CN103517792A - Method for producing polyarylene sulfide resin compositions - Google Patents
Method for producing polyarylene sulfide resin compositions Download PDFInfo
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- CN103517792A CN103517792A CN201180070428.8A CN201180070428A CN103517792A CN 103517792 A CN103517792 A CN 103517792A CN 201180070428 A CN201180070428 A CN 201180070428A CN 103517792 A CN103517792 A CN 103517792A
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- boosting section
- screw rod
- extruder
- water
- plasticizing
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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
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
- B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
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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
- B29B7/847—Removing of gaseous components before or after mixing
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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
- B29B7/88—Adding charges, i.e. additives
- B29B7/94—Liquid charges
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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
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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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
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/397—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using a single screw
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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
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
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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
- B29C48/68—Barrels or cylinders
- B29C48/681—Barrels or cylinders for single screws
Abstract
Provided is a technology for achieving the benefits of amino silane addition such as suppressed burr generation and improved weld strength and for achieving the benefits of drastically eliminating residual matter such as unreacted starting materials when producing polyarylene sulfide resin compositions. The positions of the plasticizing section and pressurizing section of the screw disposed in the cylinder of the extruder and the position of the vents provided in the cylinder are adjusted. In the invention, water is infused in the pressurizing section. It is also preferable that the pressurizing section has sealing rings at both ends thereof. A screw with multiple pressurizing sections can be used in the present invention.
Description
Technical field
The present invention relates to manufacture the method for poly arylidene thio-ester based resin composition.
Background technology
Accessory substance while understanding residual unreacted monomers, polymerization in thermoplastic resin, solvent etc.Even if these residues are made thermoplastic resin composition and are also remained in said composition through extruding operation.And known, when the injection mo(u)lding of said composition, extrusion molding etc., these residues become gaseous volatilization and cause peculiar smell or cause the harmful effects such as mold fouling.
One of thermoplastic resin as having the problem of above-mentioned residue, can list polyarylene sulfide resin.Particularly, remained unreacted raw material in polyarylene sulfide resin (for example, paracide (p-DCB)), need to be by the technology of its removal.
Also studied the method for in the polymerization process of polyarylene sulfide resin, the unreacting materials such as above-mentioned paracide being removed from polymer.In addition, also studied by manufacture poly arylidene thio-ester based resin composition extrude operation in fully carry out the method that these residues are removed in devolatilization.At present, for not needing the new reasons such as equipment cost, tend to carry out the latter's research.
For example, in patent documentation 1, recorded following technology: when poly arylidene thio-ester resinoid is melt extruded, use is provided with the double screw extruder of gas supply port and exhaust oral area, limit supplies gas to extruder limit and melt extrudes, by exhaust oral area by moisture and the oligomer removing residues that becomes to grade.And then, also to have recorded, it is the resinoid fusing department of poly arylidene thio-ester that the choosing of exhaust outlet quality award from the ministry arranges two above ，Qi positions.
Yet, while using air, oxygen isoreactivity gas as gas, may produce thermoplastic resin generation cross-linking reaction and the mobility of its composition is reduced or cause change color or because of the deteriorated problems such as mechanical property reduction that cause because of oxidation.On the other hand, use while take the non-active gas that nitrogen is representative, extruder oxygen concentration around reduces, and has the unfavorable condition that jeopardizes operator.
In patent documentation 2, recorded following technology: use the extruder with heater and exhaust oral area, when polyarylene sulfide resin is remained on to molten condition to injected water or water vapour or organic solvent in this extruder, thereby by the separation such as oligomer composition contained in poly arylidene thio-ester resinoid, limit is discharged limit from exhaust oral area by oligomer composition and is extruded together with water vapour or organic solvent.
Yet, while adopting the method for feed fluid as the technology of recording in patent documentation 2 and/or its steam, exist molten resin in extruder by liquid and/or its steam worry that makes extrudability deterioration such as cooling and curing.
In patent documentation 3, disclose and to have reduced residue and not to the method for supply gas, water, water vapour, organic solvent etc. in double screw extruder.In patent documentation 3, particularly, by adjustment, be used for the length of degassed screw rod, reduced above-mentioned residue.
