorescent Tube, Carbon Arc, Sodium vapor lamp, U.V lamp 중에서 선택되는 1종 또는 2종을 사용할 수 있으며, 특히 U.V lamp를 사용하는 것이 효과적이다. 또한, 화학반응 개시제를 사용하여 반응시킬 수 있다. 화학반응개시제는 통상의 과산화계열 촉매이면 제한되지 않으며, 예를 들면, 메틸에틸케톤퍼옥사이드, 메틸이소부틸케톤퍼옥사이드 등의 케톤퍼옥사이드류 ; 2,4,4-트리메틸펜틸-2-하이드로퍼옥사이드, 디이소프로필벤젠하이드로퍼옥사이드 등의 하이드로퍼옥사이드류; 이소부틸퍼옥사이드, 2,4-디클로로벤조일퍼옥사이드, 벤조일퍼옥사이드, 1,3-비스(터셔리-부틸퍼옥시이소프로필렌)벤젠, 2,5-디메틸-2,5-디(터셔리부틸퍼옥시)헥산 등의 디아실퍼옥사이드류; 1,1-디-터셔리-부틸퍼옥시-3,3,5-트리메틸사이클헥산, 2,2-디-(터셔리부틸퍼옥시)부탄 등의 퍼옥시케탈류; 2,2,4-트리메틸펜틸퍼옥시네오데칸노에이트, 터셔리-부틸퍼옥시-네오데칸노에이트 등의 알킬퍼에스테류; 및 디-3-메톡시부틸퍼옥시디카보네이트, 터셔리퍼옥시부틸퍼옥시이소프로필카보네이트 등의 퍼카보네이트류 중에서 선택되는 1종 또는 2종 이상이 효과적이다. 그러나 본 발명은 이들 예에만 한정되는 것은 아니며, 광조사나 화학 반응 개시제중 선택하여 사용할 수 있다. After the submersion step, it is effective to proceed with the chlorination reaction using light irradiation or a chemical reaction initiator. The reaction starting light source is not limited as long as it is a light source for photocuring reaction that is commonly used, for example, may be used one or two selected from Neon Glow Tube, Fluorescent Tube, Carbon Arc, Sodium vapor lamp, UV lamp In particular, it is effective to use a UV lamp. It can also be reacted using a chemical reaction initiator. The chemical reaction initiator is not limited as long as it is a common peroxide catalyst, and examples thereof include ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide; Hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide and diisopropylbenzenehydroperoxide; Isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, benzoyl peroxide, 1,3-bis (tert-butylperoxyisopropylene) benzene, 2,5-dimethyl-2,5-di (tert-butyl Diacyl peroxides such as peroxy) hexane; Peroxy ketals such as 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclehexane and 2,2-di- (tertarybutylperoxy) butane; Alkyl peresters such as 2,2,4-trimethylpentyl peroxy neodecannoate and tertiary-butyl peroxy-neodecannoate; And one or two or more selected from percarbonates such as di-3-methoxybutyl peroxydicarbonate and tertiary oxybutyl peroxy isopropyl carbonate. However, the present invention is not limited only to these examples, and can be used by selecting from light irradiation or a chemical reaction initiator.
상기 염소화 반응은 30 내지 70℃ 온도 및 10 내지 100psig 압력에서 진행되는 것이 효과적이다. 염소화 반응에서 온도가 30℃, 압력이 10psig 미만일 경우에는 반응시간이 지나치게 길어지고, 충분한 내열성 및 내충격성의 물성향상이 어려운 문제가 발생하고, 염소화 반응에서 온도가 70℃, 압력이 100psig 초과일 경우에는 , 반응시간은 다소 짧아지나, 균일한 염소화가 어려워 내열성 및 내충격성의 물성향상 효과를 미미하게 하는 문제가 발생한다. The chlorination reaction is effective to proceed at a temperature of 30 to 70 ℃ and 10 to 100 psig pressure. In the chlorination reaction, when the temperature is 30 ° C. and the pressure is less than 10 psig, the reaction time becomes too long, and it is difficult to improve the physical properties of sufficient heat resistance and impact resistance. In the chlorination reaction, when the temperature is 70 ° C. and the pressure is more than 100 psig. The reaction time is rather short, but it is difficult to uniform chlorination, resulting in a problem that the effect of improving the physical properties of heat resistance and impact resistance is negligible.
