CN114907532A - Process for producing oxymethylene polymer - Google Patents
Process for producing oxymethylene polymer Download PDFInfo
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- CN114907532A CN114907532A CN202210085315.5A CN202210085315A CN114907532A CN 114907532 A CN114907532 A CN 114907532A CN 202210085315 A CN202210085315 A CN 202210085315A CN 114907532 A CN114907532 A CN 114907532A
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- catalyst
- raw material
- oxymethylene polymer
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- 229920000642 polymer Polymers 0.000 title claims abstract description 60
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002994 raw material Substances 0.000 claims abstract description 62
- 239000007788 liquid Substances 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 54
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 50
- 239000000126 substance Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 239000002685 polymerization catalyst Substances 0.000 claims description 22
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical group C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 11
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 238000002156 mixing Methods 0.000 description 9
- 150000004292 cyclic ethers Chemical class 0.000 description 7
- 125000004122 cyclic group Chemical group 0.000 description 7
- 238000007865 diluting Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- -1 Hexafluorophosphate Chemical compound 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
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- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000011964 heteropoly acid Substances 0.000 description 3
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- 239000003607 modifier Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- PYOKUURKVVELLB-UHFFFAOYSA-N trimethyl orthoformate Chemical compound COC(OC)OC PYOKUURKVVELLB-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KIAMPLQEZAMORJ-UHFFFAOYSA-N 1-ethoxy-2-[2-(2-ethoxyethoxy)ethoxy]ethane Chemical compound CCOCCOCCOCCOCC KIAMPLQEZAMORJ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical class CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NAHIZHJHSUSESF-UHFFFAOYSA-N perchloryl acetate Chemical compound CC(=O)OCl(=O)(=O)=O NAHIZHJHSUSESF-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- AFSIIZRPQXBCFM-UHFFFAOYSA-N tert-butyl perchlorate Chemical compound CC(C)(C)OCl(=O)(=O)=O AFSIIZRPQXBCFM-UHFFFAOYSA-N 0.000 description 1
- AHJWSRRHTXRLAQ-UHFFFAOYSA-N tetramethoxymethane Chemical compound COC(OC)(OC)OC AHJWSRRHTXRLAQ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- MVJKXJPDBTXECY-UHFFFAOYSA-N trifluoroborane;hydrate Chemical compound O.FB(F)F MVJKXJPDBTXECY-UHFFFAOYSA-N 0.000 description 1
- AQWKGXFXWCQPDB-UHFFFAOYSA-N trimethoxy(methoxymethoxy)methane Chemical compound COCOC(OC)(OC)OC AQWKGXFXWCQPDB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Chemical class 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
- C08G2/22—Copolymerisation of aldehydes or ketones with epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/18—Copolymerisation of aldehydes or ketones
- C08G2/20—Copolymerisation of aldehydes or ketones with other aldehydes or ketones
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention relates to a method for producing an oxymethylene polymer. An object of the present invention is to provide a method for producing an oxymethylene polymer, which can continuously and stably obtain an oxymethylene polymer by a polymerizer. A method for continuously producing an oxymethylene polymer, comprising the steps of: an introduction step of introducing a raw material substance and a liquid containing a catalyst into a polymerizer using a double tube composed of an inner tube and an outer tube; and a reaction step in which the raw material substance and the catalyst are reacted in the polymerization vessel to produce the oxymethylene polymer, wherein in the introduction step, the raw material substance is passed between an inner tube and an outer tube of the double tube, the liquid containing the catalyst is passed through the inside of the inner tube of the double tube, and the tip end portion of the inner tube is tapered toward the tip end in appearance.
Description
Technical Field
The present invention relates to a method for producing an oxymethylene polymer.