But even if adopt in patent documentation 1～patent documentation 3 method described in any one, the effect that reduces residue is also insufficient, needs to improve.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 06-306170 communique
Patent documentation 2: Japanese kokai publication hei 06-306171 communique
Patent documentation 3: TOHKEMY 2010-228408 communique
Summary of the invention
the problem that invention will solve
The present invention forms in order to overcome the above problems, its object is, provide performance to suppress the effect that burr generation, improvement fusion intensity etc. obtain by adding amino silane, and when manufacturing poly arylidene thio-ester based resin composition, bring into play the technology of the effect of the residues such as unreacting material of significantly removing.
for the scheme of dealing with problems
The inventor etc. conduct in-depth research repeatedly in order to address the above problem.Found that, by adjustment, be disposed at the machine barrel of extruder the plasticizing portion of screw rod, the position of boosting section, be arranged at the position of the exhaust oral area of machine barrel, can address the above problem, thereby complete the present invention.More specifically, the invention provides following technical scheme.
(1) a kind of manufacture method of poly arylidene thio-ester based resin composition, it uses the extruder that is equipped with screw rod in machine barrel, the poly arylidene thio-ester based resin composition that manufacture comprises the polyarylene sulfide resin of having implemented in advance dry processing, described screw rod from the upstream side as raw material supplying side start to there is supply unit, plasticizing portion, boosting section, wherein, aforementioned machine barrel has the first row gas port portion that possesses decompressing unit between aforementioned plasticizing portion and aforementioned boosting section, in the more downstream of aforementioned boosting section, there is the second row gas port portion that possesses decompressing unit, in aforementioned plasticizing Bu Geng downstream, have for water being injected into the water filling port of machine barrel inside, from end of downstream side to the length L 1 of upstream-side-end of aforementioned boosting section and the ratio of the diameter D of aforementioned screw rod of aforementioned plasticizing portion, be that L1/D is more than 3.0 and below 25.0, from end of downstream side to the length L 2 of end of downstream side of aforementioned screw rod and the ratio of the diameter D of aforementioned screw rod of aforementioned boosting section, be that L2/D is more than 5.0 and below 15.0, from aforementioned supply unit, supply with the raw material that comprises polyarylene sulfide resin and amino silane, from aforementioned water filling port, to aforementioned boosting section, inject aforementioned water.
(2) according to the manufacture method of the poly arylidene thio-ester based resin composition (1) described, wherein, the two ends of aforementioned boosting section have sealing ring.
(3) a kind of manufacture method of poly arylidene thio-ester based resin composition, it uses the extruder that is equipped with screw rod in machine barrel, the poly arylidene thio-ester based resin composition that manufacture comprises the polyarylene sulfide resin of having implemented in advance dry processing, described screw rod from the upstream side as raw material supplying side start to there is supply unit, plasticizing portion, the first boosting section, the second boosting section, wherein, aforementioned machine barrel has the first row gas port portion that possesses decompressing unit between aforementioned the first boosting section and aforementioned the second boosting section, in the more downstream of aforementioned the second boosting section, there is the second row gas port portion that possesses decompressing unit, in aforementioned plasticizing Bu Geng downstream, have for water being injected to the water filling port of machine barrel inside, from end of downstream side to the length L 3 of upstream-side-end of aforementioned the second boosting section and the ratio of the diameter D of aforementioned screw rod of aforementioned the first boosting section, be that L3/D is more than 3.0 and below 15.0, from end of downstream side to the length L 2 of end of downstream side of aforementioned screw rod and the ratio of the diameter D of aforementioned screw rod of aforementioned the second boosting section, be that L2/D is more than 5.0 and below 15.0, from aforementioned supply unit, supply with the raw material that comprises polyarylene sulfide resin and amino silane, from aforementioned water filling port to aforementioned the first boosting section and/or aforementioned the second boosting section inject aforementioned water.
