WO2014185723A1 - 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치 및 방법 - Google Patents
반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치 및 방법 Download PDFInfo
- Publication number
- WO2014185723A1 WO2014185723A1 PCT/KR2014/004353 KR2014004353W WO2014185723A1 WO 2014185723 A1 WO2014185723 A1 WO 2014185723A1 KR 2014004353 W KR2014004353 W KR 2014004353W WO 2014185723 A1 WO2014185723 A1 WO 2014185723A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- reactive
- polybutene
- reactive polybutene
- catalyst
- polymerization catalyst
- Prior art date
Links
Images
Classifications
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
- C08F210/10—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
-
- 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
- C08F10/10—Isobutene
Definitions
- the present invention relates to an apparatus and method for the selective preparation of reactive polybutenes and non-reactive polybutenes, and more particularly, to the apparatus for selectively producing high-reactivity polybutenes, moderately reactive polybutenes and non-reactive polybutenes in one plant. And to a method.
- Polybutene is generally a polymerized olefin component having 4 carbon atoms (C4) derived from the decomposition of naphtha using a Friedel-Craft type catalyst, and the number average molecular weight (Mn) is about 300 to 5,000.
- C4 raffinate-1 The remaining residue after extracting 1,3-butadiene from C4 raw materials is called C4 raffinate-1, including isobutane and normalbutane paraffins and 1-butene (1-butene).
- olefins such as butene), 2-butene, and isobutene are included, and isobutene is about 30 to 50% by weight.
- the C4 residue oil-1 is mainly used for preparing methyl t-butylether (MTBE) or polybutene which is an octane number improver, and isobutene has the highest reactivity among the olefin components of the C4 residue oil-1.
- the resulting polybutenes consist primarily of isobutene units.
- Polybutenes may also be prepared from butane-butene fraction (B-B fraction), which is a C4 mixture derived from crude oil refining, or from high purity isobutene.
- Polybutenes increase in viscosity with increasing molecular weight and have a viscosity of approximately 4 to 40,000 cSt (centi-stocks) at 100 ° C.
- polybutene is pyrolyzed without leaving a residue at a temperature of 300 ° C. or higher, and has a side chain alkyl structure, so that it is highly soluble in lubricating oil or fuel, so that it is added to an engine oil and is used as an anti-scuff agent or viscosity index improver ( It can be used as viscosity index improver, or it can be mixed with fuel of internal combustion engine such as automobile and used as a detergent.
- the most widely used products obtained by introducing a polar group include polyisobutenyl succinic anhydride (PIBSA) and phenols and moderately reactive polybutenes prepared by the reaction of high-reactivity polybutene terminal double bonds and maleic anhydride by heating.
- Alkyl phenols (polybutenylphenol, etc.) are prepared through the Manich Reaction, and have the advantage of being a functional polymer.
- the PIBSA is used as an intermediate.
- the double bond of polybutene used for the production of PIBSA is located at the end of the polybutene, PIBSA is obtained in a high yield. The bond is located inside the polybutene, and in particular, the greater the number of alkyl groups substituted in the double bond, the lower the PIBSA yield due to the steric hindrance.
- PIBSA Prior to the use of highly reactive polybutenes, PIBSA was prepared from ordinary polybutenes, that is, non-reactive polybutenes.As a method of increasing the reactivity of non-reactive polybutenes, a polybutene is produced by a chlorination reaction using chlorine gas. Chlorinated, followed by reaction with maleic anhydride to produce PIBSA, and the addition and reaction of amines to complete the final product.
- chlorine gas Chlorinated, followed by reaction with maleic anhydride to produce PIBSA, and the addition and reaction of amines to complete the final product.
- maleic anhydride to produce PIBSA
- Non-reactive polybutene is highly reactive polybutene, which is widely used in adhesives, adhesives, sealants, lubricant additives, and insulating oils requiring chemical stability (non-reactive), thermal stability, moisture barrier, adhesiveness and adhesiveness, etc.
- Reactive polybutenes and non-reactive polybutenes have different uses, respectively, and need to be tailored to meet demand.
- Korean Patents 0152136 and 0154362 describe a method for producing non-reactive polybutene.
- highly reactive polybutenes moderately reactive polybutenes and non-reactive polybutenes patents
- Another object of the present invention is to selectively produce the above three kinds of polybutenes having different uses in one plant where a product is produced from the supplied raw materials, so that two plants do not need to be constructed compared to the existing manufacturing method. That is, it leads to a reduction in investment costs, and provides a method of manufacturing by adjusting three types of polybutene according to the market demand.
- a reactive polybutene polymerization catalyst supply apparatus for polymerizing high reactive polybutene and heavy reactive polybutene;
- Non-reactive polybutene polymerization catalyst feeder for polymerizing non-reactive polybutene;
- a reactor in which a reaction raw material including isobutene is supplied and polymerized into polybutene, wherein a catalyst is supplied from the reactive polybutene polymerization catalyst feeder to obtain a highly reactive polybutene and a medium reactive polybutene, and the non-reactive
- the present invention also provides a method for producing a reactive polybutene polymerization catalyst for polymerizing highly reactive polybutene and heavy reactive polybutene or a non-reactive polybutene polymerization catalyst for polymerizing non-reactive polybutene; And polymerizing a reaction raw material including isobutene in the presence of the reactive polybutene polymerization catalyst or the non-reactive polybutene polymerization catalyst, wherein when the reactive polybutene polymerization catalyst is supplied, a reactive polybutene is obtained, When the non-reactive polybutene polymerization catalyst is supplied, non-reactive polybutene is obtained, thereby providing a method for selectively preparing reactive polybutene and non-reactive polybutene.
