CN107118315A - The manufacture method of Copolyacetal - Google Patents
The manufacture method of Copolyacetal Download PDFInfo
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- CN107118315A CN107118315A CN201710103128.4A CN201710103128A CN107118315A CN 107118315 A CN107118315 A CN 107118315A CN 201710103128 A CN201710103128 A CN 201710103128A CN 107118315 A CN107118315 A CN 107118315A
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- copolyacetal
- alkane
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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
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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
- C08G2/06—Catalysts
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Abstract
The present invention relates to the manufacture method of Copolyacetal.The present invention provides a kind of method for the Copolyacetal that can be steadily in the long term continuously run with high polymerization yield while the usage amount of polymerization catalyst is reduced and can manufacture HMW.A kind of manufacture method of Copolyacetal, it is by threeAlkane, except three
Description
Technical field
The present invention relates to the manufacture method of Copolyacetal.
Background technology
Copolyacetal is the excellent resin materials such as mechanical strength, sliding, creep resistant, heat resistance, with automobile
It is widely used centered on the mechanism part such as part and electric/electronic.In addition, in recent years, due to the development of forming technique,
Demand to high molecular weight polyacetal copolymer is improved.Therefore, it is desirable to manufacture high molecular weight polyacetal copolymer with high production rate
Technology.
In order to manufacture the high molecular weight polyacetal copolymer with stabilizing quality, it is necessary in polymerisation with high production rate
Operating steady in a long-term.
But in the past since, manufacture Copolyacetal when, exist to polymer reactor base feed raw material confession
To producing fouling in portion, it is impossible to the problem of raw material stablized is supplied.The generation of fouling not only hinders operating steady in a long-term,
The reason for being reduced as polymerization yield.
As the method that this fouling is produced is suppressed, the polymerization for reducing and being used when manufacturing Copolyacetal can be enumerated
The method of the usage amount of catalyst.
As the technology of polymerization catalyst can be reduced, disclose cyclic ether and/or cyclic formals, polymerization catalyst
And low molecule amount acetal compound is pre-mixed and added and is supplied to threePolymerize in alkane technology (for example, with reference to
Patent document 1), and cyclic ether and/or cyclic formals, polymerization catalyst and organic solvent are pre-mixed, and with three
The technology that alkane is contacted and polymerize (for example, with reference to patent document 2).
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 11-255854 publications
Patent document 2：Japanese Unexamined Patent Publication 01-69616 publications
The content of the invention
Invent problem to be solved
However, from the aspect of the fouling suppressed in the raw material supply unit to polymer reactor base feed is produced,
Technology described in these patent documents can not still be said enough.In addition, there is also the actual upper limit of resulting Copolyacetal
The problem of the Copolyacetal of low molecule amount.
Therefore, problem of the invention is：A kind of method of Copolyacetal is provided, methods described can gather reducing
While closing the usage amount of catalyst, continuously run steadily in the long term with height polymerization yield, and HMW can be manufactured
Copolyacetal.
The means used to solve the problem
In order to solve above-mentioned problem, present inventor has performed further investigation.As a result find, by will containing cyclic ether and/
Or the mixed liquor of cyclic formals and polymerization catalyst by the arithmetic average roughness of inwall for less than 3 μm of pipeline supply to
Polymer reactor, can suppress the fouling in the raw material supply unit to polymer reactor base feed, and can suppress attached
The coloring fouling on polymerizer.And it was found that, can be poly- with height thus while the usage amount of polymerization catalyst is reduced
Close yield and continuously manufacture Copolyacetal steadily in the long term, so as to complete the present invention.
That is, the present invention is as described below.
[1] a kind of manufacture method of Copolyacetal, it is by threeAlkane, except threeCyclic ether beyond alkane and/or
Cyclic formals and polymerization catalyst supply the method for manufacturing Copolyacetal to polymer reactor, wherein,
The manufacture method is interior including the mixed liquor containing cyclic ether and/or cyclic formals and polymerization catalyst is passed through
The arithmetic average roughness of wall is supplied to the process of polymer reactor for less than 3 μm of pipeline.