(4) a kind of manufacture method of poly arylidene thio-ester based resin composition, it uses the extruder that is equipped with screw rod in machine barrel, the poly arylidene thio-ester based resin composition that manufacture comprises the polyarylene sulfide resin of having implemented in advance dry processing, described screw rod from the upstream side as raw material supplying side start to there is supply unit, plasticizing portion, the first boosting section, the second boosting section, wherein, aforementioned machine barrel has the first row gas port portion that possesses decompressing unit between aforementioned plasticizing portion and aforementioned the first boosting section, in the more downstream of aforementioned the second boosting section, there is the second row gas port portion that possesses decompressing unit, in aforementioned plasticizing Bu Geng downstream, have for water being injected into the water filling port of machine barrel inside, from end of downstream side to the length L 4 of upstream-side-end of aforementioned the first boosting section and the ratio of the diameter D of aforementioned screw rod of aforementioned plasticizing portion, be that L4/D is more than 3.0 and below 15.0, from end of downstream side to the length L 2 of end of downstream side of aforementioned screw rod and the ratio of the diameter D of aforementioned screw rod of aforementioned the second boosting section, be that L2/D is more than 5.0 and below 15.0, from aforementioned supply unit, supply with the raw material that comprises polyarylene sulfide resin and amino silane, from aforementioned water filling port to aforementioned the first boosting section and/or aforementioned the second boosting section inject aforementioned water.
(5) according to the manufacture method of the poly arylidene thio-ester based resin composition (3) or (4) described, wherein, the two ends of aforementioned the first boosting section and/or aforementioned the second boosting section have sealing ring.
the effect of invention
According to the present invention, when manufacturing poly arylidene thio-ester based resin composition, can significantly remove the residues such as unreacting material.
Accompanying drawing explanation
Figure 1A is the figure in cross section of the extruder of schematically illustrated the first embodiment.
Figure 1B is the figure in cross section of the extruder of schematically illustrated the second embodiment.
Fig. 1 C is the figure in cross section of the extruder of schematically illustrated the 3rd embodiment.
Fig. 2 A is the schematic diagram of the extruder of use in embodiment 1, comparative example 1.
Fig. 2 B is the schematic diagram of the extruder of use in comparative example 2.
Fig. 2 C is the schematic diagram of the extruder of use in embodiment 2, comparative example 3.
Fig. 2 D is the schematic diagram of the extruder of use in comparative example 4.
Fig. 2 E is the schematic diagram of the extruder of use in embodiment 3, comparative example 5.
Fig. 2 F is the schematic diagram of the extruder of use in comparative example 6.
The specific embodiment
Below, embodiments of the present invention are elaborated.It should be noted that, the present invention is not limited to following embodiment.
The manufacture method > of < poly arylidene thio-ester based resin composition
The manufacture method of poly arylidene thio-ester based resin composition of the present invention is used the raw material that comprises polyarylene sulfide resin and amino silane.First, these raw materials are described.
[raw material]
Polyarylene sulfide resin refers to mainly using-(Ar-S)-material (Ar represents arlydene) of forming as repetitive.In the present invention, can use the polyarylene sulfide resin of conventionally known molecular structure.For example, can use with TOHKEMY 2009-138039 communique in the same polyarylene sulfide resin of the resin recorded.
In the present invention as removing in the middle of the residue of object, as becoming especially one of residue of problem, can list in the starting monomer using while manufacturing this polyarylene sulfide resin with the residual monomer of unreacted state.
The Production Example of polyarylene sulfide resin is as undertaken by following method:
The method of other comonomer polymerization under sulphur and sodium carbonates' presence that makes di halo aromatic compound and further add as required;
Other comonomer further adding when making di halo aromatic compound and needing in polar solvent, the method for polymerization under the existence of vulcanizing agent etc.;
Other comonomer further adding when making chlorobenzene mercaptan and needing carries out the method from condensation;
In organic polar solvent, the method for other comonomer reaction of further adding when making vulcanizing agent and di halo aromatic compound and needing etc.
Especially, in poly arylidene thio-ester resinoid, the residual meeting of di halo aromatic compound becomes problem, but while adopting manufacture method of the present invention, this residue also can easily be removed.
Then, amino silane is described.The generation of burr when amino silane is manufactured formed body in order to be suppressed at, in order to improve fusion intensity, use.
As amino silane compounds, particularly, can list γ mercaptopropyitrimethoxy silane, vinyltrimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, γ aminopropyltriethoxy silane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane etc.
In the removal method of existing residue, the known method (patent documentation 2 etc.) that makes water, and in the method for recording in patent documentation 2 grades, water can be injected into the fusing department of polyarylene sulfide resin.And then, it is generally acknowledged, the polyarylene sulfide resin being added in extruder can be also the moistening powdex that comprises moisture.Yet, as described later, in boosting section, during injected water, cannot fully not obtain the removal effect of paracide.In addition, in the present invention, while supplying feedwater from hopper, amino silane can react with water and be hydrolyzed.If amino silane hydrolysis, can lose the effect obtaining by using above-mentioned amino silane.Therefore, in the present invention, need to use the polyarylene sulfide resin of having implemented in advance dry processing.Dry level is not particularly limited, and conventionally, the water content of the polyarylene sulfide resin being dried is below 0.2 quality % with respect to the polyarylene sulfide resin of 100 quality %.