상기 염소화 반응의 종료는 2내지 6시간동안 지속한 후 종료하거나, 반응기에 설치된 실린더에서 최초 충진된 염소의 양에서 손실된 염소의 중량을 측정하여 종료 시점이 결정되는 것이 효과적이다. 반응시간에 따라서 염소함유율이 결정되고, 염소화된 폴리염화비닐수지의 최적의 염소함유율은 65 내지 75%을 포함하는 것이 바람직하다. The end of the chlorination reaction is effective after lasting for 2 to 6 hours, or by determining the end point by measuring the weight of the chlorine lost from the amount of chlorine initially charged in the cylinder installed in the reactor. The chlorine content is determined according to the reaction time, and the optimal chlorine content of the chlorinated polyvinyl chloride resin preferably contains 65 to 75%.
반응 시간이 2시간 미만일 경우, 65%이하의 염소 함유된 염소화 폴리염화비닐수지를 제조할 수 있으며, 반응시간이 6시간 이상 지속되면 70%의 고염소 함유된 염소화 폴리염화비닐수지를 제조할 수 있다. If the reaction time is less than 2 hours, chlorine-containing polyvinyl chloride resin containing 65% or less can be prepared. If the reaction time lasts 6 hours or more, 70% of chlorine-containing polyvinyl chloride resin can be prepared. have.
상기 염소화 반응이 종료되면, 과량의 염산과 염소화폴리염화비닐수지를 분리하는 (c) 단계를 수행하는 것이 바람직하다. 이때 반응이 완료된 수성 슬러리를 냉각되지 않은 상태에서 원심 분리하여 염산과 염소화된 폴리염화비닐수지를 분리한다. 분리된 염소화된 폴리염화비닐수지는 통상의 알칼리 수용액으로 중화될 수 있으며, 특히 탄산수소나트륨(NaHCO3)으로 중화되는 것이 효과적이다. 이후 물을 사용하여 산도를 pH 6 내지 8 범위까지 잔류 염산을 제거하는 것이 바람직하며, 상기 중화된 염소화된 폴리염화비닐 수지를 건조장치를 이용하여 60 내지 80℃ 온도에서 3 내지 6시간 건조하는 것이 효과적이다. 건조온도가 60℃ 미만 또는 건조시간가 3시간 미만일 경우에는, 건조 시간이 길어지는 문제가 발생하고, 건조온도가 80℃초과 또는 건조시간이 6시간 초과일 경우에는, 염소화된 폴리염화비닐수지가 열화되어 내열성 및 내충격성의 향상 효과를 미미하게 하는 문제가 발생한다.
When the chlorination reaction is completed, it is preferable to perform step (c) of separating the excess hydrochloric acid and chlorinated polyvinyl chloride resin. At this time, the hydrolyzed aqueous slurry is centrifuged in an uncooled state to separate hydrochloric acid and chlorinated polyvinyl chloride resin. The separated chlorinated polyvinyl chloride resin can be neutralized with a conventional aqueous alkali solution, and particularly neutralized with sodium hydrogencarbonate (NaHCO 3). After that, it is preferable to remove residual hydrochloric acid to pH 6 to 8 range using water, and to dry the neutralized chlorinated polyvinyl chloride resin at a temperature of 60 to 80 ℃ using a drying apparatus for 3 to 6 hours. effective. If the drying temperature is less than 60 ° C. or the drying time is less than 3 hours, the drying time becomes long. If the drying temperature is more than 80 ° C. or the drying time is more than 6 hours, the chlorinated polyvinyl chloride resin deteriorates. There arises a problem that the effect of improving the heat resistance and impact resistance is negligible.
다음으로, 상기 제조방법으로 제조된 염소화된 폴리염화비닐수지에 대하여 상세히 설명한다. Next, the chlorinated polyvinyl chloride resin produced by the above production method will be described in detail.
본 발명은 중합도가 400 내지 800이고 K값이 40 내지 62인 제1폴리염화비닐수지, 중합도가 900 내지 1800이고 K값이 64 내지 81인 제2폴리염화비닐수지 및 스케일방지제를 포함하여 제조된 염소 함유율이 65 내지 75%인 염소화폴리염화비닐수지를 제공한다. The present invention includes a first polyvinyl chloride resin having a polymerization degree of 400 to 800 and a K value of 40 to 62, a second polyvinyl chloride resin having a polymerization degree of 900 to 1800 and a K value of 64 to 81 and a scale inhibitor. A chlorinated polyvinyl chloride resin having a chlorine content of 65 to 75% is provided.