[2] manufacture method of the Copolyacetal as described in [1], wherein, the polymerization catalyst is selected from by trifluoro
Change at least one of group that boron, boron trifluoride diethyl ether complexes and boron trifluoride butyl oxide complex compound are constituted.
[3] manufacture method of the Copolyacetal as described in [1] or [2], wherein, the mixed liquor is also containing organic molten
Agent.
[4] manufacture method of the Copolyacetal as described in [3], wherein, the organic solvent be selected from by n-hexane,
At least one of group that normal heptane and hexamethylene are constituted.
Invention effect
According to the present invention it is possible to suppress the fouling of the raw material supply unit to polymer reactor base feed, it is possible thereby to real
It is now steady in a long-term to operate and change in high yield.In addition, can also be kept in high yield even if the usage amount for reducing polymerization catalyst.
Embodiment
Hereinafter, the embodiment (hereinafter referred to as " present embodiment ") of the present invention is described in detail.
It should be noted that recorded the invention is not restricted to following, can carry out various modifications in the range of its purport and
Implement.
The manufacture method of the Copolyacetal of present embodiment is by threeAlkane, except threeCyclic ether beyond alkane and/
Or cyclic formals and polymerization catalyst supply the manufacture method for the Copolyacetal being polymerize to polymer reactor,
The manufacture method of the Copolyacetal is included the mixed liquor containing cyclic ether and/or cyclic formals and polymerization catalyst
Supplied by the arithmetic average roughness of inwall for less than 3 μm of pipeline to the process of polymer reactor.
(raw material etc.)
First, to being used as the three of the raw material used in the manufacture method of the Copolyacetal of present embodimentAlkane and
The material such as cyclic ether and/or cyclic formals, polymerization catalyst, solvent is illustrated.
It should be noted that in the present embodiment, threeBeyond alkane and cyclic ether and/or cyclic formals, when
So can also using can be formed block, side chain, cross-linked structure other copolymer compositions used as material combination.
<ThreeAlkane>
ThreeAlkane be formaldehyde cyclic trimer, generally can by make in the presence of acidic catalyst formaldehyde react and
Obtain.
ThreeAlkane plays the impurity of chain-transferring agent effect sometimes with water, methanol, formic acid, methyl formate etc., therefore preferably
These impurity are removed and purified by the method such as by distillation.In this case, the conjunction of the impurity of chain transfer reaction is caused
Metering is relative to three1 mole of alkane is preferably 1 × 10-3Below mole, more preferably 5 × 10-4Below mole.
When the amount of impurity is in above-mentioned number range, polymerization rate can be fully improved in practical application, and can
To obtain excellent heat endurance in the polymer generated.
<Cyclic ether and/or cyclic formals>
Cyclic ether and/or cyclic formals are except threeMaterial beyond alkane, and for can be with threeAlkane copolymerization into
Point, it can enumerate for example：Oxirane, expoxy propane, epoxy butane, epichlorohydrin, epibromohydrin, styrene oxide, oxa- ring fourth
Alkane, 1,3- dioxolane, propane diols formal, diethylene glycol formal, triethylene glycol formal, 1,4- butanediol contracting first
Aldehyde, 1,5- pentanediols formal, 1,6-HD formal etc..In them, particularly preferred 1,3- dioxolane, Isosorbide-5-Nitrae-
Butanediol formal.
They can be used alone only one kind, can also be applied in combination two or more.
Except threeThe addition of cyclic ether and/or cyclic formals beyond alkane is relative to described threeAlkane is preferably 0.1
Mole %~20 mole % scope, more preferably 0.3 mole %~15 mole %, more preferably 0.5 mole %~10
Mole %, is still more preferably 1 mole of %~5 mole %.
