CN1327414A - Extruding method for volatilization and screw type extrusion machine for volatilization - Google Patents
Extruding method for volatilization and screw type extrusion machine for volatilization Download PDFInfo
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- CN1327414A CN1327414A CN00802198A CN00802198A CN1327414A CN 1327414 A CN1327414 A CN 1327414A CN 00802198 A CN00802198 A CN 00802198A CN 00802198 A CN00802198 A CN 00802198A CN 1327414 A CN1327414 A CN 1327414A
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- devolatilization
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/765—Venting, drying means; Degassing means in the extruder apparatus
- B29C48/766—Venting, drying means; Degassing means in the extruder apparatus in screw extruders
- B29C48/767—Venting, drying means; Degassing means in the extruder apparatus in screw extruders through a degassing opening of a barrel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/84—Venting or degassing ; Removing liquids, e.g. by evaporating components
- B29B7/845—Venting, degassing or removing evaporated components in devices with rotary stirrers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/76—Venting, drying means; Degassing means
- B29C48/762—Vapour stripping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
In a method for extruding a polymer composition for volatilization which comprises supplying the polymer composition containing a polymer and volatile components to a screw type extrusion machine equipped with a cylinder having a supply port and an outlet for a polymer and an outlet for volatile components and a screw being rotatably supported within the cylinder at the supply for a polymer, and discharging volatile components from the outlet therefor, while withdrawing the polymer from the outlet therefor, an improvement wherein said supply port for a polymer has an opening area of its nozzle satisfying the formula (1): phi : polymer content based on weight (kg) of polymer composition [-] ( phi is represented as 0.50 when the polymer content is 50 %); Q: rate of supply of polymer [m<3>/min]; S: area of opening of nozzle [m<2>]; H: depth of flute of screw [m]; N: spindle speed of screw [min<-1>] ; D: diameter of screw [m] is disclosed. The improvement results in efficiently removing volatile materials while avoiding vent-up. phi x Q / H x N <= S <= 2 x D2...(1).
Description
Technical field
The present invention relates to a kind of devolatilization extruding (devolatilization extrusion) method and screw devolatilization pressurizing unit, this devolatilization pressing method is used for separating these volatilization compositions from the polymer composition that is obtained by solution polymerization process or block polymerization, comprise polymer and volatilization compositions such as unreacted monomer, solvent, the secondary biology of volatility with screw devolatilization pressurizing unit, obtains polymer.
Background technology
Isobutylene-based polymer is gazed at as optical material in recent years because of the transparency of its brilliance.In order to obtain this transparency to greatest extent, need thoroughly to get rid of the polluter (secondary biological) that on manufacture process, produces.
When the polymer that comprises polluter manufactures a product, the product that may obtain to have defective.For example, when making plastic optical fiber (the following optical fiber that is called for short sometimes), the length direction of optical fiber produces the part that the local transmission performance descends relatively.In addition, when making CD, occur as the blemish after being shaped.
For this reason, as polymerization, use special public clear 52-32665 communique, special fair 7-72212 communique, spy to open that the disclosed such polluter of flat 3-111408 communique is sneaked into the little continuous block polymerization of possibility and the continuous solution polymerization method is better.
The product that is obtained by such polymerization is the polymer composition that comprises the volatile components such as the secondary biology of volatility that generate in polymer and unreacted monomer solvent, the polymerization process.
The polymer containing ratio of this polymer composition is generally 40～70 weight %, so, thereby must a large amount of volatilization compositions of 60～30 weight % be sloughed its separation is removed from polymer composition.In addition, in the devolatilization operation, also will prevent the generation of polluter as far as possible, the occasion in that polluter produces need prevent that polluter is blended into the polymer of acquisition.
As separating the method for removing the volatilization composition, has the method for using screw rod devolatilization pressurizing unit from polymer composition.Screw devolatilization pressurizing unit generally has cylindrical shell and can be disposed at the interior screw rod of this cylindrical shell freely to rotate, and this cylindrical shell has polymer composition supply port, polymer outlet, reaches volatilization composition outlet (blow vent).That is, the polymer outlet will be delivered to from the polymer composition that the polymer composition supply port is supplied with by the revolution of screw rod in this devolatilization pressurizing unit one side, from volatilization composition export the volatilization composition of discharging polymer composition on one side.
In the public clear 52-17555 communique disclosed method of spy, the pore or the close gap of the nozzle by being located at the polymer composition supply port will be pressurized to 20kg/cm
2More than, be heated to 210 ℃～270 ℃ polymer composition and be injected in the cylindrical shell under the negative pressure～atmospheric pressure condition that is in 50Torr, direct injection supplies to screw rod.
When supplying with polymer composition under such condition, polymer composition is sharply foaming in cylindrical shell, is separated into volatilization composition and polymer, the major part of separable recovery volatilization composition.
Yet, in the method,, may stop up by the stream of polymer a period of time volatilization gas owing to, sharply foam at cylindrical shell interpolymer constituent to supply with polymer composition at a high speed, easily the generation ventilation is not smooth in the outlet of volatilization composition.When producing ventilation when smooth, the quantitative change of removing of volatilization composition gets unstablely, removes and becomes insufficient.The quality instability of the polymer that obtains becomes the reason that is occurred defective by the product of polymer manufacturing.
Therefore, not smooth in order to suppress ventilation, the setting free degree of service condition has to become very little, is difficult to set the condition that can carry out the favourable a large amount of processing of industry under many occasions.
Te Kaiping 3-49925 communique has been put down in writing the technology that improves this method.
Promptly, prepare screw devolatilization pressurizing unit, the composition that will volatilize on the length direction of cylindrical shell outlet is arranged on the drive division side (upstream side) of the screw rod of polymer composition supply port, guarantees that this polymer composition supply port and the axial distance of volatilization composition outlet are 3D (D: screw diameter).In this device, the polymer outlet is arranged on the opposition side of above-mentioned volatilization composition outlet on the cylindrical shell length direction.
Heating in advance contains the polymer composition of the composition that volatilizees, and makes the part gasification of volatilization composition, under the state of solution-air mixed flow or gas-liquid-solid mixed flow, this polymer composition is supplied in the cylindrical shell.Then, the volatilization composition that will separate from polymer exports discharge with the space of the flow velocity below the 50m/sec by being formed by cylindrical shell and screw rod from above-mentioned volatilization composition.
Open flat 3-49925 communique according to the spy and put down in writing,, discharge the volatilization composition with specific speed, thereby can eliminate the not smooth problem of ventilation substantially by setting the polymer composition supply port and the distance of volatilization composition outlet bigger by this method.
Being used for making the devolatilization pressurizing unit that is suitable for isobutylene-based polymer plastic optical fiber etc., that light transmission is good, compare with the devolatilization pressurizing unit that is used for general moulding material manufacturing, need to use very excellent material of corrosion resistance.
For example open in the clear 61-275705 communique the spy, disclosing and having used the nickel containing ratio is the screw rod of the above alloy formation of 10 weight % and the devolatilization pressurizing unit of cylindrical shell.
In addition, open in the flat 2-49005 communique the spy, disclosing and having used the chromium containing ratio is that 10～25 weight % are above, the nickel containing ratio is that 2 weight % are following, Rockwell Hardness C target hardness is the screw rod of the alloy formation more than 40 and the devolatilization pressurizing unit of cylindrical shell.There, when use surpassing the alloy of chromium containing ratio 25 weight %, chromium and mercaptan compound reaction from the isobutylene-based polymer raw material are separated out the chromic sulfide compound in the oxygen atmosphere, and the light transmission of the polymer of acquisition obviously worsens.
For silica fibre, in optical fiber, there is the cobalt ions of several ppb, optical transmission performance is extremely descended.For this reason, have the device that the material of the possibility of sneaking into cobalt constitutes as use and make plastic optical fiber, then may worsen the optical transmission performance (" macromolecule " Vol.47, p840 (1998) November number) of plastic optical fiber.Impurity when like this, plastic optical fiber is made is sneaked into the major issue that becomes left and right sides product performance.