제1폴리염화비닐수지는 중합도가 400 내지 800이고, K값이 40 내지 62인 것이 바람직하고, 보다 바람직하게는 중합도가 450 내지 800이고, K값이 52 내지 62인 것이 효과적이며, 이는 용융특성이 우수하여 가공성형성을 향상시키기 위하여 첨가된다. 또한, 제2폴리염화비닐수지는 중합도가 900 내지 1800이고, K값이 64 내지 81인 것이 바람직하고, 보다 바람직하게는 중합도가 1000 내지 1800이고, K값이 65 내지 75인 것이 효과적이며, 이는 내열성 및 내충격성을 향상시키기 위하여 첨가된다. It is preferable that the first polyvinyl chloride resin has a polymerization degree of 400 to 800, a K value of 40 to 62, more preferably a polymerization degree of 450 to 800, and a K value of 52 to 62. It is excellent and is added to improve processability. In addition, it is preferable that the second polyvinyl chloride resin has a degree of polymerization of 900 to 1800, a K value of 64 to 81, more preferably a degree of polymerization of 1000 to 1800, and a K value of 65 to 75. It is added to improve heat resistance and impact resistance.
상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지는 일반적으로 폴리염화비닐수지로 이용되는 공지의 수지를 제한 없이 사용할 수 있으며, 구체적인 예로는 염화비닐단독중합체, 염화비닐과 에틸렌, 프로필렌, 알킬비닐에테르, 비닐리덴클로라이드, 아세트산비닐, 말레인산에스테르 및 이들의 공중합체 또는 이들의 혼합물을 사용하는 것이 효과적이다. The first polyvinyl chloride resin and the second polyvinyl chloride resin can be used without limitation, known resins generally used as polyvinyl chloride resin, specific examples are vinyl chloride homopolymer, vinyl chloride and ethylene, propylene, alkyl It is effective to use vinyl ether, vinylidene chloride, vinyl acetate, maleic acid esters and copolymers thereof or mixtures thereof.
또한, 상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지의 혼합비는 5~95중량% : 95~5중량%인 것이 바람직하고, 보다 바람직하게는 상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지의 혼합비가 20~80중량% : 80~20중량%인 것이 효과적이다. In addition, the mixing ratio of the first polyvinyl chloride resin and the second polyvinyl chloride resin is preferably 5 to 95% by weight: 95 to 5% by weight, more preferably the first polyvinyl chloride resin and the second poly It is effective that the mixing ratio of vinyl chloride resin is 20 to 80% by weight: 80 to 20% by weight.
상기 혼합비로 제조하였을 경우, 가공성형성이 우수하면서 동시에 기계적 물성, 내열성 및 내충격성이 우수한 염소화된 폴리염화비닐수지 조성물을 얻을 수 있었다. 제1폴리염화비닐수지가 5 중량% 미만이거나 제2폴리염화비닐수지가 95중량% 초과일 경우에는, 용융특성 및 가공성형성이 현저히 감소되는 문제가 발생하며, 제1염화비닐수지가 95중량% 초과이거나 제2폴리염화비닐수지가 5중량% 미만일 경우에는, 내열성 및 내충격성이 현저히 감소되는 문제가 발생하였다. When prepared in the above mixing ratio, it was possible to obtain a chlorinated polyvinyl chloride resin composition excellent in formability and excellent mechanical properties, heat resistance and impact resistance. When the first polyvinyl chloride resin is less than 5% by weight or the second polyvinyl chloride resin is more than 95% by weight, there is a problem in that melting characteristics and processability are significantly reduced, and the first vinyl chloride resin is 95% by weight. In the case where the amount of the polyvinyl chloride resin is exceeded or less than 5% by weight, a problem arises in that heat resistance and impact resistance are significantly reduced.
또한, 상기 염소화 폴리염화비닐수지에 포함되는 스케일방지제는 통상의 음이온성 계면활성제, 양이온성 계면활성제, 양쪽성 계면활성제 또는 비이온성 계면활성제 중에서 선택되는 1종 또는 2종을 제한 없이 사용가능하다. 예를 들면, 비누(지방산 나트륨), 모노알킬 황산염, 알킬폴리옥시에틸렌 황산염, 알킬벤젠술폰산염, 모노알킬인산염, 모노알킬트리메틸암모늄염, 디알킬디메틸암모늄염, 알킬벤질메틸암모늄염, 알킬설포베타인, 알킬카르복시베타인, 폴리옥시에틸렌알킬에테르, 지방산 솔비탄에스테르, 지방산 디에탄올아민, 알킬모노글리세릴에테르 중에서 선택되는 1종 또는 2종 이상인 것이 효과적이다. 상기 스케일 방지제는 웨팅(Wetting)성을 높이고, 반응기 내부 벽면에 스케일 발생을 방지하므로 인해 염소화 반응에서 폴리염화비닐수지의 균일한 염소화 반응을 통한 가공성, 내열성 및 내충격성을 향상 시킬 수 있다.In addition, the scale inhibitor included in the chlorinated polyvinyl chloride resin can be used one or two selected from conventional anionic surfactants, cationic surfactants, amphoteric surfactants or nonionic surfactants without limitation. For example, soap (sodium fatty acid), monoalkyl sulfate, alkylpolyoxyethylene sulfate, alkylbenzenesulfonate, monoalkylphosphate, monoalkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzylmethylammonium salt, alkylsulfobetaine, alkyl It is effective to be 1 type or 2 or more types chosen from a carboxybetaine, polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine, and alkyl monoglyceryl ether. The anti-scaling agent improves wetting and prevents generation of scale on the inner wall of the reactor, thereby improving workability, heat resistance, and impact resistance through uniform chlorination of polyvinyl chloride resin in the chlorination reaction.