<Polymerization catalyst>
As polymerization catalyst, it can enumerate for example：Using lewis acid as the boron of representative, tin, titanium, phosphorus, arsenic and antimony change
Compound etc., in particular it is preferred to boron trifluoride, boron trifluoride hydrate and organic compound containing oxygen atom or sulphur atom with
The co-ordination complex of boron trifluoride.Specifically, boron trifluoride and boron trifluoride diethyl ether complexes or borontrifluoride can be enumerated
The boron trifluoride dialkyl ether complex compound such as boron di-n-butyl ether complex compound is used as preference.
These polymerization catalysts can be used alone only one kind, can also be applied in combination two or more.
The addition of polymerization catalyst is relative to described three1 mole of alkane is preferably 1 × 10-6Mole~1 × 10-4Mole
Scope, more preferably 3 × 10-6Mole~5 × 10-5Mole scope, more preferably 5 × 10-6Mole~4 × 10-5Rub
Your scope.
By the way that the addition of polymerization catalyst is set as in the scope, with can reduction polymer reactor confession
While to fouling yield in portion, stably implement the tendency of prolonged polymerisation.
<Organic solvent>
In the present embodiment, organic solvent can be used.Organic solvent is preferred for containing cyclic ether and/or ring-type
The purposes that the mixed liquor of formal and polymerization catalyst is diluted.
As organic solvent, as long as being not involved in polymerisation and not having a negative impact, it is not particularly limited.Can be with
Enumerate for example：The aromatic hydrocarbon such as benzene (80 DEG C of boiling point), toluene (110.63 DEG C of boiling point), dimethylbenzene (144 DEG C of boiling point)；N-hexane (boiling
Select 69 DEG C), normal heptane (98 DEG C of boiling point), the aliphatic hydrocarbon such as hexamethylene (80.74 DEG C of boiling point)；Chloroform (61.2 DEG C of boiling point), dichloro
The halogenated hydrocarbons such as methane (40 DEG C of boiling point), carbon tetrachloride (76.8 DEG C of boiling point)；Diethyl ether (35 DEG C of boiling point), diethylene glycol dimethyl ether
Ethers such as (162 DEG C of boiling point), 1,4- dioxanes (101.1 DEG C of boiling point) etc..Particularly from the viewpoint of fouling is suppressed,
The aliphatic hydrocarbons such as n-hexane, normal heptane, hexamethylene can be enumerated as preference.
These organic solvents can be used alone only one kind, can also be applied in combination two or more.
The addition of organic solvent is relative to three1 mole of alkane is preferably 1 × 10-4Mole~0.2 mole of scope, it is more excellent
Elect 2 × 10 as-4Mole~5 × 10-2Mole scope, more preferably 5 × 10-4Mole~3 × 10-2Mole scope.
When the addition of organic solvent is in the scope, original is being supplied to polymer reactor with mixed liquor can be reduced
Fouling yield in the supply unit of material and can be to obtain the tendency of copolymer in high yield.
<Low molecule amount acetal compound>
In the present embodiment, low molecule amount acetal compound can be used in aftermentioned polymerization process as chain tra nsfer
Agent.Low molecule acetal compound is that molecular weight is less than 200, preferably 60~170 acetal compound.Specifically, Ke Yilie
Lift dimethoxym ethane, methoxy methyl acetal, dimethoxy dimethoxym ethane, trimethoxy dimethoxym ethane and be used as preference.These low molecule amounts contract
Aldehyde compound can be used alone one kind, can also be applied in combination two or more.
From the viewpoint of the molecular weight of polymer is controlled in preferred scope, the addition of low molecule amount acetal compound
Amount is relative to three1 mole preferably 1 × 10 of alkane-5Mole~6 × 10-3Mole scope.
In the presence of by low molecule amount acetal with total amount and above-mentioned threeAlkane is mixed and supplied to the method for polymer reactor；Will be low
Molecular weight acetals are mixed with mixed liquor described later with total amount and supplied to the method for polymer reactor；By the one of low molecule amount acetal
Part and above-mentioned threeAlkane is mixed and supplied to mixing reactor, and remaining total amount is mixed and supplied with mixed liquor described later
Which kind of method is method to polymerizer etc., select can.Particularly from the viewpoint of dispersed, preferably by low molecule amount
More than half of acetal compound and threeAlkane is mixed.