Yet, in being recorded in the method that the spy opens flat 3-49925 communique,, have the problem of device maximization because the polymer composition supply port is long with the axial distance of volatilization composition outlet.Therefore, with the method for the public clear 52-17555 communique record of spy more as can be known, the free degree of service condition is wide, can set industrial advantageous conditions, but the big or small polymer composition treating capacity of installing relatively is little, can not obtain effect of sufficient.
In addition, though improved removing of volatilization composition, since above such reason, the easier problem of sneaking into polluter of method that exists the public clear 52-17555 communique of bit to put down in writing.
Promptly, on the length direction of cylindrical shell, though the polymer from the polymer composition supply port to polymer outlet is discharged from the polymer outlet often forcibly, but polymer easily is trapped in the space of the opposition side of polymer outlet, it is drive division (the axle envelope bearing portion) side of supporting screw, make the hot deterioration of a part of polymer by this delay, generate secondary biological.
This phenomenon takes place in the method for the public clear 52-17555 communique record of spy, but, particularly open distance between the volatilization composition of polymer composition supply port and drive division side exports in the method for flat 3-49925 communique record the spy, the volume of the polymer that is detained is big, easily produces secondary biological that hot deterioration forms.
In addition, no matter whether the distance between polymer composition supply port and the outlet of volatilization composition is long, not polymer-filled in this part.Like this, cylindrical shell directly contacts with screw rod, becomes the Metal Contact state, and the abrasive dust that is produced by adhesion becomes many, and this abrasive dust is blended in the polymer.
On the other hand, open the method that discloses use screw devolatilization pressurizing unit in the clear 59-133206 communique the spy, this screw devolatilization pressurizing unit is at the axial two ends of cylindrical shell internal support screw rod, supporting-point at the two ends of this screw rod nearby is provided with the polymer outlet respectively, at the pars intermedia of cylindrical shell length direction polymer composition supply port and the outlet of volatilization composition is set.
In the method, towards the both ends transferring polymer,,, can prevent the hot deterioration of polymer along the cylindrical shell length direction from pars intermedia in cylindrical shell so polymer is difficult for being detained with its discharge.For this reason, can obtain the few polymer of polluter.
Yet, to open the method for flat 3-49925 communique record with the spy and compare, this method is considered from the structure aspect to be difficult at polymer composition supply unit flash evapn volatilization composition to separate a large amount of volatilization compositions.Therefore, in order to reduce the remaining monomer containing ratio in the polymer composition, need the treating capacity of the size minimizing polymer composition of device relatively, it is unfavorable that this considers from industrial point of view.
Even using the occasion of opening the device that the specific materials of clear 61-275705 communique and the flat 2-49005 communique of Te Kai constitutes by the spy in addition, to the corrosion of the acid that in methylmethacrylate, can not fully prevent to contain as impurity as the main material of isobutylene-based polymer.For this reason, be blended into polymer as impurity from the metal ion of screw rod and cylindrical shell stripping, thus the problem that exists polymer light transmission etc. to descend.
Therefore, the setting free degree height that also proposes to create conditions, can fully satisfy the method that can set the problem that the problem and the contaminant restraining matter of industrial advantageous conditions are sneaked into, hope further improves.
The present invention In view of the foregoing makes, its purpose is to provide a kind of devolatilization pressing method and devolatilization pressurizing unit that comprises the polymer composition of the composition that volatilizees, the setting free degree height of creating conditions of this devolatilization pressing method and devolatilization pressurizing unit can be set industrial advantageous conditions.
In addition, the present invention also aims to provide the devolatilization pressing method and the devolatilization pressurizing unit of a kind of difficult generation ventilation polymer composition not smooth, that comprise the composition that volatilizees.
In addition, the present invention also aims to provide a kind of polluter to sneak into the devolatilization pressing method and the devolatilization pressurizing unit of polymer composition few, that comprise the composition that volatilizees.
The present invention also aims to provide a kind of devolatilization pressing method and devolatilization pressurizing unit that can make polymer composition equipment miniaturization, that comprise the composition that volatilizees to screw devolatilization pressurizing unit.
The present invention also aims to provide a kind of devolatilization pressing method of isobutylene-based polymer, this devolatilization pressing method can solve the problems referred to above of the existing devolatilization pressurizing unit that uses when making the isobutylene-based polymer that is suitable for plastic optical fiber, use can further improve the devolatilization pressurizing unit of corrosion resistance and wearability, obtains to have the isobutylene-based polymer of remarkable light transmission.
Disclosure of an invention
In order to solve above-mentioned problem, the present invention proposes following such solution mechanism.
Promptly, the application's the 1st invention provides a kind of devolatilization pressing method of polymer composition, but the screw devolatilization pressurizing unit that uses has cylindrical shell and the screw rod of free rotaring ground supporting in this, this cylindrical shell has polymer composition supply port, polymer outlet, reaches the outlet of volatilization composition, supply with the polymer composition that comprises polymer and volatilization composition to this devolatilization pressurizing unit from above-mentioned polymer composition supply port, discharge this volatilization composition from above-mentioned volatilization composition outlet, obtain above-mentioned polymer from above-mentioned polymer outlet; It is characterized in that: the nozzle opening area of above-mentioned polymer composition supply port satisfies following (1) formula.
φ: (the polymer containing ratio is the polymer containing ratio [-] of the weight in the polymer composition (kg) benchmark
φ was by 0.50 expression in 50% o'clock)
Q: polymer composition quantity delivered [m
3/ min]
S: the aperture area [m of nozzle
2]
H: the groove depth of screw rod [m]
N: the rotating speed [min of screw rod
-1]
D: screw diameter [m]
The 2nd invention provides a kind of devolatilization pressing method of polymer composition, but the screw devolatilization pressurizing unit that uses has cylindrical shell and the screw rod of free rotaring ground supporting in this, this cylindrical shell has polymer composition supply port, polymer outlet, reaches the outlet of volatilization composition, supply with the polymer composition that comprises polymer and volatilization composition to this devolatilization pressurizing unit from above-mentioned polymer composition supply port, discharge this volatilization composition from above-mentioned volatilization composition outlet, obtain above-mentioned polymer from above-mentioned polymer outlet; It is characterized in that: the polymer composition supply port upstream side on the cylindrical shell length direction is provided with the outlet of volatilization composition, the polymer outlet is set in the downstream of this polymer composition supply port, side is carried all or most of polymer downstream, and upstream side is carried the polymer of the remnants of the upstream side that moves to the polymer composition supply port.
In the 2nd invention, preferably use screw devolatilization pressurizing unit, this screw devolatilization pressurizing unit is characterised in that: the polymer composition supply port upstream side on the cylindrical shell length direction is provided with the outlet of volatilization composition, the polymer outlet is set in the downstream of this polymer composition supply port, screw flight is opposite towards on the way, to export the both direction transferring polymer to above-mentioned volatile component outlet and above-mentioned polymer.
In this screw devolatilization pressurizing unit, distance as the covert anti-switching position of the inner edge of the volatilization composition outlet side of the peristome of polymer composition supply port and above-mentioned screw flight direction is X, screw diameter is D, the peristome diameter of the spiro rod length direction of above-mentioned polymer composition supply port is Y, with above-mentioned inner edge as initial point, volatilization composition outlet side is positive coordinate, then X be preferably in-0.2Y～+ scope of 2D, 0～+ better during the scope of D.
In these devolatilization pressing methods, the polymer composition that preferably will be heated to 150 ℃～270 ℃ under the condition of not pressurizeing guides to the polymer composition supply port with foaming, supplies in the cylindrical shell under 10mmHg～atmospheric pressure.
The 3rd invention provides a kind of devolatilization pressing method of polymer composition, but the screw devolatilization pressurizing unit that uses has cylindrical shell and the screw rod of free rotaring ground supporting in this, supply with the isobutylene-based polymer constituent that comprises isobutylene-based polymer and volatilization composition to this devolatilization pressurizing unit, remove the volatilization composition, obtain isobutylene-based polymer; It is characterized in that: the screw devolatilization pressurizing unit that uses above-mentioned screw surface to cover by chromium or titanium nitride.