- the process for selectively producing high reactivity polybutene, heavy reactive polybutene and non-reactive polybutene in one plant according to the present invention is that the three types of polybutenes are currently one type of poly in each plant worldwide There is a significant difference from making butenes only. In general, the cost of constructing a plant of polybutene in consideration of profitability is about 120 billion won or more, while using the combined process of the present invention, one of the three plant polybutenes can be produced at the cost of the plant.
- the manufacturing method of the present invention it is possible to selectively manufacture and supply the three types of polybutene according to the demands of consumers according to the rapidly changing world economy and market conditions. Even if a petrochemical plant is constructed in consideration of profitability, if the plant operation rate is low, the plant operation rate may decrease according to the world economic and market conditions, such as a huge loss, but the manufacturing method of the present invention may change rapidly. By allowing you to respond flexibly to changes in market conditions, you can maximize plant utilization and profitability at the same time.
- FIG. 1 is a schematic view showing a selective manufacturing apparatus of reactive polybutene and non-reactive polybutene according to an embodiment of the present invention.
- An apparatus for the selective production of high reactivity polybutene, medium reactive polybutene and non-reactive polybutene in one plant according to the present invention is a reactive polybutene polymerization catalyst feeder for polymerizing high reactive polybutene and medium reactive polybutene, non A non-reactive polybutene polymerization catalyst feeder for polymerizing reactive polybutene and a reactor in which a reaction raw material comprising isobutene is fed and polymerized to polybutene.
- the reactive polybutene polymerization catalyst supply device (a) generates a reactive polybutene polymerization catalyst and then discharges it to the reactor 3 through the lower portion of the reactive polybutene polymerization catalyst supply device 2.
- the reactive polybutene polymerization catalyst supplied through the reactive polybutene polymerization catalyst supply device includes a Lewis acid main catalyst such as boron trifluoride, a cocatalyst and an auxiliary cocatalyst, and, depending on the configuration of the catalyst, (i) Main catalysts, cocatalysts and auxiliary cocatalysts such as boron fluoride are introduced into the reactive polybutene polymerization catalyst feeder 2 and mixed into the reactor 3, or (ii) main catalysts such as boron trifluoride, crude The catalyst and the auxiliary promoter directly meet in the pipe to form a complex and are introduced into the reactor (3), or (iii) the primary catalyst such as boron trifluoride or the like injected alone after first mixing the promoter and the auxiliary promoter into the reaction raw material.
- the catalyst may be selected from the method of introduction.
- the reactive catalyst supplied through the reactive polybutene polymerization catalyst supply device is Lewis acid, which is a catalyst of a conventional Friedelcraft type, and can be used without limitation.
- a catalyst such as boron trichloride, aluminum trichloride, and zinc chloride may be used, but the use of boron trifluoride, which is excellent in inducing production of terminal vinylidene and is also advantageous for commercial purposes, is most preferred.
- the reactive catalyst supplied through the reactive polybutene polymerization catalyst supplying device includes, as a boron trifluoride complex catalyst, in addition to the boron trifluoride as a main catalyst, a cocatalyst which is water or an alcohol compound and an auxiliary promoter which is an alkyl ether.
- the cocatalyst used in the preparation can be used without limitation, water or an alcohol compound having 1 to 4 carbon atoms, which acts as a proton (H + ) donor for the reaction initiation, methanol, ethanol, propanol, Isopropyl alcohol (isopropanol), butanol, isobutanol, etc. can be illustrated.
- the co-promoter is for stabilizing the protons produced by the co-catalyst and controlling the reactivity, and can be used without limitation, alkyl ether having 2 to 10 carbon atoms, dimethyl ether, diethyl ether, di Propyl ether, isopropyl sec-butyl ether, sec-butyl ether, isoamyl ether, isopropyl isoamyl ether, sec-butyl isoamyl ether and the like.
- the molar ratio of boron trifluoride, alcohol compound and alkyl ether is 1: 0.8 to 1.6: 0.1 to 0.9 (boron trifluoride), as shown in the following formula (1): : Alcohol compound: alkyl ether, and from the viewpoint of the reaction activity, 1: 0.8 to 1.4: 0.1 to 0.7 (boron trifluoride (BF 3 ): alcohol compound (R 1 OH): alkyl ether (R 2 -OR) 3 )) is preferred.
- the molar ratio of the alcohol compound and the alkyl ether to the boron trifluoride serving as a catalyst is 0.9 to 2.5, preferably 0.9 to 2.1.
- R 1 is an alkyl group having 1 to 4 carbon atoms
- R 2 and R 3 are each independently an alkyl group having 1 to 5 carbon atoms.