In the present invention, even if do not drop into water from hopper, also can remove fully residue, but as the polyarylene sulfide resin of putting into before hopper, can be undertaken that acid is cleaned, hot water cleans by use, organic solvent cleans (or their combinations) etc. and the material that removal such as by-product impurity have been refined further reduced from the necessity of hopper input water.
Then, other composition is described.According to object, except mentioned component, also can be used in combination on a small quantity other thermoplastic resin complementaryly.As other thermoplastic resin, such as listing aromatic polyester that PETG, polybutylene terephthalate (PBT) etc. form by aromatic dicarboxylic acid and dihydroxylic alcohols or oxygen yl carboxylic acid etc., polyamide, Merlon, ABS, polyphenylene oxide, polyalkyl acrylate, polysulfones, polyether sulfone, PEI, polyether-ketone, fluororesin, polyarylate etc.These thermoplastic resins also can be use mixing two or more.
In addition, in not damaging the scope of effect of the present invention, also can conventionally make an addition to according to the suitable interpolation of desired properties the known material of thermoplastic resin, that is, colouring agent, lubricant and crystallization promoter, the crystallization nucleating agents etc. such as the stabilizing agents such as flexibilizer, antioxidant, fire retardant, dye pigment such as glass fibre.
[extruder]
Then, the extruder of the first embodiment using in manufacture method of the present invention is described.Figure 1A is the figure in cross section of the extruder of schematically illustrated the first embodiment.
The extruder 1 using in the present invention possesses: the machine barrel 11 of the end-enclosed of screw rod 10, upstream side, the ejection mould 12 being connected with the end in machine barrel 11 downstream.It should be noted that, upstream side, downstream refer to respectively " upstream of extruding direction of extruder ", " downstream of extruding direction of extruder ".
Especially, than (L1/D) or the lower limit that is above-mentioned number range than (L2/D) when following, can produce the problem that the removal effect of paracide reduces.In addition, preferred is more than 5.0 and below 15.0 than the scope of (L1/D), and preferred is more than 7.0 and below 15.0 than the scope of (L2/D).
Supply unit has the raw material being supplied in machine barrel 11 is transported to the function of extruding direction (downstream direction).Particularly, use the screw element of the conveying use being formed by forward thread screw, make screw rod rotation, thereby raw material is transported to and extrudes direction.
Thereby plasticizing portion has and polyarylene sulfide resin of raw material etc. is applied to shearing force makes its heating make the function of the abundant melting of polyarylene sulfide resin.Plasticizing portion is used the screw element with plasticizing capacity (by the ability of resin melting).For example, can exemplify the screw elements such as reverse thread screw rod, sealing ring, forward kneading disk, reverse kneading disk, neutral kneading disk (neutral kneading disc).A plurality of use of screw element combination also these in addition, to mixing effect.In addition, even forward thread screw, during by the dark forward thread screw of screw channel and the shallow forward thread screw combination of screw channel, also can become the screw element with plasticizing capacity.
Boosting section has the abundant mixing function of the raw material of molten condition (polyarylene sulfide resin etc.).When raw material packet contains a plurality of composition, in this boosting section, mix more equably.Boosting section is also same with plasticizing portion, can use and can apply to the raw material of molten condition the screw element of compression stress, shear stress etc.
First row gas port portion 112 and second row gas port portion 113 all possess decompressing unit, reduce pressure degassed.As decompressing unit, for example, can exemplify vavuum pump.Size to vacuum is not particularly limited, and as described later, can suitably be set as preferred value according to kind of condition of molding, raw material etc.
Then, the extruder of the second embodiment using in manufacture method of the present invention is described.Figure 1B is the figure in the cross section of schematically illustrated extruder.It should be noted that, in the explanation after the second embodiment, to the identical Reference numeral of identical composed component mark, omit or simplify its explanation.
The extruder of the second embodiment is different from the extruder of the first embodiment in following formation: Liang Ge position has the formation (formation with the first boosting section and the second boosting section) of boosting section, the formation of undefined length L 1, the definition L3 that replaces configures the formation of first row gas port portion between the first boosting section and the second boosting section.Herein, L3 refers to from the length of the upstream-side-end of end of downstream side to the second boosting section of the first boosting section.