상기 스케일방지제는 상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지 혼합물 100중량부에 대하여 0.01 내지 10중량부 포함하는 것이 바람직하다. 스케일방지제의 함량이 0.01중량부 미만일 경우에는, 제1폴리염화비닐수지 및 제2폴리염화비닐수지에 대한 웨팅성(Wetting) 향상 및 스케일 제거의 효과가 미미한 문제가 발생하며, 스케일방지제의 함량이 10중량부 초과일 경우에는, 과량 첨가된 스케일방지제 성분에 의하여 염소화 반응을 방해하여, 충분한 염소화 폴리염화비닐수지를 제조할 수 없으며, 이에 따라 내열성, 내충격성 향상이 미미해지는 문제가 발생한다. The scale inhibitor may include 0.01 to 10 parts by weight based on 100 parts by weight of the mixture of the first polyvinyl chloride resin and the second polyvinyl chloride resin. When the content of the scale inhibitor is less than 0.01 part by weight, there is a problem that the effect of improving the wetting and removing the scale for the first polyvinyl chloride resin and the second polyvinyl chloride resin is insignificant. When it is more than 10 parts by weight, the chlorination reaction is prevented by the excessively added scale inhibitor component, so that sufficient chlorinated polyvinyl chloride resin cannot be produced, resulting in a problem in that heat resistance and impact resistance improvement are insignificant.
또한, 상기의 제조방법으로 제조된 염소화된 폴리염화비닐수지는 염소 함유율이 65 내지 75%이고, 인장강도가 500~600kg/㎠이고, 굴곡강도가 700~800kg/㎠이며, 충격강도가 20 내지 60kgcm/cm이고, 비커트 연화점이 100 내지 140℃인 것이 바람직하다. In addition, the chlorinated polyvinyl chloride resin prepared by the above production method has a chlorine content of 65 to 75%, a tensile strength of 500 to 600 kg / cm 2, a bending strength of 700 to 800 kg / cm 2, and an impact strength of 20 to It is 60 kgcm / cm, and it is preferable that a beaker softening point is 100-140 degreeC.
또한, 밀도가 1.5 내지 1.8g/cc(25℃)이며, 유리전이온도(Tg)가 115 내지 160℃으로, 용융특성이 향상되어 기계적 물성의 저하없이 성형 가공성이 향상되었으며, 내열성 및 내충격성이 현저히 향상되고, 반응기 내부에 스케일이 형성되지 않는 염소화된 폴리염화비닐수지를 제조할 수 있었다.
In addition, the density is 1.5 to 1.8 g / cc (25 ℃), the glass transition temperature (Tg) is 115 to 160 ℃, the melting characteristics are improved, the molding processability without degradation of mechanical properties is improved, heat resistance and impact resistance It was possible to produce chlorinated polyvinyl chloride resins that were markedly improved and did not form scale inside the reactor.
이하, 본 발명의 염소화된 폴리염화비닐 수지의 특성을 다음과 같은 시험방법으로 평가하였으며, 결과를 하기 [표 2]에 나타내었다. Hereinafter, the properties of the chlorinated polyvinyl chloride resin of the present invention were evaluated by the following test method, and the results are shown in the following [Table 2].
(1) 인장강도(1) Tensile strength
ASTM D638방법으로 Instron 인장시험기(Model 4204)를 사용하여 인장속도 50mm/min로 하여 측정하였다.Using an Instron tensile tester (Model 4204) by the ASTM D638 method was measured at a tensile rate of 50mm / min.
(2) 굴곡강도(2) Flexural strength
ASTM D790방법으로 Instron 인장시험기(Model 4204)를 사용하여 속도 10mm/min로 하여 측정하였다. Using an Instron tensile tester (Model 4204) by the ASTM D790 method was measured at a speed of 10mm / min.
(3) 비커트연화점(3) Becut softening point
ASTM D1525법으로 측정하였다. It measured by ASTM D1525 method.
(4) 충격강도(4) Impact strength
ASTM D256법으로 측정하였으며, 60kg 해머를 사용하여 Charpy type의 시편에 notching machine을 이용하여 시편에 Notch를 냈다. It was measured by ASTM D256 method, and the Notch was made to the specimen using a notching machine on the Charpy type specimen using a 60kg hammer.