- the activity of the reactive catalyst supplied through the reactive polybutene polymerization catalyst supply device is If the molar ratio of alcohol compound and alkyl ether to boron trifluoride is too large, the stability and vinylidene content of polybutene may be lowered to less than 80% (the alcohol compound and alkyl ether molar ratio to boron trifluoride). Is too small).
- the reactive catalyst supplied through the reactive polybutene polymerization catalyst supplying device is the boron trifluoride based on 100 parts by weight of isobutene in the reaction raw material, for example, C4 residue oil-1 having an isobutene content of 10% by weight or more. It is added so that the content of 0.05 to 1.0 parts by weight.
- the (b) non-reactive polybutene polymerization catalyst supply device (1) after mixing the low molecular polybutene with Lewis acid to produce a slurry non-reactive polybutene polymerization catalyst, the non-reactive polybutene polymerization catalyst supply device ( Discharge into the reactor 3 through the bottom of 1).
- the non-reactive catalyst supplied through the non-reactive polybutene polymerization catalyst supply device is a Lewis acid which is a catalyst of a conventional Friedelcraft type, and can be used without limitation.
- a Lewis acid which is a catalyst of a conventional Friedelcraft type
- aluminum trichloride, zinc chloride and iron chloride are used, the use of the aluminum trichloride is most preferred, and when using such a catalyst, isobutene having high reactivity in the mixed material having 4 carbon atoms mainly participates in the reaction, thereby making non-reactive poly Production of butenes becomes possible.
- the non-reactive catalyst supplied through the non-reactive polybutene polymerization catalyst supplying device has a content of aluminum trichloride of 0.05 to 1.0 based on 100 parts by weight of isobutene in C4 residue oil-1 having an isobutene content of 10% by weight or more. Add to weight parts.
- the said (c) reactor 3 superposes
- a catalyst is supplied from the reactive polybutene polymerization catalyst supply device to obtain high reactive polybutene and a medium reactive polybutene, and a catalyst is supplied from the non-reactive polybutene polymerization catalyst supply device to obtain a non-reactive polybutene.
- the highly reactive polybutene or the medium reactive polybutene is polymerized by the difference in molar ratio and catalyst amount of the cocatalyst and the main catalyst.
- the reactive polybutene is a polybutene having a vinylidene content of 40% or more at the molecular end, and specifically, the high reactive polybutene in the reactive polybutene has a vinylidene content of more than 70% at the molecular end, preferably 71 to 99%, more preferably 75 to 95%, most preferably 80 to 95%, the heavy reactive polybutene in the polybutene has a vinylidene content of 40-70%, preferably 41-69% And more preferably 45 to 65%.
- the non-reactive polybutene has a vinylidene content at the molecular end of less than 40%, preferably 1 to 39%, more preferably 5 to 35%.
- the reactive polybutenes and non-reactive polybutenes prepared according to the polymerization typically have a number average molecular weight (Mn) of 300 to 5,000.
- the reaction raw materials used to prepare the reactive polybutene and the non-reactive polybutene include at least 10% by weight of isobutene, preferably 25 to 60% by weight, for example, naphtha decomposition or crude oil. This is C4 residue-1 remaining after extracting 1,3-butadiene from a hydrocarbon mixture of 4 carbon atoms derived from the purification process. In addition, a method of diluting pure isobutene with alkanes is also possible. The concentration of isobutane is 25 to 60% for proper polymerization of the product.
- the reaction raw material may be supplied in a moving line between the reactive polybutene polymerization catalyst feeder 2 and the non-reactive polybutene polymerization catalyst feeder and the reactor 3.
- the neutralization and washing tank 4 which may be further included, includes the reactor 3 and the neutralization and washing tank 4 in the reactants discharged from the reactor 3.
- Water introduced in the transfer line is added to remove the catalyst component from the reactant and neutralize it, and discharge it to the separation tank 5 through the side of the neutralization and washing tank 4.
- the separation tank (5) discharges water containing the catalyst component removed from the neutralization and washing tank (4) to the lower portion of the separation tank (5) by using a layer separation, and removes the catalyst in the reaction product. The remaining organic compound is discharged to the top of the separation tank (5).
- the C4 distillation column (6) distills unreacted C4 from the organic compound introduced from the separation tank (5) and discharges and recovers the upper portion of the C4 distillation column (6). Discharged to the bottom of the) is introduced into the LP (light polymer) distillation column (7).
- the light polymer distillation column 7 distills a light polymer (LP) from the residual organic compounds from the C4 distillation column (6), and discharges and recovers the upper portion of the light polymer (7) column.
- the reactive polybutene and non-reactive polybutene are sent to the bottom of the light polymer distillation column 7 and stored in the product tank.
- Method for producing a polybutene obtained through the selective production method of the high reactivity polybutene, medium reactive polybutene and non-reactive polybutene according to the present invention, the reactive polybutene for polymerizing the high reactive polybutene and medium reactive polybutene
- the reactive polybutene for polymerizing the high reactive polybutene and medium reactive polybutene Selectively generating a polymerization catalyst or a non-reactive polybutene polymerization catalyst for polymerizing the non-reactive polybutene and a reaction raw material comprising isobutene in the presence of the reactive polybutene polymerization catalyst or the non-reactive polybutene polymerization catalyst It comprises the step of polymerizing.