(process)
Then, each operation included in the manufacture method of Copolyacetal is illustrated.
<The process for supplying the mixed liquor containing polymerization catalyst>
In the present embodiment, the mixed liquor containing polymerization catalyst is supplied to the inwall of the pipeline of polymer reactor
Surface roughness is less than 3 μm.Here, surface roughness is to be determined using assay method specified in JIS-B0601-2001
Arithmetic average roughness (Ra).In particular, from the roughness curve obtained on inwall, selected on the direction of its average line
Datum length (l) is taken, the selected part is added up to and is averaged from average line to the absolute value for the deviation for determining curve
Obtained from be worth, the value when representing roughness curve using y=f (x) to be expressed from the next.
[mathematical expression 1]
Usually, in the production line of organic compound, it is used as the pipe used when conveying the solution containing organic solvent
Road, using by by pipeline formed by the ester mouldings such as the metals such as stainless steel or Teflon.For the inwall of this pipeline, lead to
Often special smoothing techniques are not implemented, therefore, its arithmetic average roughness (Ra) is usually more than 10 μm.
However, in the present embodiment, implementing smoothing techniques etc. by the inwall to pipeline, making its arithmetic mean roughness
Spend for less than 3 μm.As one of smoothing techniques, it can enumerate：Ream machining (リ ー マ process), heat treatment process, electric discharge
Processing, polishing etc..Alternatively, it is also possible to use other method of surface finish.As one example, fluororesin processing, chromium can be enumerated
Or the plating processing of nickel etc..
Found by the research of the present inventor, by the way that the arithmetic average roughness of the inwall of pipeline is set as into less than 3 μm,
Surprisingly, can suppress to convey the generation of blocking or the fouling of the pipeline of mixed liquor.The arithmetic average of the inwall of pipeline is thick
Rugosity is preferably less than 3 μm, more preferably more preferably less than 2 μm, less than 1 μm.In the present embodiment, as pipeline
Material, material, fluororesin (Teflon (registration mark)), the glass of acid resistance, pitting corrosion resistance preferably with more than SUS304
Glass.
<The preparation section of mixed liquor>
In the manufacture method of the Copolyacetal of present embodiment, contain cyclic ether and/or cyclic formals and poly-
Closing the mixed liquor of catalyst can be prepared by will be each introduced into pipeline and collaborating in pipeline, will can also mixed
Liquid is supplied to before the process of polymer reactor by pipeline, by least a portion of cyclic ether and/or cyclic formals and poly-
Close catalyst and the organic solvent according further to needs is mixed in stainless steel etc. in advance, so as to obtain mixed liquor.
In the process, preferably polymerization catalyst is added in stainless steel (pipeline) (using organic solvent first
In the case of, polymerization catalyst and organic solvent are added in stainless steel (pipeline) and mixed first), then mix cyclic ether
And/or cyclic formals.Now, for cyclic ether and/or cyclic formals, it can enter to be about to total amount to be mixed into mixed liquor
In, or a part is mixed into mixed liquor and surplus is mixed into threeThe medium operation of alkane, is then added to polymerization anti-
Answer in device.From the viewpoint of the easiness of operation, preferably total amount is mixed into mixed liquor.
By being mixed with this order, the viscosity rising drastically of mixed liquor can be suppressed, can be reliably carried out
Operating steady in a long-term.Particularly in the case of using organic solvent, it is believed that by first by polymerization catalyst and organic solvent
Mixing, finally mixes cyclic ether and/or cyclic formals, it is possible thereby to suppress viscosity rising drastically.
In addition, being preferably from more than 15 DEG C to less than organic as the temperature for mixing polymerization catalyst and organic solvent
The scope of the boiling point of solvent, more preferably from more than 25 DEG C to the boiling point less than organic solvent scope, be more preferably from
More than the 35 DEG C scopes to the boiling point less than organic solvent.