In the 3rd invention, preferably at least one side of the screw spiral sheet of screw devolatilization pressurizing unit and cylindrical shell inner face (preferably both sides) is that 50～95 weight %, chromium containing ratio are that 5～35 weight %, iron containing ratio are that 0～5 weight %, Rockwell Hardness C target hardness (hereinafter to be referred as hardness) are that cobalt 40 or more is the alloy covering by the cobalt containing ratio.
The simple declaration of accompanying drawing
Fig. 1 is the partial side sectional drawing that used screw devolatilization pressurizing unit one example of the application's the 1st invention is shown.
Fig. 2 (a) is the ideograph that refractive index profile shape one example of core-sheath-type optical fiber is shown, and Fig. 2 (b) is the ideograph that refractive index profile shape one example of distributed refractive index optical fiber is shown.
Fig. 3 (a) invents the partial side sectional drawing of used screw devolatilization pressurizing unit one example for the 2nd of the application is shown, and Fig. 3 (b) is for illustrating the partial side sectional drawing of wanting portion of Fig. 3 (a).
The optimised form that carries out an invention
The present invention pushes applicable to the devolatilization of the thermoplastic polymer constituent of the volatilization compositions such as the secondary biology of volatility that comprise polymer, unreacted monomer, solvent (atent solvent), generate in polymerization (coincidences) process that for example obtained by polymerisation in solution or block polymerization.
As long as the polymer that constitutes this constituent is the polymer for obtaining as the polymer composition that comprises the composition that volatilizees behind polymerization process as described above, then be not particularly limited, for example, for the homopolymers of vinyl compounds such as acrylic acid and derivative (for example (methyl) alkyl-acrylates) and styrene or based on copolymer of these vinyl compounds etc.When particularly application is of the present invention in the processing of the isobutylene-based polymer that uses as optical material, can obtain big effect.For example, be preferably the homopolymers of methylmethacrylate or based on copolymer of methylmethacrylate etc.Based on the copolymer of methylmethacrylate be more than the 50 weight % of methylmethacrylate unit and can with the copolymer that constitutes below other monomer unit 50 weight % of methylmethacrylate polymerization.As be that copolymer more than the 80 weight % of methylmethacrylate unit is then even more ideal.But, be preferably methylmethacrylates such as methyl acrylate, fluoro (methyl) alkyl acrylate, metering system benzyl acetate various (methyl) acrylate in addition as other monomer unit of copolymerization.
As other composition that is contained in the volatile component in the polymer composition, in the occasion of block polymerization, can list secondary biology of unreacted monomer, volatility, remaining chain mobile agent, and monomer such as organic acidity compound in the compositions etc. that volatilize such as impurity.In addition, in the occasion of solution polymerization process, also can list solution etc.
The polymer containing ratio of polymer composition is not particularly limited, but is preferably more than the 30 weight %, and is better when being 30～80 weight %, then even more ideal when being 40～75 weight %.When the polymer containing ratio was very few, volatile quantity was many, and the energy burden is big, and it is unfavorable to consider from the angle of industry.In the time of too much, the characteristic of polymer and service condition make the viscosity of polymer composition rise change greatly, and may become difficulty smooth separation of volatilization composition and polymer.
Below, illustrate the application the 1st, the 2nd, and the 3rd the invention each form of implementation.(the 1st form of implementation)
Fig. 1 illustrates an example of the screw devolatilization pressurizing unit (hereinafter to be referred as the devolatilization pressurizing unit) of the 1st invention that is used for the application.Configuration is roughly columned screw rod 2 in the hollow bulb 1a of columned cylindrical shell 1.This screw rod 2 is in that but it is one-sided as the axle envelope bearing 2a of the portion free rotaring ground supporting of drive division.In addition, spiral helicine groove 2b is set in the side of this screw rod 2, forms screw thread.The devolatilization pressurizing unit can be the single axle that 1 screw rod is set, and also can be two shaft types that 2 screw rods are set.
In addition, in the side of above-mentioned cylindrical shell 1, polymer composition supply port 3 is set, this polymer composition supply port 3 has the nozzle 3a at the hollow bulb 1a of cylindrical shell 1 inner opening.This nozzle 3a for example can use multiple shapes such as cylinder, rectangle slit, porous mouth, many slits, but in order to supply with even velocity in the area of guaranteeing to volatilize, then is preferably rectangle slit or many shape of slit.
In addition, in the way of nozzle 3a, valve 3c is set preferably.Owing to there is this valve 3c, so such as described later, the pressure in the place ahead (upside of the valve 3c in Fig. 1) by adjusting valve 3c can suppress the foaming of polymer composition, and polymer composition is stably supplied in the cylindrical shell 1.As long as valve 3c has voltage regulation function, then be not particularly limited, but specifically, be preferably needle-valve etc.In addition, in order to carry out operational management easily, preferably use valve with automatic Regulation function.
On the other hand, the front at the screw rod 2 of cylindrical shell 1 is provided with polymer outlet 4.Between the axle envelope bearing 2a of portion of cylindrical shell 1 side and polymer composition supply port 3, be provided with and supply with oral-lateral and evaporate into a part outlet (to call the back passage in the following text) 5, between polymer composition supply port 3 and polymer outlet 4, set out oral-lateral volatilization composition outlet (with passage after calling in the following text) 6.As long as can discharge volatilization composition, passage 6 before then not necessarily needing fully by back passage 5.In addition, the difference according to composition of polymer composition etc. can be provided with the preceding passage 6 more than 1 or 2 on demand.That is, when having preceding passage 6, in this devolatilization pressurizing unit, drive division (the axle envelope bearing 2a of the portion) side along the length direction of cylindrical shell 1 from screw rod 2 disposes back passage 5, polymer composition supply port 3, preceding passage 6, and polymer outlet 4 successively.Back passage 5 preferably forms towards horizontal direction or towards level direction down, and is better as vertical downward formation side.
In the present invention, satisfy the peristome that polymer composition supply port 3 is set on above-mentioned (1) formula ground, promptly the aperture area S of the peristome 3b of nozzle 3a sets service condition.(1) the screw diameter D in the formula and the groove depth H of screw rod are shown among Fig. 1.Screw diameter D is the diameter of screw rod of the position of polymer composition supply port 3.The groove depth H of screw rod is the groove depth of screw rod of the position of polymer composition supply port 3.
In addition, preferably satisfy following (2) formula ground and set aperture area S, set service condition.
The condition of above-mentioned by satisfying (1) formula; in the inwall of cylindrical shell 1 and the gap between screw rod 2 outsides; can get by scraping of screw rod 2 polymer is delivered to polymer outlet 4, not be aggregated thing and stop up the stream that this guarantees volatilization gas with gap, discharge the volatilization composition effectively from back passage 5.
As aperture area S during less than the left side of above-mentioned (1) formula, the speed of getting of scraping of the relative screw rod 2 of the spouting velocity of polymer becomes too fast, is full of by polymer in the above-mentioned gap, and towards the stream deficiency of the volatilization gas of back passage 5, the volatilization composition is difficult for discharging.As a result, polymer is accompanied by desires the volatilization gas that passage 5 backwards moves, and passage 5 side polymer easily produce expansion in the back, back passage 5 is stopped up, so, become the not smooth reason of ventilation.
Bigger as aperture area S than the right of (1) formula, the polymer composition foam overblow of the peristome 3b in the nozzle 3a then, in foaming body, form big air flue, so, uniform foamed state can not be become, the space that appearance is only formed by foaming body part and volatilization composition, the size in this space changes often, so 1 interior polymeric quantity delivered produces change from polymer composition supply port 3 to cylindrical shell, the quantity delivered of polymer becomes inhomogeneous, becomes the reason of fluctuation.
Below concrete operational example is described.