- the raw material such as C4 residue oil-1 and the catalyst, such as boron trifluoride, cocatalyst and auxiliary cocatalyst according to the configuration of the catalyst is introduced into the reactor (3) to react It is disclosed, in the reactor (3) to adjust the temperature control, catalyst strength and isobutene content after the reaction and the like to adjust the molecular weight and vinylidene content of the product.
- the polymerization method of the highly reactive polybutene and the medium reactive polybutene may be carried out under ordinary reaction conditions, for example, at a temperature of ⁇ 40 to 20 ° C., preferably at ⁇ 35 to 10 ° C.
- the conversion rate of isobutene is 70% or more, preferably, in polymerization of the medium-reactive polybutene. 5 to 100 minutes, preferably 80 to 95% so that the conversion rate of isobutene which can maintain high terminal vinylidene at the time of superposition
- the method for producing the non-reactive polybutene will be described in detail.
- aluminum trichloride in the non-reactive polybutene polymerization catalyst feeder 1 it is mixed with the low molecular polybutene and made into a slurry, followed by a C4 glass.
- the reactor 3 is fed to the reactor 3 together with raw materials such as Reason-1, and in addition to the initiation of the reaction, temperature control, catalyst strength, and isobutene content after the reaction are controlled. Adjust vinylidene content and the like.
- the polymerization method of the non-reactive polybutene may be carried out under ordinary reaction conditions, for example, at a temperature of ⁇ 20 to 60 ° C., preferably at ⁇ 10 to 50 ° C., the reaction raw material may maintain a liquid state. So that it is usually set at a pressure of 3 kg / cm 2 or more, preferably 3.5 to 10 kg / cm 2 , so that the conversion of isobutene is 70% or more, preferably 90 to 95% or more in the polybutene polymerization, It is economical to react for a residence time of 5 to 100 minutes, preferably 10 to 45 minutes.
- the production method of the present invention it is possible to further prepare high reactive polybutene and heavy reactive polybutene in a plant for producing non-reactive polybutene as in the above process, the order is optional.
- the injection of aluminum trichloride catalyst is stopped and converted to a form capable of producing highly reactive polybutene and heavy reactive polybutene.
- the reactor pressure was maintained at 3 kg / cm 2 or more to maintain the liquid phase, the average residence time was 45 minutes, and the catalyst amount was 100 parts by weight of isobutene in the raw material of boron trifluoride (BF 3 ) in the catalyst. It was injected so as to be 0.27 parts by weight.
- the reactant from the reactor was taken up in a 5 wt% caustic soda solution and transferred to a neutralization and washing bath to stop the polymerization and remove the catalyst.
- the wastewater containing the washed catalyst was discharged and removed to the bottom of the separation tank, and the reactants were introduced into the C4 distillation column through the top of the separation tank.
- the reactants in the C4 distillation column are heated to 100 ° C., unreacted C4 is distilled off and recovered to the top of the tower, and the remaining reactants are transferred to the LP distillation column through the bottom of the tower.
- the reactant introduced into the LP distillation column is heated at 230 ° C.
- the reactor pressure was maintained at 3 kg / cm 2 or more to maintain the liquid phase, the average residence time was 45 minutes, and the catalyst amount was 100 parts by weight of isobutene in the raw material of boron trifluoride (BF 3 ) in the catalyst.
- Polymerization was carried out in the same manner as in Example 1, except that 0.17 parts by weight of the compound was injected.
- Reason-1) was injected continuously.
- the reactor pressure was maintained at 3 kg / cm 2 or more so as to keep the raw material in a liquid phase, and the average residence time was 45 minutes, except that the amount of catalyst was injected such that aluminum trichloride was 0.07 parts by weight based on 100 parts by weight of isobutene.
- the polymerization was carried out in the same manner as in 1 to obtain a product.
- the invention can effectively produce at least three kinds of polybutenes in one plant.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
성 분 | 이소부탄 | n-부탄 | 1-부텐 | C-2-부텐 | T-2-부텐 | 이소부텐 |
함량(중량%) | 2.7 | 10.0 | 26.1 | 4.5 | 9.3 | 47.4 |
Claims (13)
- 하나의 플랜트에서 고반응성 폴리부텐, 중반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치.
- 청구항 1에 있어서, 상기 고반응성 폴리부텐 및 중반응성 폴리부텐을 중합하기 위한 반응성 폴리부텐 중합 촉매 공급장치;상기 비반응성 폴리부텐을 중합하기 위한 비반응성 폴리부텐 중합 촉매 공급장치; 및이소부텐을 포함하는 반응원료가 공급되어 폴리부텐으로 중합되는 반응기를 포함하며,상기 반응성 폴리부텐 중합 촉매 공급장치로부터 촉매가 공급되어 고반응성 및 중반응성 폴리부텐이 얻어지고, 상기 비반응성 폴리부텐 중합 촉매 공급장치로부터 촉매가 공급되어, 비반응성 폴리부텐이 얻어지는, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치.