It can suppress the generation of fouling by carrying out mixing more than 15 DEG C, pass through the temperature in the boiling point less than organic solvent
The lower progress mixing of degree can prevent the volatilization of organic solvent.
In addition, after being prepared from mixed liquor to polymer reactor supply mixed liquor process, in order to keep mixing
Each raw material, is preferably sufficiently mixed by the uniformity of liquid in the preparation section of mixed liquor.
As mixed method, it can enumerate for example：Each raw material is continually introduced into pipeline, and it is collaborated simultaneously in pipeline
The method of mixing；Each raw material is continually introduced into pipeline, it is collaborated in pipeline, and utilizes the static state for being arranged at pipe downstream
The method that blender is mixed；Method of each raw material etc. is mixed in the container for possess mixer.
In addition, being used as the temperature for implementing mixing, preferably greater than 0 DEG C and the scope less than 80 DEG C.
, can be with low cost implementation by implementing mixing in the temperature range, and viscosity can be suppressed drastically
Rise, so as to operating steady in a long-term.
In addition, being used as the time for implementing mixing, the more preferably scope of preferably 0.01 minute~120 minutes, 0.01 point
The scope of clock~60 minute.
By the way that mixing temperature and time are set as in above range, each raw material can be sufficiently mixed, and can press down
The viscosity drastically of mixture processed rises, so as to operating steady in a long-term.
<Supply threeThe step of alkane>
In the present embodiment, also by threeAlkane is supplied to the polymer reactor for implementing polymerisation process described later.
ThreeAlkane may be embodied in the mixed liquor containing cyclic ether and/or cyclic formals and polymerization catalyst, with mixing
Liquid is closed to supply together to polymer reactor；Can also be by being supplied from by mixed liquor to the different pipeline of the pipeline of polymer reactor
Supply to polymer reactor.
By threeIn the case that alkane is supplied to polymer reactor by the pipeline different from mixed liquor, supply threeAlkane
Do not limit, can supply simultaneously with the order of mixed liquor, any one can also be first supplied to polymer reactor, then supplied again
To another one.In addition, on by threeAlkane supplies the pipeline used during to polymer reactor, and the arithmetic for preferably using its inwall is put down
Equal roughness is less than 3 μm of pipeline.In addition it is also possible to by other raw materials (low molecule amount acetal compound etc.) and threeAlkane one
Supply is played to polymer reactor.
<Polymerisation process>
In the manner by threeAlkane and mixed liquor are supplied to polymer reactor, are then carried out polymerisation, are obtained
To Copolyacetal.
As the polymerization of Copolyacetal, such as can use slurry process, substance law, fusion method.
In addition, the shape (structure) of used polymer reactor is not particularly limited, for example it is preferable to use can
Make paddle or screw stirring mixed type polyplant of the twin shaft that thermal medium circulates in chuck etc..
The temperature of polymer reactor is preferably maintained at 63 DEG C~135 DEG C, more preferably 70 DEG C~120 in polymerisation process
DEG C scope, more preferably 70 DEG C~100 DEG C of scope.Delay (reaction) time in polymer reactor is preferably 0.1
Minute~30 minutes, more preferably 0.1 minute~25 minutes, more preferably 0.1 minute~20 minutes.
It is anti-with the lasting polymerization stablized if the temperature of polymer reactor and holdup time are within the above range
The tendency answered.
By above-mentioned polymerisation process, thick Copolyacetal can be obtained.
<Inactivate process etc.>
After thick Copolyacetal is obtained, the inactivation process for inactivating polymerization catalyst can be set.Urged as polymerization
The method for deactivating of agent, can be enumerated for example：The thick Copolyacetal input discharged from polymer reactor is contained into ammonia, three second
Nertralizer/the deactivators such as the amines such as amine, tri-n-butylamine, the hydroxide of alkali metal or alkaline-earth metal, inorganic salts, acylate
In at least one kind of aqueous solution or organic solution in (neutralizing inactivation drug), and under slurry state below room temperature~100 DEG C
In the range of continuously stir the methods of several minutes~a few hours.Now, in the thick polyacetals copolymerization obtained by polymerisation process
In the case that thing is big bulk, preferably first carry out crushing and then carrying out inactivation processing after polymerisation.