At first, in advance polymer composition is heated to 150 ℃～270 ℃, preferably is heated to 170～250 ℃, supply to nozzle 3a.Cross when low when preheat temperature, the volatilization composition may be difficult to abundant separation.When too high, the generation of two amount bodies becomes many, and the content of polluter increases.Generally speaking, two amount bodies etc. are secondary biological than monomer boiling point height, the difficult separation, so the transparency of isobutylene-based polymer descends, promptly become the reason that polluter produces.
At this moment, preferably, prevent the foaming of polymer composition to the polymer composition pressurization.Under the state of polymer composition foaming, be difficult in the hollow bulb 1a of cylinder 1, stably supply with by nozzle 3a.In addition, when the polymer composition at the pipe arrangement portion foamable state of the front side of valve 3c, polymer composition is trapped in the pipe arrangement, becomes painted reason.
Heating, the pressure method of polymer composition are not particularly limited, applicable known method.For example, preferably heating pressurization in the pipe arrangement of band water jacket on one side Yi Bian transfer polymer composition, supplies to nozzle 3a.
In nozzle 3a, keep pressure by the aperture adjusting of valve 3c, prevent the foaming of the polymer composition of valve 3c front.Then, make this polymer composition by nozzle 3c, in hollow bulb 1a, supply with continuously from the peristome 3b of nozzle 3a Yi Bian moderately foam.
Like this,, can stably in the hollow bulb 1a of cylindrical shell 1, supply with polymer composition by suppressing foaming by the polymer composition before the valve 3c, and, can in hollow bulb 1a, make polymer composition moderately foaming continuously, remove the volatilization composition effectively.
At this moment, the pressure in the hollow bulb 1a of cylindrical shell 1 is adjusted into negative pressure state, is in 10Torr～atmospheric pressure, and is better during for 50Torr～atmospheric pressure, for 50Torr～atmospheric pressure then even more ideal when following.
When this hypertonia, the evaporation capacity of volatilization composition tails off, the decrease in efficiency of removing of the composition that volatilizees.
In addition, when being negative pressure state in the hollow bulb 1a of cylindrical shell 1, promoted the evaporation of volatilization composition.But when the hypotony in the hollow bulb 1a, the volumetric expansion of volatilization gas accelerates the flow velocity of volatilization gas, and the volatilization gas of passage 5 side flow is attended by polymer backwards, so, not perfect condition.
Supply to like this in the hollow bulb 1a of cylindrical shell 1 polymer composition by the pressure before the valve 3c with pass through after hollow bulb 1a in the effect of difference of pressure under, foaming continuously on one side, conflict with screw rod 2 on one side, the volatilization composition separates with polymer, reclaims the part of volatilization composition from back passage 5.On the other hand, polymer passes out to polymer outlet 4 by the revolution of screw rod 2.At this moment, residual volatilization composition is discharged from back passage 5 and preceding passage 6, obtains polymer from polymer outlet 4.
Like this, in the 1st form of implementation, by under the condition that satisfies above-mentioned (1) formula, moving, because the speed of the gas-liquid mixed that the polymer composition that is supplied to the hollow bulb 1a of cylindrical shell 1 by polymer composition supply port 3 can be constituted stream and the speed of getting of scraping of screw rod maintain optimum value respectively, so, the volatilization composition can be removed effectively, and the not smooth generation of ventilating can be prevented.Therefore, the free degree height of service condition is suitable for industrial favourable a large amount of processing.
In addition, the distance of polymer composition supply port 3 and back passage 5 for example, as is not about a times of screw diameter D not as not long the method for having now, and is then more abundant.As a result, can shorten the length of cylindrical shell 1, make equipment miniaturization, and, can reduce to be stranded in the amount of polymers of cylindrical shell 1, prevent that the byproduct that the hot deterioration of polymer causes from producing.In addition, the adhesion of cylindrical shell 1 and screw rod 2 is difficult to take place, the sneaking into of the powder that can suppress to wear and tear.
Therefore, can set industrial advantageous conditions, and form and stablize, can obtain the few polymer of polluter at small-sized device.
Particularly when carrying out the devolatilization extruding of isobutylene-based polymer, compare, can make the good polymer of the transparency in a large number, consider favourable from the angle of industry with the existing apparatus of identical size.
The transparent good isobutylene-based polymer of Huo Deing for example is suitable for the core of optical fiber like this, this be because, for the good more transmission characteristic that then can improve optical fiber more of the core transparency of optical fiber.In addition also because by stably removing sneaking into of volatilization composition and contaminant restraining, the length direction that can be suppressed at optical fiber produces the phenomenon of transmission loss deterioration partly.
Structure to the optical fiber that used polymer of the present invention does not limit especially, for example can list core (core) 10 such shown in Fig. 2 (a) and sheath (cladding part) 11 with the concentric circles lamination, at its interfacial refraction rate core-sheath-type optical fiber jumpy, and such center 10 from core (core) shown in Fig. 2 (b) towards periphery 10 ', 10 ' ' the distributed refractive index optical fiber of the stepped variation of refractive index etc.
Such optical fiber usually uses the composite spinning nozzle that multiple material is sprayed after with the concentric circles lamination to carry out spinning, but this is not limited.For example for core-sheath-type optical fiber, also can be earlier only to the spinning of core composition, shaping, then at its outer fusion coating sheath composition.
As the sheath composition of core-sheath-type optical fiber, for example can use the copolymer of vinylidene fluoride and fluoroalkyl vinyl acetate, methacrylate, acrylate, tetrafluoroethene, HFC-236fa or vinyl acetate etc.In addition, also can use the copolymer etc. of fluorinated methyl alkyl acrylate, fluorinated acrylamide acid alkyl ester etc. and methacrylate, acrylate etc.
As comparatively ideal material, can enumerate with the vinylidene fluoride is the polymer of main component.As polymer, for example can list and contain 1,1 of 1-difluoroethylene 75～99 weight %, the copolymer of 1-difluoroethylene and tetrafluoroethene, 1, the copolymer that 1-difluoroethylene 75～95 weight %, tetrafluoroethene 4～20 weight %, HFC-236fa 1～10 weight % constitute reaches the copolymer of vinylidene fluoride 75～95 weight %, tetrafluoroethene 4～20 weight %, PVF 1～5 weight % formation etc.
In the occasion of distributed refractive index optical fiber shown in Fig. 2 (b), polymer of the present invention is used as its center material, the polymer or the copolymer of more than one that configuration refractive index descends successively outside it.The polymer or the copolymer that are disposed at the outside also can be according to method manufacturings of the present invention.(the 2nd form of implementation)
The purpose of the 2nd invention is particularly to prevent that the polluter in the polymer composition devolatilization operation from sneaking into.
Fig. 3 illustrates an example of the 2nd the used devolatilization pressurizing unit of invention, and Fig. 3 (a) is the partial side sectional drawing, and Fig. 3 (b) illustrates the portion that wants of device.The formation identical with Fig. 1 adopts same-sign, omits explanation.
This device is characterised in that screw thread opposite towards on the way of screw rod 2.
That is, be divided into polymer along the length direction of cylindrical shell 1 in the hollow bulb 1a of cylindrical shell 1 and export the polymer Way out stream 1c of 4 sides and the back passage direction stream 1d of back passage 5 sides.
At polymer Way out stream 1c, the outlet semi-finals system ground transferring polymer from polymer composition supply port 3 towards polymer.In addition, at back passage direction stream 1d, from polymer composition supply port 3 passage 5 transferring polymer forcibly backwards.
, the secondary biology of the polymer of existing devolatilization pressurizing unit is sneaked into and is mostly to take place because of following such process.Describe below with reference to Fig. 3 (a).Existing apparatus is different with Fig. 3 (a) shown device, and the groove 2b that is located at screw rod 2 with helical form can be provided with towards unidirectional transferring polymer ground, only outlet 4 conveyings from polymerization constituent supply port 3 towards polymer of the polymer in the hollow bulb 1a of cylindrical shell 1.