- 청구항 2에 있어서, 상기 고반응성 폴리부텐은 분자 말단의 비닐리덴 함량이 70%를 초과하는 폴리부텐이며, 상기 중반응성 폴리부텐은 분자 말단의 비닐리덴 함량이 40 내지 70%인 폴리부텐이며, 상기 비반응성 폴리부텐은 분자 말단의 비닐리덴 함량이 40% 미만인 것인, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치.
- 청구항 2에 있어서, 상기 반응성 폴리부텐 중합 촉매 공급 장치를 통해 공급되는 반응성 촉매는 삼불화붕소, 삼염화붕소, 삼염화알루미늄 및 염화아연으로 이루어진 군으로부터 선택되는 루이스산을 포함하고, 상기 비반응성 폴리부텐 중합 촉매 공급 장치를 통해 공급되는 비반응성 촉매는 삼염화알루미늄, 염화아연 및 염화철로 이루어진 군으로부터 선택되는 루이스산을 포함하는 것인, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치.
- 청구항 2에 있어서, 상기 반응성 폴리부텐의 중합 촉매 공급 장치를 통해 공급되는 반응성 촉매는, 주촉매로서 삼불화붕소, 조촉매로서 물 또는 알코올 화합물 및 보조 조촉매로서 알킬에테르를 포함하는 것인, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치.
- 청구항 2에 있어서, 상기 반응성 폴리부텐 중합 촉매는, 이소부텐 100 중량부에 대하여, 삼불화붕소의 함량이 0.05 내지 1.0 중량부가 되도록 투입하며, 상기 비반응성 폴리부텐 중합 촉매는, 이소부텐 100 중량부에 대하여, 삼염화알루미늄의 함량이 0.05 내지 1.0 중량부가 되도록 투입하는 것인, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치.
- 청구항 2에 있어서, 상기 반응성 폴리부텐 중합 촉매 공급 장치는, (i) 삼불화붕소 등의 주촉매, 조촉매 및 보조 조촉매가 상기 반응성 폴리부텐 중합 촉매 공급 장치로 투입 및 혼합되어 반응기로 투입되거나, (ii) 삼불화붕소 등의 주촉매, 조촉매 및 보조 조촉매가 배관에서 직접 만나 착물을 형성하는 동시에 반응기로 투입되거나, (iii) 조촉매 및 보조 조촉매를 반응 원료에 먼저 혼합 후, 단독으로 주입된 삼불화붕소 등의 주촉매가 투입되는 방법 중 선택되는, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치.
- 하나의 플랜트에서 고반응성 폴리부텐, 중반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조방법.
- 청구항 8에 있어서, 상기 고반응성 폴리부텐 및 중반응성 폴리부텐을 중합하기 위한 반응성 폴리부텐 중합 촉매 또는 상기 비반응성 폴리부텐을 중합하기 위한 비반응성 폴리부텐 중합 촉매를 선택적으로 생성하는 단계; 및상기 반응성 폴리부텐 중합 촉매 또는 상기 비반응성 폴리부텐 중합 촉매의 존재 하에서, 이소부텐을 포함하는 반응원료를 중합하는 단계를 포함하며,상기 반응성 폴리부텐 중합 촉매가 공급되면 반응성 폴리부텐이 얻어지고, 상기 비반응성 폴리부텐 중합 촉매가 공급되면 비반응성 폴리부텐이 얻어지는, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조방법.
- 청구항 9에 따른, 고반응성 폴리부텐, 중반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조방법을 통하여 얻어지는 폴리부텐.
- 청구항 9에 있어서, 상기 고반응성 폴리부텐은 분자 말단의 비닐리덴 함량이 70%를 초과하는 폴리부텐이며, 상기 중반응성 폴리부텐은 분자 말단의 비닐리덴 함량이 40 내지 70%인 폴리부텐이며, 상기 비반응성 폴리부텐은 분자 말단의 비닐리덴 함량이 40% 미만인 것인, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조방법.
- 청구항 9에 있어서, 상기 고반응성 폴리부텐 및 중반응성 폴리부텐의 중합은 -40 내지 20℃의 온도 및 3kg/cm2이상의 압력에서, 5 내지 100분의 체류 시간 동안 반응시키는 것이고, 비반응성 폴리부텐의 중합은 -20 내지 60℃의 온도 및 3kg/cm2이상의 압력에서, 5 내지 100분의 체류 시간 동안 반응시키는 것인, 반응성 폴리부텐 및 비반응성 폴리부텐의 제조방법.