Then, the extruder of the 3rd embodiment using in manufacture method of the present invention is described.Fig. 1 C is the figure in the cross section of schematically illustrated extruder.
The extruder of the 3rd embodiment is different from the extruder of the first embodiment in following formation: Liang Ge position has the formation (formation with the first boosting section and the second boosting section) of boosting section, the formation of undefined length L 1, the definition L4 that replaces disposes the formation of first row gas port portion between plasticizing portion and the first boosting section.Herein, L4 refers to from the length of the upstream-side-end of end of downstream side to the first boosting section of plasticizing portion.
[manufacture method of resin combination]
Then, the situation of the extruder that uses the first embodiment of take is example, and the manufacture method of poly arylidene thio-ester based resin composition of the present invention is described.First, the raw material that comprises polyarylene sulfide resin and amino silane is dropped into from hopper 111.Then, by making screw rod 10 rotations that raw material is transported to and extrudes direction.Raw material is delivered to plasticizing portion, thereby raw material is applied to shearing force in plasticizing portion, plastifies.The raw material having plastified by plasticizing portion is further transported to downstream direction towards boosting section.
While shifting to boosting section by the raw material after plasticizing portion, utilize first row gas port portion 112 in the scope of length L 1, to reduce pressure degassed.By this degassed removal residue that reduces pressure.As mentioned above, owing to being more than 3.0 than (L1/D), therefore increased the removal effect of the residue of integral body of the present invention.
So utilize the decompressing unit of first row gas port portion 112 to carry out degassed, it is above and below 100Torr that vacuum is for example preferably 10Torr.For 10Torr is when above, from can be preferred by the reason that the vavuum pump of standard specification is dealt with, for 100Torr is when following, even be preferred from not carrying out especially the reason that the management of vacuum also can produce.The size of preferred vacuum is more than 10Torr and below 80Torr.
The raw material of having removed residue by first row gas port portion 112 is transported to boosting section by the rotation of screw rod 10.In boosting section, water is supplied with from water filling port 114.Amount to the water of supplying with is not particularly limited, with respect to the spray volume of every 1kg/Hr, more than being preferably 2g/Hr and below 10g/Hr (that is,, with respect to spray volume, preferably supplying with the water of 0.2 quality %～1.0 quality %).With respect to the spray volume of 1kg/Hr, be that 2g/Hr is when above, from can be preferred by the reason that the injection pump size of standard is dealt with, for 10g/Hr is when following, from dealing with but also the reason that can moisture more than necessity not removed by vaccum exhaust outlet is preferred by the injection pump size of standard.More preferably, the spray volume with respect to 1kg/Hr is more than 2g/Hr and below 6g/Hr.
The such device of camera cylinder pump is preferably used in the supply of water, adopts the method being pressed into.This is because for feedwater, mixing effect is high, brings into play fully the effect of the foaming being obtained by the supply of water by such.It should be noted that, boosting section is that the resin combination of molten condition is exerted pressure and carried out mixing part, uses method that the such device of camera cylinder pump is pressed into etc. if do not adopt, and is difficult to for feedwater.In addition, conventionally, in boosting section, polyarylene sulfide resin finishes with reacting of amino silane.
It should be noted that, in present embodiment, supply water to boosting section, but the position that is not limited to adopt in present embodiment for the position of feeding water.As long as for the position of feedwater be arranged at polyarylene sulfide resin and amino silane react the more boosting section in downstream of end point, can be the more upstream side of the position of present embodiment, also can Wei Geng downstream.
Herein, the effect being obtained by injected water is described.The water of supplying with is mixed in the raw material of molten condition, after just having mixed, utilizes the heat of raw material, and water becomes steam.In raw material, water becomes steam and causes foaming to occur.Due to this foaming, make the residue in raw material separated from raw material, from second row gas port portion, discharge together with water vapour.
In order to improve the removal effect of the residue being obtained by the foaming of water as above, need to promote the foaming of the raw material of molten condition.In order to promote the foaming of the raw material of molten condition, need water to be fully mixed in the inside of the raw material of molten condition.Therefore, preferably in boosting section to the raw material supplying water in mixing.This is because water, to the promotion that is mixed to get in raw material, can obtain larger removing residues effect.