Yet in fact change of the quantity delivered of the polymer composition of polymer composition supply port 3 etc. may make the part of polymer spill into back passage 5 sides of polymer composition supply port 3 upstream sides.Like this, between back passage 5 and polymer composition supply port 3, be detained a part of polymer.The polymer that is stranded in this part is not discharged to the outside, but is gathered in the hollow bulb 1a, and when being in high temperature for a long time, deterioration produces color, carbonization or generates secondary biological gradually.
Do not overflow even if be transported to the polymer of polymer outlet 4 from polymer composition supply port 3, move yet for the reason identical passage 5 sides expansion astablely backwards with above-mentioned occasion.
Like this, above-mentioned secondary biological (polluter) contact with polymer towards the upstream side shifting, is accompanied by polymer outlet 4, exports the polymer that 4 acquisitions contain this pair biology from polymer.
On the other hand, in devolatilization pressurizing unit of the present invention shown in Fig. 3 (a), from polymer composition supply port 3 with polymer transport to back passage 5 sides.For this reason, back passage 5 sides, the mobile polymer of expansion that spill into upstream side are transported to back passage 5 forcibly, discharge from back passage 5.As a result, can prevent that polymer unnecessarily is detained, and prevents that polluter is blended into polymer in cylindrical shell 1.
In this device, the distance X towards (screw thread towards) covert anti-switching position of the inner edge of back passage 5 sides of the peristome 3b of polymer composition supply port 3 (nozzle 3a) and the groove 2b of screw rod 2 designs with preferably can satisfying following relation.
Here, establishing screw diameter is D, and the peristome diameter of the length direction of the screw rod of polymer composition supply port 3 (diameter of peristome b) is Y.With the inner edge of back passage 5 sides of the peristome 3b of polymer composition supply port 3 is initial point, when after passage 5 sides be the central seats that directly face the stage timestamp, distance X is set in-0.2Y～+ scope of 2D in.That is, be configured in the occasion of back passage 5 sides (+side), be configured in the scope from initial point to+2D from the above-mentioned former above-mentioned switching position of naming a person for a particular job.In addition, be configured to the occasion that polymer exports 4 sides (side), be configured in scope from initial point to-0.2Y from the former switching position of naming a person for a particular job.
Ratio+2D is big as distance X, and switching position passage 5 sides change backwards then may be difficult to discharge the polymer that moves to back passage 5 sides.In addition, be negative value as the value of distance X, the become absolute value of ratio-0.2Y of its absolute value is big, switching position exports the change of 4 sides towards polymer, and the polymer quantitative change that then is transported to back passage 5 is many, and becomes unstable towards the conveying capacity in extruder the place ahead, so, be difficult to stably obtain polymer.In order to prevent that as much as possible passage 5 sides backward from carrying too much polymer, preferably this distance is set in 0～+ 2D.In addition, be detained in order further to prevent polymer, preferably this distance X is set in 0～+ D.These position relations are shown in Fig. 3 (b).
In addition, the preferably vertical back passage 5 that down forms, like this, polymer can be flowed down and be discharged by its deadweight.
In addition, preceding passage 6 is as the side ventilating mode, is preferably in the following mode of scraping one side of the breather port effect of preceding passage 6 is provided with flight 2c (blade).As a result, can suppress the back passage 6 ventilation not smooth.In addition, even it is not smooth to occur ventilation suddenly, the volatilization composition does not turn back in the cylindrical shell 1 once more yet, but is discharged to the outside of cylindrical shell 1.
In addition, not smooth in order to prevent ventilation generally speaking, have the gimmick that the blow vent periphery in cylindrical shell reams and processes.Yet, owing to be easy to be detained polymer in the part of having carried out fraising processing, so, in the present invention, preferably not to the ream processing of back passage 5 and preceding passage 6.
In addition, be detained polymer in the cylindrical shell 1 in order to be suppressed at up hill and dale, the flight 2c (blade) and the gap between cylindrical shell 1 inwall of screw rod 2 are preferably as far as possible little.Yet as too small, screw rod 2 contacts with cylindrical shell 1, easily adhesion.Therefore, this gap preferably is set in the scope of 0.05～0.2mm.
The devolatilization operation of the polymer composition of this devolatilization pressurizing unit can similarly be carried out with the 1st form of implementation.In addition, can in midget plant, set industrial advantageous conditions, can obtain the polymer that polluter has further reduced, fully removed the volatilization composition.
Therefore, same with the 1st form of implementation, being suitable for isobutene is the devolatilization extruding of polymerization constituent, can improve the characteristic of the goods such as optical fiber that use the isobutylene-based polymer that obtains.(the 3rd form of implementation)
The purpose of the 3rd invention particularly is to prevent to cause this metal ion to be blended into polymer as impurity from screw rod and cylindrical shell stripping metal ion, thereby suppresses the declines such as light transmission of polymer.
In this form of implementation, the screw surface of screw devolatilization pressurizing unit need be covered by chromium or titanium nitride.
Main material at isobutylene-based polymer is the organic acidity compound that contains several ppm in the methylmethacrylate as impurity generally speaking.The nitrided steel that is usually used in screw rod is by this organic acidity compound corrosion, stripping iron ion.On the other hand, when isobutylene-based polymer is carried out polymerization, add mercaptan (メ Le ヵ プ Application) compound as chain mobile agent usually.
By volatilization composition evaporation is isolated from polymer in the devolatilization device of volatilization composition owing to there is not oxygen basically, so, the iron ion of stripping at high temperature with the mercaptan compound reaction, become iron sulfide, be blended into polymer as impurity.
When covering screw surface, can suppress the stripping of this iron ion by chromium or titanium nitride.
The method that is covered screw surface by chromium is preferably galvanoplastic.The tectal thickness that is made of chromium is preferably 20～80 μ m.The method that is covered screw surface by titanium nitride is preferably vapour deposition method.The tectal thickness that titanium nitride constitutes is preferably 10～100 μ m.
Be used for the devolatilization pressurizing unit by the screw rod that will cover chromium or titanium nitride, can suppress from screw rod stripping iron ion, impurity such as inhibition iron sulfide are blended into polymer, make the isobutylene-based polymer with good light transmission.
, when covering screw rod surperficial by chromium or titanium nitride, may produce pin hole at the cover layer of screw surface.At this moment, even also may be from this pin hole stripping metal ion at the screw rod that covers chromium or titanium nitride.Therefore, use general steel such as nitrided steel at screw rod self with it, not as using the stainless steel of fine corrosion resistance.As stainless steel, adopt SUS316, SUS630 better, wherein SUS630 is good especially.
In this screw devolatilization pressurizing unit, at least one side in screw spiral sheet and the cylindrical shell inner face (preferably both sides) is that 50～95 weight %, chromium containing ratio are that 5～35 weight %, iron containing ratio are that 0～5 weight %, Rockwell Hardness C target hardness are that cobalt 40 or more is the alloy covering by the cobalt containing ratio.
Cobalt is that alloy also can add other metal ingredient in the scope that does not worsen its corrosion resisting property and hardness.
When covering the screw spiral sheet, preferably adopt the method that covers in screw spiral sheet built-up welding deposite metal by above-mentioned alloy.The tectal thickness that is made of this alloy is preferably 1～3mm.The screw spiral sheet can be all covered by alloy, can make also that this alloy only covers the screw spiral sheet with cylindrical shell inner face side end face in opposite directions.
In screw rod, the part that is covered by this alloy is not preferably covered by chromium or titanium nitride as described above.
In order to cover the inner face of cylindrical shell by alloy, preferably by the inner surface covering alloy of centre spinning at cylindrical shell.The tectal thickness that is made of alloy is preferably 1～3mm.
The light transmission of existing plastic optical fiber may produce harmful effect by cobalt ions, is the stripping that alloy suppresses iron ion but can use cobalt like this, suppresses impurity and is blended into polymer.
In addition, in order to make the better polymer of light transmission, be preferably in the devolatilization pressurizing unit the strict galling powder that suppresses and sneak into.For this reason, preferably becoming the screw spiral sheet self of sliding part and cylindrical shell inner face self is the good material of anti-wear performance more than 40 by Rockwell Hardness C target hardness also, as is that material more than 50 is then better.