- 청구항 9에 있어서, 상기 반응성 폴리부텐 중합 촉매는, (i) 삼불화붕소 등의 주촉매, 조촉매 및 보조 조촉매가 상기 반응성 폴리부텐 중합 촉매 공급장치로 투입 및 혼합되어 반응기로 투입되거나, (ii) 삼불화붕소 등의 주촉매, 조촉매 및 보조 조촉매가 배관에서 직접 만나 착물을 형성하는 동시에 반응기로 투입되거나, (iii) 조촉매 및 보조 조촉매를 반응 원료에 먼저 혼합 후, 단독으로 주입된 삼불화붕소 등의 주촉매가 투입되는 방법 중 선택되는, 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조방법.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016513876A JP6454327B2 (ja) | 2013-05-16 | 2014-05-15 | 反応性ポリブテンおよび非反応性ポリブテンを選択的に製造するための装置および方法 |
SG11201509314YA SG11201509314YA (en) | 2013-05-16 | 2014-05-15 | Apparatus and method for selectively preparing reactive polybutene and nonreactive polybutene |
EP14797177.4A EP2998324B1 (en) | 2013-05-16 | 2014-05-15 | Apparatus and method for selectively preparing reactive polybutene and nonreactive polybutene |
US14/890,489 US10059786B2 (en) | 2013-05-16 | 2014-05-15 | Apparatus and method for selectively preparing reactive polybutene and nonreactive polybutene |
CN201480028233.0A CN105246920B (zh) | 2013-05-16 | 2014-05-15 | 选择性制备反应性聚丁烯和非反应性聚丁烯的装置和方法 |
BR112015028534-1A BR112015028534B1 (pt) | 2013-05-16 | 2014-05-15 | Aparelho e método para preparar seletivamente polibuteno reativo e polibuteno não reativo |
SA515370147A SA515370147B1 (ar) | 2013-05-16 | 2015-11-15 | جهاز وطريقة للتحضير الانتقائي للبولي بيوتين التفاعلي والبولي بيوتين غير التفاعلي |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020130055713A KR101523568B1 (ko) | 2013-05-16 | 2013-05-16 | 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치 및 방법 |
KR10-2013-0055713 | 2013-05-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014185723A1 true WO2014185723A1 (ko) | 2014-11-20 |
Family
ID=51898627
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2014/004353 WO2014185723A1 (ko) | 2013-05-16 | 2014-05-15 | 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치 및 방법 |
Country Status (10)
Country | Link |
---|---|
US (1) | US10059786B2 (ko) |
EP (1) | EP2998324B1 (ko) |
JP (1) | JP6454327B2 (ko) |
KR (1) | KR101523568B1 (ko) |
CN (2) | CN105246920B (ko) |
BR (1) | BR112015028534B1 (ko) |
MY (1) | MY176816A (ko) |
SA (1) | SA515370147B1 (ko) |
SG (1) | SG11201509314YA (ko) |
WO (1) | WO2014185723A1 (ko) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR102118800B1 (ko) * | 2018-10-19 | 2020-06-03 | 한화토탈 주식회사 | 비반응성 폴리부텐의 제조방법, 비반응성 폴리부텐의 제조장치 및 이에 의해 제조된 비반응성 폴리부텐 |
CN113597419A (zh) | 2019-03-13 | 2021-11-02 | Tpc集团有限责任公司 | 选择性地生产不同线性α-烯烃的弹性制造系统 |
KR102202777B1 (ko) * | 2019-09-16 | 2021-01-13 | 한화토탈 주식회사 | 비반응성 폴리부텐의 제조시 원료의 재순환 장치 및 그 방법 |
JP7508908B2 (ja) | 2020-07-13 | 2024-07-02 | 東ソー株式会社 | 石油樹脂の製造方法 |
Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4605808A (en) | 1983-11-01 | 1986-08-12 | Bp Chemicals Limited | Cationic polymerization of 1-olefins |
US5068490A (en) | 1989-08-18 | 1991-11-26 | Amoco Corporation | BF3-tertiary etherate complexes for isobutylene polymerization |
US5191044A (en) | 1990-10-19 | 1993-03-02 | Basf Aktiengesellschaft | Preparation of polyisobutene |
US5408018A (en) | 1991-06-22 | 1995-04-18 | Basf Aktiengesellschaft | Preparation of highly reactive polyisobutenes |
KR0152136B1 (ko) * | 1994-05-31 | 1998-10-15 | 성기웅 | 폴리부텐류의 제조방법 |
KR0154362B1 (ko) * | 1994-05-31 | 1998-12-01 | 성기웅 | 새로운 촉매조성물에 의한 폴리부텐류의 제조방법 |
US5962604A (en) | 1995-06-07 | 1999-10-05 | Basf Aktiengesellschaft | Process for preparing low molecular weight, highly reactive polyisobutylene |
US6300444B1 (en) | 1998-08-25 | 2001-10-09 | Nippon Petrochemicals Company, Limited | Process for producing butene polymer |
US7037999B2 (en) | 2001-03-28 | 2006-05-02 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product and process for producing the same |