Background
Since the oxymethylene polymer is excellent in processability and productivity, it has an advantage that a product or a part having a desired shape can be efficiently produced by a molding method such as melt injection molding or melt extrusion molding. By utilizing such advantages, oxymethylene polymers are widely used in the fields of electric and electronic materials, automobiles, other various industrial materials, food packaging, and materials for parts. In the production of products for these applications, a method for producing an oxymethylene polymer, which comprises a polymerization step of mixing a raw material with a polymerization catalyst to continuously and stably obtain an oxymethylene polymer, is required.
In the method for obtaining the oxymethylene polymer, various methods have been proposed as a method for mixing a raw material substance with a polymerization catalyst and then supplying the mixture to a polymerization reactor.
For example, the following methods exist: a method in which a polymerization catalyst solution line introduced into a mixed raw material liquid line of a monomer and a comonomer is continuously operated without causing clogging of the line due to a polymer and a supply failure into a polymerizer due to a constriction by changing a feeding angle of the polymerization catalyst solution line (for example, see patent document 1); in the step of mixing a comonomer with a polymerization catalyst in advance and then mixing the mixture with a monomer, the comonomer is supplied in the same direction as the polymerization catalyst and the comonomer is brought into contact with the polymerization catalyst and mixed (see, for example, patent document 2).
Documents of the prior art
Patent document
[ patent document 1] Japanese patent No. 4092545 publication
[ patent document 2] Japanese patent No. 3208377 publication
Disclosure of Invention
Problems to be solved by the invention
In the above-mentioned patent document 1, the polymerization reaction is carried out by mixing the raw material substance and the catalyst, and the time from the mixing contact portion to the arrival at the polymerizer is specified, but the residence time in the contact portion becomes long due to the fluctuation of the supply amount of the raw material substance and the catalyst liquid and the fluctuation of the pressure in the polymerizer, and there is a possibility that the polymerization is stopped due to the sticking of the polymer to the front end portion of the pipe and the clogging of the supply portion.
In patent document 2, the catalyst liquid and the comonomer are mixed in advance to prepare a mixture, and the linear velocity and the mixing time of the mixed stream when the catalyst liquid, the comonomer and the trioxymethylene are mixed as the raw material are specified, but the possibility that the solid matter is adhered and the pipe of the supply part is clogged when the catalyst liquid, the comonomer and the trioxymethylene are mixed cannot be denied.
Accordingly, an object of the present invention is to provide a method for producing an oxymethylene polymer, which can continuously and stably obtain an oxymethylene polymer by a polymerizer.
Means for solving the problems
The present inventors have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, have found that: polymerization is inhibited by the adhesion of a pipe to a solid material to be polymerized, which is generated by the retention of a mixed liquid of the raw material and a catalyst liquid in the vicinity of the pipe when the raw material and the catalyst liquid (hereinafter also referred to as "catalyst liquid") are brought into contact with each other in the pipe for supplying the raw material and the catalyst liquid to the polymerization reactor. Furthermore, the present inventors have found that: the above problems can be solved by supplying a raw material substance and a catalyst liquid to a polymerizer using a double-walled tube having a specific structure, and the present invention has been completed.
That is, the present embodiment is as follows.
[1]
A method for continuously producing an oxymethylene polymer, comprising the steps of:
an introduction step of introducing a raw material substance and a liquid containing a catalyst into a polymerizer using a double tube composed of an inner tube and an outer tube; and
a reaction step of reacting the raw material substance with the catalyst in the polymerization reactor to produce an oxymethylene polymer,
in the introduction process, the introduction step is carried out,
the raw material passes through the space between the inner pipe and the outer pipe of the double-layer pipe,
the liquid containing the catalyst passes through the inside of the inner tube of the double tube, and
the front end portion of the inner tube is tapered toward the front end in appearance.
[2]
The process for producing an oxymethylene polymer according to [1], wherein the contacting of the raw material substance with the catalyst-containing liquid and the introduction into the polymerizer are carried out simultaneously.
[3]
The process for producing an oxymethylene polymer as set forth in [1] or [2], wherein the raw material is trioxane.