The best hardness ratio screw spiral of cylindrical shell inner face sheet is high more than 5.
This screw devolatilization pressurizing unit can be any form among single shaft or two, but is preferably the form of the device component parts single shaft that contact is few each other.
Because it is few to utilize the isobutylene-based polymer of this screw devolatilization pressurizing unit manufacturing to sneak into impurity, so light transmission is good.Particularly be suitable for the core of plastic optical fiber, can obtain the very good plastic optical fiber of optical transmission performance.
Be not particularly limited by structure, can example illustrate with the structure identical construction of the 1st working of an invention form record etc. by the optical fiber of the polymer manufacturing of this method devolatilization extruding.
The polymer composition devolatilization operation of this devolatilization pressurizing unit can be carried out in the same manner with the above-mentioned the 1st and the 2nd form of implementation.Polluter is sneaked into few, can obtain fully to remove the good polymer of light transmission of volatilization composition.
Invent in the used devolatilization pressurizing unit at the 1st, under the condition that satisfies above-mentioned (1) formula, move, and use used screw rod in the 2nd invention, when under the condition of the position of polymer composition supply port that satisfies the 2nd invention and screw rod relation, moving, can obtain the few polymer composition of polluter.By using the devolatilization pressurizing unit of making by the specific materials of the 3rd invention, the isobutylene-based polymer constituent is carried out the devolatilization extruding, can make the good isobutylene-based polymer of light transmission that is applicable to plastic optical fiber etc.
Embodiment
Specify the present invention by embodiment below.(embodiment 1～2, comparative example 1)
In single axle devolatilization pressurizing unit shown in Figure 1,, carried out the devolatilization experiment of embodiment 1～2 and comparative example 1 under the same conditions except that using respectively at the polymer composition supply port shown in the table 1 nozzle.The structural environment and the service condition of shared device are set as described above.The structure of device:
Screw diameter D 40mm
Cylindrical shell length L 1200mm
The groove depth H 9.0mm of the screw rod of polymer composition supply unit
Gap 0.1mm between screw spiral sheet and cylindrical shell
Back passage and polymer composition supply port apart from 1.5D
Preceding passage quantity 1 service condition:
The outlet pressure 100mmHg of back passage
210 ℃ of average barrel temperatures from the polymer composition supply port to preceding blow vent
In the past the average barrel temperature that exports to polymer of passage is 235 ℃
The outlet pressure 20mmHg of preceding passage
Screw speed 60 (min
-1)
In addition, polymer composition uses methylmethacrylate separately as monomer, polymerization begin agent, mercaptan be chain mobile agent in the presence of to carry out the polymer containing ratio that block polymerization obtains be 42 weight % (φ=0.42).
At 16kg/cm
2The adding to depress of G, be heated to 200 ℃ with this polymer composition, with 3.3 * 10
-4m
3The flow of/min supplies to the devolatilization pressurizing unit continuously, obtains the polymer of devolatilization.Interval by per 10 days (once) is observed each operation conditions of this moment, is shown in Table 1.[table 1]
| The supply port nozzle form | Operation conditions | ||||
| Shape | Aperture area S[m 2] | ?φQ/(H·N) ????[m 2] | ??2D 2[m 2] | ||
| Embodiment 1 | Rectangle gap nozzle 14mm * 80mm | ?0.00112 | ??0.000257 | ??0.0032 | Smooth pressurizing unit forefront pressure amplitude of fluctuation 10kg/cm does not ventilate 2 |
| | Article three, gap nozzle 4mm * 80mm * 3 | ?0.00096 | ??0.000257 | ??0.0032 | Smooth pressurizing unit forefront pressure amplitude of fluctuation 10kg/cm does not ventilate 2 |
| Comparative example 1 | 3mm diameter one hole nozzle | ?0.0000071 | ??0.000257 | ??0.0032 | Has not smooth (10 times) the pressurizing unit forefront pressure amplitude of fluctuation 30kg/cm of sudden ventilation 2 |
As shown in Table 1, among the embodiment 1～2 that moves under by the condition that satisfies (1) formula, ventilation is not smooth, can carry out stable operation, but the production ventilation is not smooth in comparative example 1, and the forefront pressure amplitude of fluctuation of devolatilization pressurizing unit is big.
Then, the polymer of the embodiment 1 that obtains like this and comparative example 1 as core, is made core-sheath-type optical fiber respectively.
That is, prepare as the material of covering make separately 2,2, the polymer of 2-trifluoro ethyl methacrylate.Double-deck composite spinning nozzle is installed in polymer outlet at the devolatilization pressurizing unit, core material is supplied to the internal layer of double-deck composite spinning nozzle under 210 ℃ temperature conditions.In addition, at the skin that under 210 ℃ temperature conditions, clad material is supplied to double-deck composite spinning nozzle, carry out melt composite spinning, obtain optical fiber by other extruder.And the external diameter of this optical fiber is 1mm, and the independent thickness of covering is 10 μ m.
At this moment, spinning 150,000 m (10 days) continuously measure the transmission loss of the wavelength 650nm of the optical fiber that obtains along total length, and mean value is shown in Table 2.In addition, transmission loss surpasses 150dB/km, the big frequency table of change is shown in Table 2.[table 2]
| The transmission loss of wavelength 650nm | ||||
| 10 days operation conditions | ||||
| Mean value (dB/km) | The above 200dB/km of 150dB/km less than number of times | The above 300dB/km of 200dB/km less than number of times | The number of times that 300dB/km is above | |
| Embodiment 1 | ????133 | ??????????7 | ???????????2 | ???????0 |
| Comparative example 2 | ????135 | ??????????10 | ???????????15 | ???????5 |
| Embodiment 3 | ????133 | ??????????0 | ???????????0 | ???????0 |
As shown in Table 2, in embodiments of the invention 1, obtained the little and equable stable optical fiber of transmission loss of transmission loss.Therefore, in embodiment 1, obtained transparent good and composition stable polymer.(embodiment 3)
In the devolatilization pressurizing unit of single axle shown in Figure 3, use similarly to Example 1 nozzle and polymer composition to move.The structure condition and the service condition of device are set as described below.In addition, make the optical fiber of the polymer that this devolatilization is refining similarly to Example 1 as core.The structure of device:
Screw diameter D 40mm
Gap 0.1mm between screw spiral sheet and cylindrical shell
Cylindrical shell length L 1200mm
The groove depth H 9.0mm of the screw rod of polymer composition supply unit
Preceding passage quantity 1
Distance X 20mm
Back passage and polymer composition supply port apart from the 60mm service condition:
The outlet pressure 200mmHg of back passage
210 ℃ of average barrel temperatures from the polymer composition supply port to preceding blow vent
In the past the average barrel temperature that exports to polymer of passage is 235 ℃
The outlet pressure 20mmHg of preceding passage
Screw speed 60 (min
-1)
At 16kg/cm
2The adding to depress of G, be heated to 200 ℃ with polymer composition, with 3.3 * 10
-4m
3The flow of/min supplies to the devolatilization pressurizing unit continuously, obtains the polymer of devolatilization.
Make the optical fiber of this polymer similarly to Example 1 as core.
At this moment, the optical fiber to 150,000 m (10 days) carries out spinning continuously, measures the transmission loss of wavelength 650nm along the total length of the optical fiber that obtains.The frequency table that exists that transmission loss surpasses 150dB/km is shown in Table 2.In measurement result shown in the table 2.
As shown in Table 2, in the embodiments of the invention 3, obtained the transmission loss change optical fiber littler than embodiment 1.Therefore, the devolatilization of embodiment 3 in service obtained transparent good and also sneak into polluter few, form stable polymer.(comparative example 2)
Passage is installed valve in the back, is keeping pressure 20kg/cm
2, make polymer composition not discharge polymer composition from the back passage with not foaming, do not discharge the volatilization composition that separates from the back breather port, in addition, other moves under such condition similarly to Example 3, makes the polymer of the devolatilization extruding optical fiber as core.Yet under the polymer composition quantity delivered identical with embodiment 3, it is not smooth that ventilation takes place preceding passage often.In addition, in the optical fiber that obtains, find numerous air-bubble, can not be used as optical fiber.The remaining amount of monomer of measuring in the polymer that obtains is learnt, and is high by 4.5%.