KR20060126591A (ko) * | 2004-02-13 | 2006-12-07 | 토탈 페트로케미칼스 리서치 펠루이 | 촉매 슬러리의 제조 및 중합 반응기로의 공급을 위한 방법및 장치 |
KR100787851B1 (ko) | 2006-12-05 | 2007-12-27 | 대림산업 주식회사 | 폴리부텐 중합체 조성물 및 그 제조방법 |
KR20100069011A (ko) * | 2008-12-15 | 2010-06-24 | 대림산업 주식회사 | 삼불화붕소 착화합물 촉매 및 이를 이용한 고반응성 폴리부텐의 제조방법 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4849572A (en) * | 1987-12-22 | 1989-07-18 | Exxon Chemical Patents Inc. | Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts (PT-647) |
KR0154363B1 (ko) | 1994-05-31 | 1998-12-01 | 성기웅 | 부텐중합체의 정제방법 |
JP3795666B2 (ja) * | 1997-03-07 | 2006-07-12 | 新日本石油化学株式会社 | ブテンポリマーの製造方法 |
US6407186B1 (en) * | 1997-12-12 | 2002-06-18 | Basf Aktiengesellschaft | Method for producing low-molecular, highly reactive polyisobutylene |
DE19825334A1 (de) * | 1998-06-05 | 1999-12-09 | Basf Ag | Verfahren zur Herstellung hochreaktiver Polyisobutene |
US6884858B2 (en) * | 1999-10-19 | 2005-04-26 | Texas Petrochemicals Lp | Process for preparing polyolefin products |
US6562913B1 (en) * | 1999-09-16 | 2003-05-13 | Texas Petrochemicals Lp | Process for producing high vinylidene polyisobutylene |
US6399722B1 (en) * | 1999-12-01 | 2002-06-04 | Univation Technologies, Llc | Solution feed of multiple catalysts |
GB0008770D0 (en) * | 2000-04-10 | 2000-05-31 | Bp Chem Int Ltd | Polymerisation process |
JP4562882B2 (ja) * | 2000-08-23 | 2010-10-13 | Jx日鉱日石エネルギー株式会社 | 化粧料および基礎化粧品 |
WO2004052950A1 (en) * | 2002-12-05 | 2004-06-24 | Exxonmobil Chemical Patents Inc. | High temperature bulk polymerization of branched crystalline polypropylene |
JP4922294B2 (ja) * | 2005-07-12 | 2012-04-25 | ビーエーエスエフ ソシエタス・ヨーロピア | 高品質のポリイソブテンの製造方法 |
DE102005048698A1 (de) * | 2005-10-11 | 2007-04-12 | Basf Ag | Verfahren zur Herstellung von Polyisobuten |
CA2529920C (en) * | 2005-12-13 | 2013-08-20 | Nova Chemicals Corporation | On the fly catalyst transitions |
CN101460530A (zh) * | 2006-06-06 | 2009-06-17 | 巴斯夫欧洲公司 | 由低异丁烯的c4烃混合物制备反应性且基本上无卤聚异丁烯的方法 |
US7939610B2 (en) * | 2008-05-22 | 2011-05-10 | Exxonmobil Research And Engineering Company | Polymerization processes for broadened molecular weight distribution |
DK2387590T3 (da) * | 2009-12-18 | 2013-05-06 | Total Res & Technology Feluy | Fremgangsmåde til erstatning af kompatible ethylenpolymeriseringskatalysatorer |
KR101522080B1 (ko) | 2009-12-18 | 2015-05-20 | 토탈 리서치 앤드 테크놀로지 펠루이 | 비호환성 에틸렌 중합 촉매 대체 방법 |
CN102464736B (zh) * | 2010-11-19 | 2013-07-24 | 北京化工大学 | 制备聚异丁烯的工艺方法及聚合装置 |
CA2852752A1 (en) * | 2011-10-26 | 2013-05-02 | Tpc Group Llc | Mid-range vinylidene content, high viscosity polyisobutylene polymers |
BR112014009478B1 (pt) * | 2011-10-26 | 2021-09-21 | Tpc Group Llc | Método de preparação de um polímero de poli-isobutileno em um reator loop de recirculação |
-
2013
- 2013-05-16 KR KR1020130055713A patent/KR101523568B1/ko active IP Right Grant
-
2014
- 2014-05-15 MY MYPI2015704047A patent/MY176816A/en unknown
- 2014-05-15 EP EP14797177.4A patent/EP2998324B1/en active Active
- 2014-05-15 BR BR112015028534-1A patent/BR112015028534B1/pt active IP Right Grant
- 2014-05-15 WO PCT/KR2014/004353 patent/WO2014185723A1/ko active Application Filing
- 2014-05-15 JP JP2016513876A patent/JP6454327B2/ja active Active
- 2014-05-15 SG SG11201509314YA patent/SG11201509314YA/en unknown
- 2014-05-15 CN CN201480028233.0A patent/CN105246920B/zh active Active
- 2014-05-15 US US14/890,489 patent/US10059786B2/en active Active
- 2014-05-15 CN CN201811365761.1A patent/CN109535288A/zh active Pending
-
2015
- 2015-11-15 SA SA515370147A patent/SA515370147B1/ar unknown
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4605808A (en) | 1983-11-01 | 1986-08-12 | Bp Chemicals Limited | Cationic polymerization of 1-olefins |