[4]
The process for producing an oxymethylene polymer according to any one of [1] to [3], wherein the catalyst is a cationic polymerization catalyst.
[5]
The process for producing an oxymethylene polymer according to any one of [1] to [4], wherein a ratio of a linear velocity of the raw material substance to a linear velocity of the catalyst-containing liquid in at least a part of a distal end portion of the double tube is in a range of 0.4 to 8.9.
[6]
The process for producing an oxymethylene polymer according to any one of [1] to [5], wherein, in the cross section of the inner tube, an angle of a taper angle formed by a line constituting the inner surface of the inner tube and a straight line connecting a point at which the thickness of the wall of the inner tube starts to gradually decrease and a point at which the thickness of the wall of the inner tube becomes minimum is within a range of 10 ° to 70 °.
[7]
The process for producing an oxymethylene polymer as set forth in [6], wherein the angle of the taper is in the range of 10 ° to 30 °.
Effects of the invention
The process for producing an oxymethylene polymer of the present invention can continuously and stably produce an oxymethylene polymer.
Drawings
Fig. 1 is a cross-sectional view of a double tube used in the present embodiment cut along a plane along its axis.
Detailed Description
Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. The following embodiments are illustrative of the present invention, and the present invention is not limited to the following. The present invention can be variously modified within the scope of the gist thereof.
(Process for producing oxymethylene Polymer)
The method for producing an oxymethylene polymer of the present embodiment is characterized by comprising the steps of: an introduction process in which a raw material substance and a liquid containing a catalyst are introduced into a polymerizer using a double tube; and a reaction step in which the raw material and the catalyst are reacted in the polymerization reactor to produce the oxymethylene polymer, wherein in the introduction step, the raw material passes through an outer-side liquid flow portion (between the inner tube and the outer tube) of the double tube, the catalyst liquid passes through an inner-side liquid flow portion (inside the inner tube) of the double tube, and the inner tube is tapered toward the tip in appearance at the tip end thereof. The tip portion does not strictly refer to only the tip of the tube, and includes a range that is reasonable for understanding the shape of the tube as shown in fig. 1.
[ introducing step ]
The method for producing an oxymethylene polymer according to the present embodiment includes an introducing step of supplying a raw material and a liquid containing a catalyst (catalyst liquid) to a polymerizer through a double-layer pipe composed of an inner pipe and an outer pipe. In the introduction step, optional components such as a molecular weight modifier described later, together with the raw material and the catalyst liquid, may be supplied to the polymerization reactor using a double tube.
In this step, it is preferable that the raw material and the catalyst liquid are contacted with each other and introduced into the polymerization reactor at the same time. Here, the phrase "the contact of the raw material substance with the catalyst liquid and the introduction into the polymerizer are performed simultaneously" means that the time difference between the point of time at which at least a part of the raw material substance is in contact with at least a part of the catalyst liquid and the point of time at which the raw material substance is introduced into the polymerizer is less than 0.1 second. Here, the "time point of introduction into the polymerization vessel" refers to a time point at which the mixed liquid formed by contacting the raw material substance with the catalyst liquid is located inside the polymerization vessel from the opening of the polymerization vessel (may be the tip of the double tube).
< double-layer pipe >
Fig. 1 shows a cross-sectional view of a double tube used in the present embodiment, the cross-sectional view being taken along a plane of the double tube along an axis thereof.
The double tube used in the present embodiment is a pipe for supplying the raw material and the catalyst liquid into the polymerization reactor, and is provided at the forefront part and the upper side of the polymerization reactor. The double tube is configured to allow the raw material to flow between the inner tube and the outer tube and allow the catalyst liquid to flow inside the inner tube. Here, the space inside the inner tube forms a double-layer tube-inside liquid portion, and the space between the inner tube and the outer tube forms a double-layer tube-outside liquid portion (see fig. 1). The cross-sectional area of the double-layer tube inner-side liquid flow portion may be constant over the predetermined extending length of the distal end portion of the inner tube, and the cross-sectional area of the double-layer tube outer-side liquid flow portion may be constant over the predetermined extending length of the distal end portion of the inner tube (see fig. 1).