(5) 가공성(5) processability
하기 표 1에 기재된 조성비로 2분간 혼합하고, 혼합된 분말을 190℃- 200℃의 20mm 단축압출기에 3분간 압출시켰을 때 용융되어 나오는 수지의 압출량를 측정하였으며, 압출량이 450g 초과일 경우 가공성이 우수(◎)하고, 압출량이 450g 미만일 경우 가공성이 불량(X)한 것으로 판단하였으며, 그 결과를 하기 표 2에 나타내었다. After mixing for 2 minutes at the composition ratio shown in Table 1, and the mixed powder was extruded for 3 minutes in a 20mm single screw extruder of 190 ℃-200 ℃ was measured the extrusion amount of the resin, which is excellent in workability when the extrusion amount is more than 450g (◎), and the extrusion amount was less than 450g was determined to be poor workability (X), the results are shown in Table 2 below.
(6) 염소함량측정(6) Chlorine content measurement
음이온 분석(Ion chromatography)방법을 이용하여 Metrohm 833 Basic IC plus기기를 이용하여 염소 이온 함량을 측정하였다.Chlorine ion content was measured using a Metrohm 833 Basic IC plus instrument using an ion chromatography method.
(7) 스케일 측정(7) scale measurement
반응 종결 후 수성슬러리로부터 염산용액과 슬러리를 분리시킨 다음 반응기 내벽에 생성된 스케일을 육안으로 관찰하였으며, 하기 표 2에 스케일이 발생하여 단단한 덩어리가 형성되었을 경우, 스케일 有로 스케일의 발생이 없거나, 파우더 상태의 미미한 스케일이 발생되었을 경우, 스케일 無로 나타내었다.
After completion of the reaction, the hydrochloric acid solution and the slurry were separated from the aqueous slurry, and the scale produced on the inner wall of the reactor was visually observed. When the scale is formed in Table 2 below and a hard mass is formed, no scale is generated due to the presence of scale. When a slight scale in the powder state occurred, it was indicated as no scale.
[실시예 1]Example 1
온도 조절을 위한 외부에 재킷이 있으며, U.V lamp(250nm - 500nm파장과 광도 200mW - 7200mW를 가지는 고압수은등) 삽입이 가능하며 균일한 교반이 가능한 고압 반응기에 반응온도 65℃로 물 1.5L에 K-값 58.5, 중합도 700인 제1폴리염화비닐수지 30g과 K-값 65.5, 중합도 1000인 제2폴리염화비닐수지 70g 및 계면활성제인 알킬모노글리세릴에테르 1g 넣고 잘 교반하면서 반응기의 압력이 70psig가 될 때까지 염소를 투입하여 가압시킨 후, 광염소화 반응을 5시간 진행하여 염소의 함량이 68%되는 시점에서 염소의 공급을 중단하고 반응을 종료 시켰다. 반응이 종료된 후 반응기의 현탁액으로부터 염소화된 폴리염화비닐수지를 분리하고 탄산수소나트륨으로 중화 처리한 후 물로 세척하였다. 이후에 70℃에서 4시간 건조하여 수분을 증발시킨 후 염소화된 폴리염화비닐수지를 얻었으며, 염소화도를 측정하여 하기 표 2에 나타내었다. Outer jacket for temperature control, UV lamp (high pressure mercury lamp with 250nm-500nm wavelength and luminous intensity 200mW-7200mW) can be inserted and high temperature reactor with uniform agitation K- 1.5L of water at 65 ℃ 30 g of the first polyvinyl chloride resin having a value of 58.5 and a degree of polymerization of 700 and 70 g of the second polyvinyl chloride resin having a K-value of 65.5 and a degree of polymerization of 1000 and 1 g of alkyl monoglyceryl ether as a surfactant are stirred, and the pressure of the reactor is 70 psig. After the chlorine was added and pressurized, the photochlorination reaction was carried out for 5 hours to stop the supply of chlorine at the time when the chlorine content was 68%, and the reaction was terminated. After the reaction was completed, the chlorinated polyvinyl chloride resin was separated from the suspension of the reactor, neutralized with sodium hydrogen carbonate, and washed with water. After drying for 4 hours at 70 ℃ to evaporate water to obtain a chlorinated polyvinyl chloride resin, the degree of chlorination is shown in Table 2 below.
또한, 제조된 염소화된 폴리염화비닐수지를 Tin계 열안정제 1.5중량부, PE wax계 윤활제 2.5중량부, MBS계 충격보강제 5중량부를 처방하여 3분간 Dry Blend를 하였고, Dry Blend한 분말을 190℃의 Roll Mill에서 3분간 성형하여 제조된 Sheet를 잘게 잘라서 Press 시편 Mold에 넣고 정밀 Press성형기 195℃에서 저압 3분, 고압 3분, 냉각 3분 동안 하여 3mm의 Sample 측정용 Sheet를 얻었으며, 물성을 측정한 결과를 하기 표 2에 나타내었다.