US5068490A (en) | 1989-08-18 | 1991-11-26 | Amoco Corporation | BF3-tertiary etherate complexes for isobutylene polymerization |
US5191044A (en) | 1990-10-19 | 1993-03-02 | Basf Aktiengesellschaft | Preparation of polyisobutene |
US5408018A (en) | 1991-06-22 | 1995-04-18 | Basf Aktiengesellschaft | Preparation of highly reactive polyisobutenes |
KR0152136B1 (ko) * | 1994-05-31 | 1998-10-15 | 성기웅 | 폴리부텐류의 제조방법 |
KR0154362B1 (ko) * | 1994-05-31 | 1998-12-01 | 성기웅 | 새로운 촉매조성물에 의한 폴리부텐류의 제조방법 |
US5962604A (en) | 1995-06-07 | 1999-10-05 | Basf Aktiengesellschaft | Process for preparing low molecular weight, highly reactive polyisobutylene |
US6300444B1 (en) | 1998-08-25 | 2001-10-09 | Nippon Petrochemicals Company, Limited | Process for producing butene polymer |
US7037999B2 (en) | 2001-03-28 | 2006-05-02 | Texas Petrochemicals Lp | Mid-range vinylidene content polyisobutylene polymer product and process for producing the same |
KR20060126591A (ko) * | 2004-02-13 | 2006-12-07 | 토탈 페트로케미칼스 리서치 펠루이 | 촉매 슬러리의 제조 및 중합 반응기로의 공급을 위한 방법및 장치 |
KR100787851B1 (ko) | 2006-12-05 | 2007-12-27 | 대림산업 주식회사 | 폴리부텐 중합체 조성물 및 그 제조방법 |
KR20100069011A (ko) * | 2008-12-15 | 2010-06-24 | 대림산업 주식회사 | 삼불화붕소 착화합물 촉매 및 이를 이용한 고반응성 폴리부텐의 제조방법 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2998324A4 |
Also Published As
Publication number | Publication date |
---|---|
EP2998324A1 (en) | 2016-03-23 |
BR112015028534A2 (pt) | 2017-07-25 |
SG11201509314YA (en) | 2015-12-30 |
KR20140135452A (ko) | 2014-11-26 |
CN105246920A (zh) | 2016-01-13 |
JP2016519197A (ja) | 2016-06-30 |
KR101523568B1 (ko) | 2015-05-28 |
CN105246920B (zh) | 2021-05-25 |
JP6454327B2 (ja) | 2019-01-16 |
EP2998324B1 (en) | 2022-01-19 |
SA515370147B1 (ar) | 2018-05-24 |
US10059786B2 (en) | 2018-08-28 |
MY176816A (en) | 2020-08-21 |
US20160108155A1 (en) | 2016-04-21 |
CN109535288A (zh) | 2019-03-29 |
BR112015028534B1 (pt) | 2020-09-01 |
EP2998324A4 (en) | 2017-02-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2014112768A1 (ko) | 폴리부텐의 제조 방법 | |
WO2014185723A1 (ko) | 반응성 폴리부텐 및 비반응성 폴리부텐의 선택적 제조장치 및 방법 | |
WO2015016577A1 (ko) | 폴리부텐 제조 시 사용되는 원료의 재순환 장치 및 방법 | |
US7411104B2 (en) | Method for producing polybutene | |
WO2015102423A1 (ko) | 에틸렌과 알파-올레핀의 중합 장치 및 제조방법 | |
WO2016028123A1 (ko) | 폴리부텐의 제조방법 | |
WO2015030489A1 (ko) | 폴리부텐 제조 시 발생되는 할로겐의 제거 장치 및 방법 | |
JP2019090052A (ja) | 多様な分子量を有するポリブテンの製造装置および方法 | |
WO2015012550A1 (ko) | 메틸올알칸알의 제조방법 | |
WO2010071307A2 (ko) | 삼불화붕소 착화합물 촉매 및 이를 이용한 고반응성 폴리부텐의 제조방법 | |
WO2012112003A2 (ko) | 글리콜에테르를 이용한 고순도 이소부텐의 제조 방법 | |
KR101871071B1 (ko) | 폴리부텐의 제조방법, 이에 의해 제조된 폴리부텐, 및 이에 의해 제조된 폴리부텐의 제조장치 | |
WO2015002509A1 (ko) | 폴리부텐 제조 시 발생되는 폐수의 처리 장치 및 방법 | |
KR20130115624A (ko) | 삼불화붕소 착물 촉매 및 이를 이용한 고반응성 폴리부텐의 제조방법 | |
WO2015194874A1 (ko) | 노르말 프로판올을 포함한 촉매를 이용한 폴리부텐의 제조방법 | |
KR101511707B1 (ko) | 분자량 조절이 용이한 폴리부텐의 제조장치 및 방법 | |
WO2020080647A1 (ko) | 비반응성 폴리부텐의 제조방법, 비반응성 폴리부텐의 제조장치 및 이에 의해 제조된 비반응성 폴리부텐 | |
KR101457452B1 (ko) | 다양한 분자량을 가지는 폴리부텐의 제조 장치 및 방법 | |
KR102203006B1 (ko) | 고반응성 폴리부텐의 제조 방법 | |
EP2563748A1 (en) | Method of preparing alkene compound | |
WO2019139264A1 (ko) | 디메틸뮤코네이트의 부가 고리화 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14797177 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14890489 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2016513876 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014797177 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015028534 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112015028534 Country of ref document: BR Kind code of ref document: A2 Effective date: 20151113 |