Specifically, in the case of a homopolymer, for example, trioxane and an optional molecular weight modifier as raw material substances are previously mixed, and in the case of a copolymer, for example, trioxane and a cyclic ether and/or a cyclic formal as comonomers and an optional molecular weight modifier as raw material substances are previously mixed and passed through a double-layer pipe outside stream part. A catalyst liquid obtained by mixing a catalyst and a diluent solvent in advance is passed through the inner-side liquid flow portion.
At least a part of the front end of the double tube, for example, in a part where the raw material and the catalyst liquid flow at a constant linear velocity before coming into contact (a part where both the cross-sectional area of the double-tube inside-side liquid part and the cross-sectional area of the double-tube outside-side liquid part are constant), a ratio (ratio of the linear velocity of the raw material to the linear velocity of the catalyst liquid) obtained by dividing the linear velocity of the raw material by the linear velocity of the catalyst liquid is in a range of 0.4 to 8.9, and more preferably 0.9 to 8.4. Here, m/s is used as a unit of linear velocity.
As shown in fig. 1, the front end portion of the inner tube of the double tube has a shape (tapered shape) that is tapered toward the front end in appearance. Here, the cross-sectional area of the double-layer tube inner-side liquid flow portion at the leading end portion may be the same as the cross-sectional area of the double-layer tube inner-side liquid flow portion at the non-leading end portion. That is, in the inner tube of the double tube, at the leading end portion, the thickness of the wall of the inner tube of the double tube gradually decreases toward the leading end. In the cross section of the inner pipe (see fig. 1), a line constituting the inner surface of the inner pipe intersects with a straight line-shaped angle (taper angle) connecting a point at which the thickness of the wall of the inner pipe starts to gradually decrease and a point at which the thickness of the wall of the inner pipe reaches a minimum. In the cross section of the inner pipe, an end of a wire constituting an inner surface of the inner pipe is located at a position closer to an axially outer side of the double-walled pipe than an end of a wire constituting an outer surface of the inner pipe.
The angle of the taper angle is preferably 10 ° to 70 °, more preferably 10 ° to 30 °, and still more preferably 10 ° to 20 °. The angle of the taper angle may be set to be a small angle among angles formed by a line forming the inner surface of the inner tube and a straight line connecting a point at which the thickness of the wall of the inner tube starts to gradually decrease and a point at which the thickness of the wall of the inner tube is minimized.
In the present embodiment, when the range of the ratio obtained by dividing the linear velocity of the raw material by the linear velocity of the catalyst liquid and the angle of the tip of the inner tube are within the above range, continuous polymerization can be stably performed without the mixed liquid of the raw material and the catalyst liquid staying at the tip of the double tube.
< raw Material substance >
As the raw material used in the present embodiment, for example, trioxymethylene can be used.
Trioxymethylene can be produced by reacting formaldehyde in the presence of an acidic catalyst.
Water, formic acid, is generally included as an impurity in the raw material. These impurities act as a chain transfer agent, and the polymer terminal groups of the oxymethylene polymer obtained by polymerization may be in a thermally unstable state, and it may be difficult to obtain an oxymethylene polymer having high thermal stability. Therefore, it is preferred to purify these impurities to a certain concentration before the start of the polymerization. The total content of these impurities in the raw material substance is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, and further preferably 30 mass ppm or less, based on the mass of the raw material substance.
< raw Material substance of copolymer >
In the present embodiment, in the case of producing a copolymer of an oxymethylene polymer, a cyclic ether and/or a cyclic formal may be used as a comonomer component added to a raw material substance. Specifically, examples of the cyclic ether and/or cyclic formal include: ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, phenyloxirane, oxetane, 1, 3-dioxolane, ethylene glycol formal, propylene glycol formal, diethylene glycol formal, triethylene glycol formal, 1, 4-butanediol formal, 1, 5-pentanediol formal, 1, 6-hexanediol formal, and the like. These may be used alone or in combination of two or more.