In comparative example 2,, the output of optical fiber need be reduced to 1/4 of embodiment 3 in order to obtain the optical fiber with embodiment 3 identical performances.(embodiment 4～6)
Screw devolatilization pressurizing unit uses the single shaft extruder of following structure.The structure of device:
Screw diameter D 40mm
Cylindrical shell length L 1200mm
Gap 0.1mm between screw spiral sheet and cylindrical shell
The screw rod that uses among the embodiment and the material of cylindrical shell and cladding material thereof are as shown in Figure 3.
In screw rod, the tectal thickness of the part beyond the screw spiral sheet is 40 μ m.
The cover layer of screw spiral sheet is by forming the end face of built-up welding behind the metal molten to the screw spiral sheet, and thickness is 2mm.The cover layer of cylindrical shell inner face is formed by centre spinning, and thickness is 2mm.
Use methylmethacrylate separately as monomer, begin agent and be to carry out block polymerization in the presence of the n-butyl mercaptan 1700ppm of chain mobile agent as mercaptan in polymerization, obtaining the polymer containing ratio is the isobutylene-based polymer constituent of 42 weight %.
At 16kg/cm
2Add to depress this mixture be heated to 200 ℃, supply to screw devolatilization pressurizing unit continuously with the flow of 20kg/hr, remove the volatilization composition, supply to the composite spinning nozzle of the bilayer of installing at the front end of screw rod devolatilization pressurizing unit.In addition, with 2,2 of polymerization separately, the polymer of 2-trifluoro ethyl methacrylate supplies to the skin of double-deck composite spinning nozzle from other extruder as the sheath material.Under 210 ℃, carry out melt composite spinning, obtain the plastic optical fiber of core sheath double-layer structural.
The external diameter of this optical fiber is 1mm, and the thickness of sheath layer is 10 μ m.
Measure the containing ratio of the metal ingredient that comprises in the core of this optical fiber by induction coupling high-frequency plasma luminescence analysis.In addition, measure the transmission loss of the wavelength 650nm of optical fiber.Measurement result is as shown in table 4.(comparative example 3～4)
Use the screw devolatilization extruder of material shown in the table 3, except that not covering, other is identical with embodiment 4, makes plastic optical fiber under this condition, obtains the result of table 4.[table 3]
[table 4]
(embodiment 7)
| Screw rod | Cylindrical shell | ||||||
| The screw rod material | The cladding material of the part beyond the screw spiral sheet | The cladding material of screw spiral sheet | The hardness of the cladding material of screw spiral sheet | The material of cylindrical shell | The cladding material of inner face | Interior facial case hardness | |
| Embodiment 4 | SUS630 (stainless steel) | Chromium plating | Cobalt 64% chromium 28% iron 3% tungsten 4% carbon 1% | 44 | SUS316 (stainless steel) | Cobalt 69% chromium 25% iron 1% boron 3% manganese 1% silicon 1% | 65 |
| Embodiment 5 | SACM645 (carburizing steel) | The same | The same | 44 | The same | The same | 65 |
| Embodiment 6 | SUS630 (stainless steel) | Titanium nitride evaporation (TiN) | The same | 44 | The same | The same | 65 |
| Comparative example 3 | SACM645 (nitrided steel) | Do not have | Do not have | 65 | SACM645 (nitrided steel) | Do not have | 65 |
| Comparative example 4 | SUS630 (stainless steel) | Do not have | Do not have | 44 | SUS630 (stainless steel) | Do not have | 44 |
| Metal containing ratio (ppb) in the core | The transmission loss of wavelength 650nm (dB/km) | |
| Embodiment 4 | ???????????27 | ?????????????????132 |
| Embodiment 5 | ???????????31 | ?????????????????133 |
| Embodiment 6 | ???????????26 | ?????????????????132 |
| Comparative example 3 | ???????????20000 | ?????????????????410 |
| Comparative example 4 | ???????????106 | ?????????????????151 |
Titanium nitride at the part evaporation thickness 40 μ m except that the screw spiral sheet of the screw rod of devolatilization extruder, by cobalt 64 weight %, chromium 28 weight %, iron 3 weight %, tungsten 4 weight %, the cover layer of the thick 2mm that the alloy of the hardness 44 that carbon 1 weight % constitutes forms covers the screw spiral sheet, cobalt 69 weight %, chromium 25 weight %, iron 1 weight %, boron 3 weight %, manganese 1 weight %, the alloy of the hardness 65 that silicon 1 weight % constitutes covers the cylindrical shell inner face with the cover layer of 2mm, in addition, under the condition identical, move, make with the polymer that carried out the devolatilization extruding optical fiber as core with embodiment 3.
Continuously 150,000 m (10 days) optical fiber is carried out spinning, measure the transmission loss of wavelength 650nm along the total length of the optical fiber that obtains.The mean value of transmission loss is 132dB/km, and transmission loss is 0 time at the number of times more than the 150dB/km, below the 200dB/km, is 0 time at the number of times more than the 200dB/km, below the 300dB/km, and the number of times more than 300dB/km is 0 time.
In service at 10 days, ventilation freely is not 0 time, pressurizing unit forefront pressure amplitude of fluctuation is 10kg/cm
2
The containing ratio that includes metal ingredient in the core of the optical fiber that obtains is 26ppb.
The possibility of utilizing on the industry
As described above, in the 1st invention of the present invention, can effectively remove the volatilization composition, and can prevent that ventilation is not smooth. Therefore, the free degree of service condition is high, is suitable for industrial favourable a large amount of processing. In addition, but the miniaturization of implement device prevent from cylindrical shell, being detained polymer, prevent the hot deteriorated of polymer. Therefore, can set industrial favourable condition by small-sized device, and can obtain to form the polymer stable, that polluter is few.
In addition, in the 2nd invention, further contaminant restraining matter sneaks into. For this reason, can further improve from the characteristic of the product of this polymer acquisition.
In addition, by heating adding the polymer composition of depressing before importing to cylindrical shell, can stably supply with, suppress the delay of the polymer in the cylindrical shell. In addition, be 10Torr～atmospheric pressure by the pressure that makes cylindrical shell, can effectively remove the volatilization composition.
In addition, in the 3rd invention, the isobutylene-based polymer that can obtain to have remarkable light transmission. This isobutylene-based polymer that light transmission is good is applicable to optical applications, is specially adapted to the core of plastic optical fiber.
Claims (12)
1, a kind of devolatilization pressing method of polymer composition, but the screw devolatilization pressurizing unit that uses has cylindrical shell and the screw rod of free rotaring ground supporting in this, this cylindrical shell has polymer composition supply port, polymer outlet, reaches the outlet of volatilization composition, supply with the polymer composition that comprises polymer and volatilization composition to this devolatilization pressurizing unit from above-mentioned polymer composition supply port, discharge this volatilization composition from above-mentioned volatilization composition outlet, obtain above-mentioned polymer from above-mentioned polymer outlet; It is characterized in that: the nozzle opening area of above-mentioned polymer composition supply port satisfies following (1) formula.