In addition,, when boosting section has neutral kneading disk, preferably the part at neutral kneading disk supplies feedwater.This is because neutral kneading disk is the screw element that melting effect is very high, supplies water to while utilizing in the mixing raw material of this element, can further promote the mixing of water and raw material.
In addition, the method as improving by the effect obtaining for feedwater, has the method that at the two ends of boosting section, sealing ring is set in advance and supplies water to this boosting section.By utilizing sealing ring to make the two ends of boosting section become airtight conditions, can significantly reducing, be not mixed in raw material and after supply, become immediately the amount of the water that steam is discharged from.Its result, the amount of the water that the foaming in raw material is made contributions increases, and by the effect obtaining for feedwater, is improved.
On the other hand, even if supply water to the screw portion of the conveying use consisting of forward thread screw etc., water also only can slip over the surface of the resin combination of molten condition, and the water of supply and resin combination be not by mixing.Its result, the not foaming of the water in generation tree oil/fat composition, a water direct gasification, therefore cannot obtain by the effect obtaining for feedwater.
Having passed through the raw material of boosting section carries to ejection mould 12.In this process, utilize second row gas port portion 113 in the scope of length L 2, to reduce pressure degassed.By this degassed removal residue that reduces pressure.As mentioned above, than (L2/D), be more than 5.0, therefore, increased the removal effect of the residue of integral body of the present invention.
So utilize the decompressing unit of second row gas port portion 113 to carry out degassed, and that vacuum is for example preferably 10Torr is above and below 100Torr.For 10Torr is when above, from can be preferred by the reason that the vavuum pump of standard specification is dealt with, for 100Torr is when following, even be preferred from not carrying out especially the reason that the management of vacuum also can produce.The size of preferred vacuum is more than 10Torr and below 80Torr.
Finally, from ejection mould 12, extrude the raw material of molten condition, obtain poly arylidene thio-ester based resin composition.
As mentioned above, manufacturing method according to the invention, when manufacturing poly arylidene thio-ester based resin composition, can significantly remove the residues such as unreacting material.Above-mentioned residue is discharged to extruder from first row gas port portion 112 and second row gas port portion 113.In the present invention, first row gas port Bu112 position is between the position of two screw elements with mixing effect, by the distance (L1/D) between these two screw elements is made as to specific scope, can promote the discharge at the above-mentioned residue of first row gas port portion.That is,, in the situation of the extruder of the second embodiment, by the L3/D between the first boosting section and the second boosting section is made as to specific scope, can promote equally the discharge at the above-mentioned residue of first row gas port portion 112.In addition, in the situation of the extruder of the 3rd embodiment, by the L4/D between plasticizing portion and the first boosting section is made as to specific scope, can promote equally the discharge at the above-mentioned residue of first row gas port portion 112.
It should be noted that, the extruder of the extruder of the first embodiment, the second embodiment, the extruder of the 3rd embodiment all have second row gas port portion 113 in the more downstream of boosting section, at boosting section injected water.Therefore, even the extruder of the extruder of the second embodiment, the 3rd embodiment also can promote the discharge at the above-mentioned residue of second row gas port portion 113 equally with the extruder of the first embodiment.
Embodiment
Below, enumerate embodiment and further describe the present invention, and the present invention is not limited to these embodiment.
< evaluates 1 >
In embodiment 1, use following extruder 1(JSW system, " Tex-44 α II ").
The summary of the screw rod of extruder 1 is shown in to Fig. 2 A.
C0: hopper (raw material supplying portion) (111)
C3: plasticizing portion
C8: first row gas port portion (112)
C9: boosting section, water filling port (114)
C11: second row gas port portion (113)
Ejection mould (12)
In addition, than (L1/D), be recorded in table 1 than (L2/D).
In embodiment 1, as raw material, the material of the polyphenylene sulfide (KUREHA CORPORATION system, " FORTRON KPS W-220A ") that use comprises 99.3 quality % and the amino silane (γ aminopropyltriethoxy silane) of 0.7 quality %.The paracide (p-DCB) that comprises 20～50ppm in above-mentioned polyphenylene sulfide.The content of paracide is by being used the headspace gas chromatography of flame ionization ditector to measure under sample size 0.05g, the heating condition condition of 180 ℃ * 1 hour.
Use the above-mentioned raw materials of embodiment 1, under following condition of molding, implement extrusion molding, obtain pellet.