Then, for example, being filtered by using centrifugal separator, and it is dried under a nitrogen, target can be obtained and gathered
Acetal copolymer.
Embodiment
Hereinafter, enumerating specific embodiment and comparative example, the present invention is described in detail, but the invention is not restricted to following
Embodiment.
It should be noted that the assay method of the term and characteristic in embodiment and comparative example is as follows.
<The arithmetic average roughness (Ra) of the inwall of pipeline>
The arithmetic average roughness of the inwall of pipeline is measured according to JIS-B0601-2001 as described above.
Specifically, for from inwall randomly selected more than 4 positions use contact pin type surfagauge (strain
Manufactured Surfcoder of the small slope research of formula commercial firm etc.), it is measured for the length direction of pipeline.
Evaluation length (datum length) for measure is set as 400 μm.
<It polymerize yield (%)>
With the discharge rate (g/ hours) of the time per unit for the thick Copolyacetal discharged from polymer reactor divided by complete
The inlet amount (g/ hours) of the time per unit of portion's monomer, so as to calculate.
It should be noted that polymerization yield is calculated after polymerization starts 1 hour and after 240 hours.
<The production of the fouling of polymer reactor supply unit>
The polymer reactor after terminating will be continuously run to open, visually confirm the fouling condition of supply unit.
When fouling produces less, it is judged as representing that operating is stable.
<The generation situation of coloring material in polymer reactor>
Open and continuously run the polymer reactor after terminating, visually confirm the situation of the coloring in polymer reactor.Profit
Judged with following benchmark.
○：It is attached with white polyacetals.
×：It is colored as brown or yellow.
[embodiment 1]
By dual-axis paddle continuous polymerization reactor (this ironworker of Co., Ltd.'s chestnut with the chuck that can make medium passing
It is manufactured, diameter 2B, L/D=14.8) it is adjusted to 80 DEG C.
To be 0.5 μm of deformation Y-piece road by the arithmetic average roughness of the inwall comprising SUS316 of custom fabricated
(downstream connection of Y character segments has lateral) is connected to the polymer reactor.
First using as the boron trifluoride di-n-butyl ether complex compound of polymerization catalyst using 0.18g/ hours, be used as organic solvent
Hexamethylene (boiling point：80.74 DEG C) adjusted to 28 DEG C and be continually introduced into above-mentioned pipeline jointly with 6.5g/ hours, and mixed
Close (pipe temperature：28 DEG C), then from the lateral (pipe temperature being connected to downstream：25 DEG C) will as cyclic ether and/
Or 1, the 3- dioxolane of cyclic formals to 25 DEG C and was continually introduced into regulation in 120.9g/ hours, make its with upstream
Mixed polymerization catalyst and organic solvent collaborate and mixed, so as to obtain mixed liquor.
The mixed liquor was continuously fed into by polymer reactor with 127.58g/ hours by above-mentioned pipeline, while will include
The three of 3500g/ hoursThe three of alkane and the dimethoxym ethane as low molecule amount acetal compound of 3.9g/ hoursAlkane mixture
Polymer reactor is continuously fed into by other pipeline, so as to start polymerization.
After polymerization starts 1 hour and after 240 hours, the thick Copolyacetal discharged from polymer reactor is sampled to
In triethylamine aqueous solution (0.5 mass %), stirring in 1 hour is then implemented at normal temperatures, is then filtered using centrifugal separator,
The drying of 120 DEG C × 3 hours has been carried out under a nitrogen, so as to obtain Copolyacetal.
Commented after polymerization starts 1 hour and to the polymerization yield of resulting Copolyacetal after 240 hours
Valency.In addition, visually confirming the fouling production of polymerization stability and polymerizer supply unit after operating in 240 hours, polymerization
The generation situation of coloring material in reactor.Polymerize yield after 1h, after 240 hours be up to 95%, the generation of fouling
It is considerably less, it is white in polymer reactor, and the visual valuation of the generation situation of coloring material is zero.