φ: (the polymer containing ratio is the polymer containing ratio [-] of the weight in the polymer composition (kg) benchmark
φ was by 0.50 expression in 50% o'clock)
Q: polymer composition quantity delivered [m
3/ min]
S: the aperture area [m of nozzle
2]
H: the groove depth of screw rod [m]
N: the rotating speed [min of screw rod
-1]
D: screw diameter [m]
2, a kind of devolatilization pressing method of polymer composition, but the screw devolatilization pressurizing unit that uses has cylindrical shell and the screw rod of free rotaring ground supporting in this, this cylindrical shell has polymer composition supply port, polymer outlet, reaches the outlet of volatilization composition, supply with the polymer composition that comprises polymer and volatilization composition to this devolatilization pressurizing unit from above-mentioned polymer composition supply port, discharge this volatilization composition from above-mentioned volatilization composition outlet, obtain above-mentioned polymer from above-mentioned polymer outlet; It is characterized in that: the polymer composition supply port upstream side on the cylindrical shell length direction is provided with the outlet of volatilization composition, the polymer outlet is set in the downstream of this polymer composition supply port, side is carried all or most of polymer downstream, and upstream side is carried the polymer of the remnants of the upstream side that moves to the polymer composition supply port.
3, devolatilization pressing method as claimed in claim 2 is characterized in that: the nozzle opening area of polymer composition supply port satisfies following (1) formula.
φ: (the polymer containing ratio is the polymer containing ratio [-] of the weight in the polymer composition (kg) benchmark
φ was by 0.50 expression in 50% o'clock)
Q: polymer composition quantity delivered [m
3/ min]
S: the aperture area [m of nozzle
2]
H: the groove depth of screw rod [m]
N: the rotating speed [min of screw rod
-1]
D: screw diameter [m]
4, as any one described devolatilization pressing method among the claim 1-3, it is characterized in that: above-mentioned polymer composition is the isobutylene-based polymer constituent.
5, a kind of polymer is characterized in that: obtained by each described devolatilization pressing method among the claim 1-3.
6, as each described devolatilization pressing method among the claim 1-4, it is characterized in that: the polymer composition that will be heated to 150 ℃～270 ℃ under pressurized conditions guides to the polymer composition supply port, supplies in the cylindrical shell under 10mmHg～atmospheric pressure.
7, a kind of screw devolatilization pressurizing unit, but have cylindrical shell and the screw rod of free rotaring ground supporting in this, this cylindrical shell has polymer composition supply port, polymer outlet, reaches the outlet of volatilization composition, it is characterized in that: the polymer composition supply port upstream side on the cylindrical shell length direction is provided with the outlet of volatilization composition, the polymer outlet is set in the downstream of this polymer composition supply port, screw flight is opposite towards on the way, to export the both direction transferring polymer to above-mentioned volatile component outlet and above-mentioned polymer.
8, screw devolatilization pressurizing unit as claimed in claim 7, it is characterized in that: the distance as the covert anti-switching position of the inner edge of the volatilization composition outlet side of the peristome of polymer composition supply port and above-mentioned screw flight direction is X, screw diameter is D, the peristome diameter of the spiro rod length direction of above-mentioned polymer composition supply port is Y, with above-mentioned inner edge as initial point, volatilization composition outlet side is positive coordinate, then X-0.2Y～+ scope of 2D.
9, screw devolatilization pressurizing unit as claimed in claim 8 is characterized in that: above-mentioned distance X 0～+ scope of D.
10, a kind of devolatilization pressing method of polymer composition, but the screw devolatilization pressurizing unit that uses has cylindrical shell and the screw rod of free rotaring ground supporting in this, supply with the isobutylene-based polymer constituent that comprises isobutylene-based polymer and volatilization composition to this devolatilization pressurizing unit, remove the volatilization composition, obtain isobutylene-based polymer; It is characterized in that: the screw devolatilization pressurizing unit that uses screw surface to cover by chromium or titanium nitride.
11, devolatilization pressing method as claimed in claim 10 is characterized in that: at least one side of screw spiral sheet and cylindrical shell inner face is that 50～95 weight %, chromium containing ratio are that 5～35 weight %, iron containing ratio are that 0～5 weight %, Rockwell Hardness C target hardness are that cobalt more than 40 is that alloy covers by the cobalt containing ratio.
12, a kind of isobutylene-based polymer is characterized in that: obtained by claim 10 or 11 described devolatilization pressing methods.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01767999A JP3760059B2 (en) | 1999-01-26 | 1999-01-26 | Devolatilization extrusion method and screw type devolatilization extrusion equipment |
| JP17679/99 | 1999-01-26 | ||
| JP17679/1999 | 1999-01-26 | ||
| JP26460/1999 | 1999-02-03 | ||
| JP26460/99 | 1999-02-03 | ||
| JP11026460A JP2000226410A (en) | 1999-02-03 | 1999-02-03 | Purification of methacrylic polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1327414A true CN1327414A (en) | 2001-12-19 |
| CN1321793C CN1321793C (en) | 2007-06-20 |
Family
ID=26354238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB008021988A Expired - Fee Related CN1321793C (en) | 1999-01-26 | 2000-01-24 | Extruding method for volatilization and screw type extrusion machine for volatilization |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN1321793C (en) |
| WO (1) | WO2000044549A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103842150A (en) * | 2011-09-28 | 2014-06-04 | 朗盛德国有限责任公司 | Method for removing volatile components from polymer-containing media and degassing devices therefor |
| CN104097312A (en) * | 2013-04-08 | 2014-10-15 | 上海华明高技术（集团）有限公司 | Exhaust-driven extruder and method for producing polymer by using the extruder |
| CN105102202B (en) * | 2013-04-04 | 2018-06-29 | 阿朗新科德国有限责任公司 | Method for removing volatile component from medium containing elastomer and the degasser for this method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116920435B (en) * | 2023-09-14 | 2023-11-21 | 天津君宇科技股份有限公司 | Polymer devolatilization concentrating equipment |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1467045A (en) * | 1973-08-15 | 1977-03-16 | Mitsubishi Rayon Co | Process for removal of volatile component form methacrylate polymer composition |
| US4134714A (en) * | 1977-04-18 | 1979-01-16 | General Electric Company | Multi-stage continuous plastic extrusion apparatus, and extrusion screw |
| JPH01165779A (en) * | 1987-12-21 | 1989-06-29 | Fukuda Metal Foil & Powder Co Ltd | Hardening material for inside of cylinder |
| JP2782810B2 (en) * | 1989-07-17 | 1998-08-06 | 住友化学工業株式会社 | Method for devolatilizing extrusion of thermoplastic polymer composition |
| JPH03205123A (en) * | 1990-01-05 | 1991-09-06 | Mitsubishi Heavy Ind Ltd | Surface treating process for screw for plastic molding machine |
| JP2698855B2 (en) * | 1990-01-26 | 1998-01-19 | 住友重機械工業株式会社 | Method of manufacturing screw for plastic molding machine and method of forming alloy layer |
| JPH057435U (en) * | 1991-07-12 | 1993-02-02 | 積水化学工業株式会社 | Extruder for extrusion molding equipment |
| JPH08318529A (en) * | 1995-05-26 | 1996-12-03 | Idemitsu Petrochem Co Ltd | Manufacture of styrenic resin |
-
2000
- 2000-01-24 WO PCT/JP2000/000313 patent/WO2000044549A1/en active Application Filing
- 2000-01-24 CN CNB008021988A patent/CN1321793C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103842150A (en) * | 2011-09-28 | 2014-06-04 | 朗盛德国有限责任公司 | Method for removing volatile components from polymer-containing media and degassing devices therefor |
| TWI611903B (en) * | 2011-09-28 | 2018-01-21 | 艾朗希歐德意志有限公司 | Process for removing volatile constituents from polymer-containing media and devolatilisation apparatuses for this purpose and use of screw elements having a pitch t |
| CN103842150B (en) * | 2011-09-28 | 2018-04-13 | 阿朗新科德国有限责任公司 | The application of degassing method, degasser and screw element |
| CN105102202B (en) * | 2013-04-04 | 2018-06-29 | 阿朗新科德国有限责任公司 | Method for removing volatile component from medium containing elastomer and the degasser for this method |
| CN104097312A (en) * | 2013-04-08 | 2014-10-15 | 上海华明高技术（集团）有限公司 | Exhaust-driven extruder and method for producing polymer by using the extruder |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000044549A8 (en) | 2000-09-14 |
| CN1321793C (en) | 2007-06-20 |
| WO2000044549A1 (en) | 2000-08-03 |
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