In addition, the prepared chlorinated polyvinyl chloride resin was prescribed by 1.5 parts by weight of Tin-based heat stabilizer, 2.5 parts by weight of PE wax-based lubricant, 5 parts by weight of MBS-based impact modifier, and then dry blended for 3 minutes, and the dry blended powder was 190 ° C. The sheet manufactured by molding for 3 minutes in a roll mill of 3 mm was cut finely into a press specimen mold, and a 3 mm sample measuring sheet was obtained by performing a low pressure 3 minutes, a high pressure 3 minutes, and a cooling 3 minutes at a precision press molding machine at 195 ° C. The measurement results are shown in Table 2 below.
[[ 실시예2Example 2 ]]
실시예1에 있어서, K-값 58.5, 중합도 700인 제1폴리염화비닐수지 50g과 K-값 65.5, 중합도 1000인 제2폴리염화비닐수지 50g를 사용한다는 것을 제외하고 실시예 1과 동일하게 실시하여 물성 측정 결과를 표 2에 나타내었다.
In the same manner as in Example 1, except that 50 g of the first polyvinyl chloride resin having a K-value of 58.5 and a polymerization degree of 700 and 50 g of the second polyvinyl chloride resin having a K-value of 65.5 and a polymerization degree of 1000 were used. The physical property measurement results are shown in Table 2.
[[ 실시예3Example 3 ]]
실시예1에 있어서, K-값 58.5, 중합도 700인 제1폴리염화비닐수지 80g과 K-값 80, 중합도 1300인 제2폴리염화비닐수지 20g를 사용한다는 것을 제외하고 실시예 1과 동일하게 실시하여 물성 측정 결과를 표 2에 나타내었다.
Example 1 was carried out in the same manner as in Example 1 except that 80 g of the first polyvinyl chloride resin having a K-value of 58.5 and a polymerization degree of 700 and 20 g of the second polyvinyl chloride resin having a K-value of 80 and a polymerization degree of 1300 were used. The physical property measurement results are shown in Table 2.
[[ 비교예1Comparative Example 1 ] ]
실시예1에 있어서, K-값 58.5, 중합도 700인 제1폴리염화비닐수지 4g과 K-값 80, 중합도 1000인 제2폴리염화비닐수지 96g를 사용한다는 것을 제외하고 실시예 1과 동일하게 실시하여 물성 측정 결과를 표 2에 나타내었다.
In the same manner as in Example 1, except that 4 g of the first polyvinyl chloride resin having a K-value of 58.5 and a polymerization degree of 700 and 96 g of the second polyvinyl chloride resin having a K-value of 80 and a polymerization degree of 1000 were used. The physical property measurement results are shown in Table 2.
[[ 비교예2Comparative Example 2 ] ]
실시예1에 있어서, K-값 58.5, 중합도 700인 제1폴리염화비닐수지 96g과 K-값 80, 중합도 1000인 제2폴리염화비닐수지 4g를 사용한다는 것을 제외하고 실시예 1과 동일하게 실시하여 물성 측정 결과를 표 2에 나타내었다.
In the same manner as in Example 1, except that 96 g of the first polyvinyl chloride resin having a K-value of 58.5 and a polymerization degree of 700 and 4 g of the second polyvinyl chloride resin having a K-value of 80 and a polymerization degree of 1000 were used. The physical property measurement results are shown in Table 2.
[[ 비교예3Comparative Example 3 ]]
실시예1에 있어서, K-값 58.5, 중합도 700인 제1폴리염화비닐수지 100g를 사용한다는 것을 제외하고 실시예 1과 동일하게 실시하여 물성 측정 결과를 표 2에 나타내었다.
In Example 1, except that 100g of the first polyvinyl chloride resin having a K-value of 58.5, the degree of polymerization 700 is used, and the physical properties measurement results are shown in Table 2 in the same manner as in Example 1.
[[ 비교예4Comparative Example 4 ] ]
실시예1에 있어서, K-값 80, 중합도 1000인 제2폴리염화비닐수지 100g를 사용한다는 것을 제외하고 실시예 1과 동일하게 실시하여 물성 측정 결과를 표 2에 나타내었다.
In Example 1, the measurement results of the physical properties are shown in Table 2, except that 100 g of a second polyvinyl chloride resin having a K-value of 80 and a polymerization degree of 1000 is used.