In the polymerization, the amount of the cyclic ether and/or the cyclic formal to be added is preferably in the range of 0.01 to 0.2 mol, more preferably in the range of 0.01 to 0.15 mol, further preferably in the range of 0.01 to 0.1 mol, and particularly preferably in the range of 0.01 to 0.05 mol, based on 1 mol of the raw material. When the amount of the cyclic ether and/or the cyclic formal added is within the above range, the polymerization rate tends to be increased to some extent, the polymerization yield tends to be sufficiently high, and the oxymethylene polymer can be stably produced.
< catalyst >
The catalyst used in the production method of the present embodiment is not particularly limited as long as it can stably produce the oxymethylene polymer, and a cationic polymerization catalyst is preferred. Examples of the cationic polymerization catalyst include Lewis acids, protonic acids, and esters or anhydrides thereof. Examples of the lewis acid include halides of boron, tin, titanium, phosphorus, arsenic and antimony, and boron trifluoride, boron trifluoride hydrate, and a coordination complex of an organic compound containing an oxygen atom or a sulfur atom and boron trifluoride are particularly preferable. Examples of the protonic acid and its ester or anhydride include perchloric acid, trifluoromethanesulfonic acid, tert-butyl perchlorate, acetyl perchlorate, and trimethyloxy
Hexafluorophosphate, heteropolyacid, isopolyacid, acid salt of heteropolyacid and acid salt of isopolyacid, and heteropolyacid is particularly preferable. These may be used alone or in combination of two or more.
From the viewpoint of stably carrying out continuous polymerization, the amount of the polymerization catalyst to be added is preferably 1X 10 relative to 1 mol of the raw material -9 mole-1X 10 -2 In the molar range, more preferably 2X 10 -9 mol-1X 10 -2 In the molar range, it is more preferably 5X 10 -9 mole-1X 10 -3 In the molar range.
< catalyst liquid >
The catalyst solution used in the production method of the present embodiment is prepared by diluting the polymerization catalyst with an inert diluent solvent which does not adversely affect the polymerization reaction.
The diluting solvent used for diluting the polymerization catalyst is preferably a hydrocarbon compound having no hydroxyl group. Specific examples of the hydrocarbon compound include: aromatic hydrocarbon compounds such as benzene, toluene and xylene; aliphatic hydrocarbon compounds such as n-hexane, n-heptane and cyclohexane; ether compounds such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol diethyl ether, and 1, 4-dioxane can be appropriately selected depending on the solubility of the cationic polymerization catalyst to be used. The above hydrocarbon compounds having no hydroxyl group may be used alone or in combination of two or more. By using such a hydrocarbon compound having no hydroxyl group as a diluting solvent, the molecular weight of the oxymethylene polymer can be easily controlled.
In the polymerization, the amount of the diluting solvent to be added is preferably 0.1X 10 relative to 1 mole of the raw material -3 The molar ratio is in the range of 0.2 mol, more preferably 0.2X 10 mol -3 The molar ratio is in the range of 0.1 mol to 0.5X 10 mol, preferably 0.5X 10 mol -3 The molar amount is in the range of 0.05 mol. When the amount of the diluting solvent is within the above range, the polymerization reaction is not inhibited and the oxymethylene polymer can be obtained in a higher yield.
< molecular weight regulator >
In the present embodiment, a low molecular weight acetal compound may be used as the molecular weight regulator. The low-molecular-weight acetal compound functions as a chain transfer agent in polymerization of a raw material substance and a cyclic ether and/or a cyclic formal, and has a molecular weight of 200 or less, preferably 60 to 170. Specifically, as the molecular weight regulator, there can be suitably mentioned: methylal, methoxy methylal, dimethoxy methylal and trimethoxy methylal. These may be used alone or in combination of two or more. In addition, from the viewpoint of controlling the molecular weight of the oxymethylene polymer within an appropriate range, the amount of the low-molecular acetal compound added is preferably 0.1X 10 relative to 1 mole of the raw material during polymerization -4 molar-0.6X 10 -2 In the molar range.