[embodiment 2]
Except the arithmetic of the inwall in the deformation Y-piece road for being used to preparing/supplying mixed liquor by polymer reactor is connected to
Mean roughness is adjusted to beyond 2.8 μm, and Copolyacetal has been obtained in the same manner as example 1.
Commented after polymerization starts 1 hour and to the polymerization yield of resulting Copolyacetal after 240 hours
Valency.In addition, visually confirming the fouling production of polymerization stability and polymerizer supply unit after operating in 240 hours, polymerization
The generation situation of coloring material in reactor.Polymerize yield after 1h, after 240 hours be up to 95%, the generation of fouling
It is few, it is white in polymer reactor, and the visual valuation of the generation situation of coloring material is zero.
[comparative example 1]
Except having used, the arithmetic average roughness of commercially available inwall is 25 μm of the pipeline comprising SUS316 as composition
Beyond the pipeline for deforming Y-piece, Copolyacetal has been manufactured in the same manner as example 1.
When having carried out 25 hours and continuously running, the supply flow rate of boron trifluoride di-n-butyl ether complex compound becomes non-constant,
Can not stably it be supplied.
Pipeline inside is checked, as a result thick substances and coloring material in pipeline inside confirmation.
<Evaluation result>
It is less than in the arithmetic average roughness of the inwall of the pipeline of supply mixed liquor in 3 μm of embodiment 1,2, it is long-term continuous
The generation of fouling is few after polymerization, can be produced steadily in the long term.
On the other hand, in a comparative example, because the arithmetic average roughness of the inwall of pipeline is up to 25 μm, thus it is long-term steady
Qualitative difference.
Industrial applicability
Manufacturing method according to the invention, can manufacture the high molecular weight polyacetal with stable quality with high production rate
Copolymer, therefore, the present invention can suitably be used in the manufacture of various parts.
Especially, manufacturing method according to the invention, even if continuously being polymerize for a long time, the fouling of raw material supply unit
Produce also less, therefore the present invention is suitable for continuous manufacture.
Claims (4)
1. a kind of manufacture method of Copolyacetal, it is by threeAlkane, except threeCyclic ether and/or ring-type contracting beyond alkane
Formaldehyde and polymerization catalyst supply the method for manufacturing Copolyacetal to polymer reactor, wherein,
The manufacture method includes the mixed liquor containing cyclic ether and/or cyclic formals and polymerization catalyst passing through inwall
Arithmetic average roughness is supplied to the process of polymer reactor for less than 3 μm of pipeline.
2. the manufacture method of Copolyacetal as claimed in claim 1, wherein, the polymerization catalyst is selected from by trifluoro
Change at least one of group that boron, boron trifluoride diethyl ether complexes and boron trifluoride butyl oxide complex compound are constituted.
3. the manufacture method of Copolyacetal as claimed in claim 1 or 2, wherein, the mixed liquor is also containing organic molten
Agent.
4. the manufacture method of Copolyacetal as claimed in claim 3, wherein, the organic solvent be selected from by just oneself
At least one of group that alkane, normal heptane and hexamethylene are constituted.
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|---|---|---|---|
| JP2016034003A JP2017149853A (en) | 2016-02-25 | 2016-02-25 | Method for producing polyacetal copolymer |
| JP2016-034003 | 2016-02-25 |
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| CN114907532A (en) * | 2021-02-09 | 2022-08-16 | 旭化成株式会社 | Process for producing oxymethylene polymer |
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| JP2017149854A (en) * | 2016-02-25 | 2017-08-31 | 旭化成株式会社 | Liquid feeding method of solution containing cationic polymerization catalyst |
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| CN114907532A (en) * | 2021-02-09 | 2022-08-16 | 旭化成株式会社 | Process for producing oxymethylene polymer |
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