[[ 비교예5Comparative Example 5 ]]
실시예1에 있어서, 계면활성제를 사용하지 않은 것을 제외하고 실시예 1과 동일하게 실시하여 물성 측정 결과를 표 2에 나타내었다.In Example 1, the physical properties measurement results are shown in Table 2 in the same manner as in Example 1 except that no surfactant was used.
[표 1][Table 1]
[표 2][Table 2]
상기 표 2를 참고하면, 실시예 1 내지 3과 비교예 1 내지 5를 비교했을 때, 실시예 1 내지 3에서 나타난 바와 같이 제1폴리염화비닐수지, 제2폴리염화비닐수지 및 스케일방지제가 최적의 함량으로 포함되었을 때, 보다 효과적으로 충격강도를 향상시키고, 반응기 내부 벽면에 스케일이 발생하지 않았으며, 가공성도 향상되었음을 알 수 있다. Referring to Table 2, when Examples 1 to 3 and Comparative Examples 1 to 5 are compared, as shown in Examples 1 to 3, the first polyvinyl chloride resin, the second polyvinyl chloride resin, and the scale inhibitor are optimal. When included in the content of the more effectively improve the impact strength, the scale did not occur on the inner wall of the reactor, it can be seen that the workability is also improved.
비교예 1 내지 4에 나타난 바와 같이 제1폴리염화비닐수지 및 제2폴리염화비닐수지가 최적의 함량으로 포함되지 않거나, 제1폴리염화비닐수지 또는 제2폴리염화비닐수지 단독으로 사용했을 경우에는 충격강도 및 가공성이 저하되는 것을 알 수 있으며, 일부 스케일이 심해지는 것을 알 수 있었다. As shown in Comparative Examples 1 to 4, when the first polyvinyl chloride resin and the second polyvinyl chloride resin are not included in an optimal content, or when the first polyvinyl chloride resin or the second polyvinyl chloride resin is used alone It can be seen that the impact strength and workability are reduced, and some scales are increased.
또한, 비교예 5에 나타난 바와 같이, 스케일방지제를 사용하지 않았을 경우에는 스케일방지제를 사용했을 경우보다 훨씬 많고 단단한 스케일이 형성됨으로써, 인장강도, 굴곡강도, 충격강도 등의 기계적 물성 및 가공성을 현저히 감소시키는 것을 알 수 있었다.
In addition, as shown in Comparative Example 5, when the scale inhibitor is not used, a much larger and harder scale is formed than when the scale inhibitor is used, thereby significantly reducing the mechanical properties and workability of tensile strength, flexural strength, impact strength, and the like. I could see that.
이상에서 본 발명의 바람직한 실시예를 설명하였으나, 본 발명은 다양한 변화와 균등물을 사용할 수 있으며, 상기 실시예를 적절히 변형하여 동일하게 응용할 수 있음이 명확하다. 따라서, 상기 기재 내용은 하기의 특허청구범위의 한계에 의해 정해지는 본 발명의 범위를 한정하는 것이 아니다.
While the present invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the invention. Accordingly, the above description should not be construed as limiting the scope of the present invention defined by the limits of the following claims.
Claims (9)
(b) 상기 수성 슬러리에 염소를 투입하고 가압하여 염소화하는 단계; 및
(c) 과량의 염산과 염소화폴리염화비닐수지를 분리하는 단계;를 포함하는 염소화폴리염화비닐수지의 제조방법
(a) a first polyvinyl chloride resin having a polymerization degree of 400 to 800, a K value of 40 to 62, a second polyvinyl chloride resin having a polymerization degree of 900 to 1800 and a K value of 64 to 81, and a scale inhibitor; Mixing to prepare an aqueous slurry;
(b) chlorination by adding chlorine to the aqueous slurry and pressing; And
(c) separating the excess hydrochloric acid and chlorinated polyvinyl chloride resin;
상기 (a)단계에서 슬러리에 포함되는 산소의 농도가 100ppm 미만이 되도록 제어하는 염소화폴리염화비닐수지의 제조방법
The method of claim 1,
Method for producing a chlorinated polyvinyl chloride resin to control the concentration of oxygen contained in the slurry in step (a) is less than 100ppm
상기 (b)단계에서 염소화단계는 10 내지 100psig의 압력에서 5 내지 50분간 진행하는 염소화폴리염화비닐수지의 제조방법
The method of claim 1,
The chlorination step in the step (b) is a method for producing a chlorinated polyvinyl chloride resin proceeding for 5 to 50 minutes at a pressure of 10 to 100 psig
상기 (a)단계에서 제1폴리염화비닐수지 및 제2폴리염화비닐수지의 혼합비는 95~5중량% : 95~5중량%이며, 상기 스케일방지제는 상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지 혼합물 100중량부에 대하여 0.01 내지 10중량부인 염소화폴리염화비닐수지의 제조방법
The method of claim 1,
The mixing ratio of the first polyvinyl chloride resin and the second polyvinyl chloride resin in step (a) is 95 to 5% by weight: 95 to 5% by weight, the scale inhibitor is the first polyvinyl chloride resin and the second poly A method for producing chlorinated polyvinyl chloride resin in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of a vinyl chloride resin mixture
Chlorinated polyvinyl chloride resin having a chlorine content of 65 to 75% prepared by the method for producing a chlorinated polyvinyl chloride resin according to any one of claims 1 to 4.