[ reaction Process ]
The production method of the present embodiment includes a reaction step of reacting a raw material substance with a catalyst in a polymerization reactor to produce an oxymethylene polymer. The oxymethylene polymer is polymerized by cationic polymerization using a bulk polymerization method. The shape (structure) of the polymerization reactor to be used is not particularly limited, and a biaxial paddle type or screw type stirring/mixing type polymerization reactor capable of passing a heat medium through a jacket can be suitably used in general.
The polymerization temperature is preferably maintained in the range of 63 ℃ to 135 ℃. The polymerization reaction temperature is more preferably in the range of 70 to 120 ℃ and still more preferably in the range of 70 to 100 ℃.
The residence (reaction) time in the polymerization reactor is preferably 0.1 to 30 minutes, more preferably 0.1 to 25 minutes, and still more preferably 0.1 to 20 minutes.
By adjusting the polymerization reaction temperature and the residence time in the polymerization reactor to the above ranges, respectively, thermal decomposition of the oxymethylene polymer can be more effectively suppressed, and a more thermally stable oxymethylene polymer can be produced.
< washing, filtration, drying after polymerization >
Then, the polymerization catalyst can be removed by, for example, washing from the resulting oxymethylene polymer after the polymerization. As the method for washing and removing the polymerization catalyst, conventionally proposed methods can be used, and for example, the oxymethylene polymer discharged from the polymerization reactor can be charged into water alone or into an amine containing ammonia, triethylamine, tri-n-butylamine, or the like; an aqueous solution of at least one deactivator selected from hydroxides of alkali metals or alkaline earth metals, inorganic salts, organic acid salts and the like is stirred continuously in a slurry state at room temperature to 100 ℃ or lower for several minutes to several hours while cleaning and removing the polymerization catalyst. When the oxymethylene polymer is in the form of a large block, it is preferable to pulverize and miniaturize the oxymethylene polymer so as to facilitate cleaning and removal, from the viewpoint of improving the cleaning and removal efficiency of the polymerization catalyst. After the polymerization catalyst is washed and removed, the objective oxymethylene polymer can be obtained by filtration with a centrifuge or the like and drying in a nitrogen atmosphere or the like.
[ examples ]
The present embodiment will be described in detail below by referring to specific examples and comparative examples, but the present embodiment is not limited to the following examples unless the gist thereof is exceeded.
The evaluation methods and raw materials used in the examples and comparative examples are as follows.
[ method for evaluating operational stability ]
When a raw material and a catalyst liquid were supplied to a polymerization reactor through a double tube and continuously polymerized, the continuous operation time was evaluated until the rate of pressure change of the raw material supply unit and the catalyst liquid supply unit, which is caused by clogging of the tip of the double tube, was observed to be 50% or more of the value at which the rate of pressure change was stable.
[ example 1]
As a polymerizer, a biaxial paddle type continuous polymerization reactor (manufactured by Tanbo iron works Co., Ltd., diameter 2B, L/D: 14.8) rotating in the same direction set at 80 ℃ was used. In order to prevent the incorporation of oxygen, 60 liters of nitrogen gas was introduced from the vicinity of the feed port of the polymerization reactor every 1 hour. A double tube having a tapered shape at the tip end of the inner tube is used, and the angle θ of the taper angle is as described later. Then, trioxymethylene was supplied to the polymerization reactor through the double-layer tube outside-side liquid portion at 4000 g/hr. In addition, 0.045 mole (148.0 g/hr) of 1, 3-dioxolane as cyclic ether and/or cyclic formal relative to 1 mole of trioxane was fed to the polymerization reactor. Then, ferric chloride as a polymerization catalyst was diluted with 1, 4-dioxane as a diluting solvent at an appropriate ratio, and the obtained polymerization catalyst liquid was supplied to the polymerizer through the inside flow liquid portion of the double-layer tube, and polymerization was started. The time difference between the point of contact between the mixture of trioxymethylene and 1, 3-dioxolane and the 1, 4-dioxane solution of ferric trichloride and the point of contact between the mixture thereof and the point of contact between them which is located on the inner side of the opening of the polymerization reactor is less than 0.1 second.