상기 염소화폴리염화비닐수지는 중합도가 400 내지 800이고 K값이 40 내지 62인 제1폴리염화비닐수지, 중합도가 900 내지 1800이고 K값이 64 내지 81인 제2폴리염화비닐수지 및 스케일방지제를 포함하는 염소화폴리염화비닐수지
6. The method of claim 5,
The chlorinated polyvinyl chloride resin has a polymerization degree of 400 to 800 and a first polyvinyl chloride resin having a K value of 40 to 62, a second polyvinyl chloride resin having a polymerization degree of 900 to 1800 and a K value of 64 to 81 and a scale inhibitor. Chlorinated polyvinyl chloride resin
상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지의 혼합비는 95~5중량% : 5~95중량%이고, 상기 스케일방지제는 상기 제1폴리염화비닐수지 및 제2폴리염화비닐수지 혼합물 100중량부에 대하여 0.01 내지 10중량부 포함하는 염소화폴리염화비닐수지
The method according to claim 6,
The mixing ratio of the first polyvinyl chloride resin and the second polyvinyl chloride resin is 95 to 5% by weight: 5 to 95% by weight, the scale inhibitor is the mixture of the first polyvinyl chloride resin and the second polyvinyl chloride resin 100 Chlorinated polyvinyl chloride resin containing 0.01 to 10 parts by weight based on parts by weight
상기 스케일방지제는 비누(지방산 나트륨), 모노알킬 황산염, 알킬폴리옥시에틸렌 황산염, 알킬벤젠술폰산염, 모노알킬인산염, 모노알킬트리메틸암모늄염, 디알킬디메틸암모늄염, 알킬벤질메틸암모늄염, 알킬설포베타인, 알킬카르복시베타인, 폴리옥시에틸렌알킬에테르, 지방산 솔비탄에스테르, 지방산 디에탄올아민, 알킬모노글리세릴에테르 중에서 선택되는 1종 또는 2종 이상인 염소화폴리염화비닐수지
The method according to claim 6,
The scale inhibitor is soap (sodium fatty acid), monoalkyl sulfate, alkylpolyoxyethylene sulfate, alkylbenzene sulfonate, monoalkyl phosphate, monoalkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylbenzylmethylammonium salt, alkylsulfobetaine, alkyl 1 or 2 or more types of chlorinated polyvinyl chloride resins selected from carboxybetaine, polyoxyethylene alkyl ether, fatty acid sorbitan ester, fatty acid diethanolamine and alkyl monoglyceryl ether
상기 염소화폴리염화비닐수지는 인장강도가 500~600kg/㎠이고, 굴곡강도가 700~800kg/㎠이며, 충격강도가 20 내지 60kgcm/cm이고, 비커트 연화점이 100 내지 140℃인 염소화폴리염화비닐수지
6. The method of claim 5,
The chlorinated polyvinyl chloride resin has a tensile strength of 500 ~ 600kg / ㎠, flexural strength of 700 ~ 800kg / ㎠, impact strength of 20 to 60kgcm / cm, beaker softening point 100 ~ 140 ℃ polyvinyl chloride polyvinyl chloride Suzy
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| WO2018043945A1 (en) * | 2016-09-02 | 2018-03-08 | 한화케미칼 주식회사 | Method for preparing chlorinated vinyl chloride resin |
| CN116790081A (en) * | 2023-07-28 | 2023-09-22 | 新疆至臻化工工程研究中心有限公司 | Method for producing chlorinated polymer mixture by coupling chlorination process |
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| JPH0776608A (en) * | 1993-09-07 | 1995-03-20 | Tokuyama Sekisui Ind Corp | Production of chlorinated vinyl chloride resin |
| KR100452391B1 (en) | 1996-05-24 | 2005-04-06 | 노베온 아이피 홀딩스 코프. | Chlorinated polyvinyl chloride compounds with excellent physical and chemical resistance and processing characteristics |
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| CN116790081A (en) * | 2023-07-28 | 2023-09-22 | 新疆至臻化工工程研究中心有限公司 | Method for producing chlorinated polymer mixture by coupling chlorination process |
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