The results are shown in table 1.
[ examples 2 to 7]
The same procedure as in example 1 was repeated, except that the linear velocity ratio of the raw material to the catalyst liquid and the tube tip angle were set to the conditions shown in table 1.
The results are shown in table 1.
[ Table 1]
Comparative examples 1 and 2
The same procedure as in example 1 was repeated, except that the linear velocity ratio of the raw material to the catalyst liquid and the tube end angle were set to the conditions shown in table 2.
The results are shown in table 2.
[ Table 2]
| Comparative example 1 | Comparative example 2 | |
| Angle theta (°) | 90 | 90 |
| Linear velocity ratio | 3.2 | 6.9 |
| Run time (hours) | 3 | 2 |
As shown in table 1, in examples 1 to 7, since the front end portion of the inner tube has a shape narrowing toward the front end, there is no pressure fluctuation in the supply line, and the operation can be continued for 7 hours or more without any problem.
As shown in Table 2, in comparative examples 1 to 2, since the front end portion of the inner tube was not tapered toward the front end, the pressure fluctuation of the supply line was significant, and the operation of the polymerization reactor was stopped shortly after the start of polymerization. The end of the double tube was observed after the polymerization vessel was stopped, and as a result, clogging of the tube due to polymer deposition was observed, which was not practical.
Industrial applicability
The process for producing an oxymethylene polymer of the present invention can continuously and stably produce an oxymethylene polymer.
Claims (7)
1. A method for continuously producing an oxymethylene polymer, comprising the steps of:
an introduction step of introducing a raw material substance and a liquid containing a catalyst into a polymerizer using a double-layer tube composed of an inner tube and an outer tube; and
a reaction step of reacting the raw material substance with the catalyst in the polymerization vessel to produce an oxymethylene polymer,
in the introduction process, the introduction step is carried out,
the raw material passes through the space between the inner pipe and the outer pipe of the double-layer pipe,
the liquid containing the catalyst passes through the inside of the inner tube of the double tube, and
the front end portion of the inner tube is tapered toward the front end in appearance.
2. The process for producing an oxymethylene polymer as set forth in claim 1, wherein said raw material substance is contacted with said catalyst-containing liquid and introduced into a polymerizer at the same time.
3. The process for producing an oxymethylene polymer as set forth in claim 1 or 2, wherein said raw material substance is trioxymethylene.
4. The process for producing an oxymethylene polymer as set forth in any one of claims 1 to 3, wherein said catalyst is a cationic polymerization catalyst.
5. The process for producing an oxymethylene polymer as set forth in any one of claims 1 to 4, wherein a ratio of a linear velocity of said raw material to a linear velocity of said catalyst-containing liquid in at least a part of a front end portion of said double tube is in a range of 0.4 to 8.9.
6. The process for producing an oxymethylene polymer as set forth in any one of claims 1 to 5, wherein, in the cross-section of said inner tube, the angle of the taper angle formed by a line constituting the inner surface of said inner tube and a straight line connecting a point at which the thickness of the wall of said inner tube starts to gradually decrease and a point at which the thickness of the wall of said inner tube becomes minimum is within the range of 10 ° to 70 °.
7. The process for producing an oxymethylene polymer as set forth in claim 6, wherein the angle of said taper angle is in the range of 10 ° to 30 °.
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