(extrusion condition)
Screw speed: 180rpm
Spray volume: 60kg/Hr
Barrel zone temperature: as follows to die end from resin feed-side:
(C1) 50-(C2) 150-(C3) 250-(C4) 250-(C5) 320-(C6) 300-(C7) 260-(C8) 260-(C9) 260-(C10) 260-(C11) 260-(C12) 260-(mould) 300
Vacuum: be recorded in table 1
The quantity delivered of water: be recorded in table 1
The extrudate utilization of the embodiment 1 obtaining and the same gimmick of above-mentioned gimmick are measured to the content of paracide.Measurement result is shown in to table 1.
Then, comparative example 1 is described.Except not carrying out the supply of water, by method similarly to Example 1, make extrudate, measure the content of paracide contained in extrudate.Measurement result is shown in to table 1.
Then, comparative example 2 is described.Except replacing extruder 1 with extruder 2, by method similarly to Example 1, make extrudate, measure the content of paracide contained in extrudate.Measurement result is shown in to table 1.It should be noted that, extruder 2 except machine barrel does not have first row gas port portion, with extruder 1 be same.The summary of the screw rod of extruder 2 is shown in to Fig. 2 B.
[table 1]
By evaluate 1 results verification to, in the first embodiment, by carrying out the supply of water and two exhaust oral areas being set, can significantly reduce the content of paracide.
< evaluates 2 >
C0: hopper (raw material supplying portion) (111)
C4: plasticizing portion
C6: the first boosting section
C9: first row gas port portion (112)
C10: the second boosting section, water filling port (114)
C11: second row gas port portion (113)
Ejection mould (12)
In addition, than (L3/D), be recorded in table 2 than (L2/D).
Comparative example 3 is described.Except not for feedwater, by method similarly to Example 2, make extrudate, measure the content of paracide contained in extrudate.Measurement result is shown in to table 2.
Then, comparative example 4 is described.Except replacing extruder 3 with extruder 4 and the quantity delivered of water being changed into the condition described in table 2, by method similarly to Example 2, make extrudate, measure the content of paracide contained in extrudate.Measurement result is shown in to table 2.It should be noted that, extruder 4 is same with extruder 3 except machine barrel does not have first row gas port portion.The summary of the screw rod of extruder 4 is shown in to Fig. 2 D.
[table 2]
By evaluate 2 results verification to, in the second embodiment, by carrying out the supply of water and two exhaust oral areas being set, also can significantly reduce the content of paracide.
< evaluates 3 >
C0: hopper (raw material supplying portion) (111)
C5: plasticizing portion
C6: first row gas port portion (112)
C7: the first boosting section
C10: the second boosting section, water filling port (114)
C11: second row gas port portion (113)
Ejection mould (12)
In addition, than (L4/D), be recorded in table 3 than (L2/D).
Then, comparative example 5 is described.Except not for feedwater, by method similarly to Example 3, make extrudate, measure the content of paracide contained in extrudate.Measurement result is shown in to table 3.
Then, comparative example 6 is described.Except replacing extruder 5 with extruder 6, by method similarly to Example 3, make extrudate, measure the content of paracide contained in extrudate.Measurement result is shown in to table 3.It should be noted that, extruder 6 is same with extruder 5 except machine barrel does not have first row gas port portion.The summary of the screw rod of extruder 6 is shown in to Fig. 2 F.
Then, comparative example 7 is described.Except replacing extruder 5 with extruder 7, by method similarly to Example 3, make extrudate, measure the content of paracide contained in extrudate.Measurement result is shown in to table 3.It should be noted that, extruder 7 is same except L4/D being made as 2.5 with extruder 5.
[table 3]
By evaluate 3 results verification to, in the 3rd embodiment, by carrying out the supply of water and two exhaust oral areas being set, also can significantly reduce the content of paracide.In addition, by comparative example 7 and embodiment 1～3, confirmed, by adjusting the situation of L4/D(embodiment 3), the situation of L1/D(embodiment 1) or the situation of L3/D(embodiment 2) and the length of L2/D to make their summation be more than 10, can bring into play effect of the present invention.
< evaluates 4 >
Embodiment 4 is described.Except extruder 3 is changed into extruder 7, by method similarly to Example 2, make extrudate, measure the content of paracide contained in extrudate.Measurement result is 0.2ppm.It should be noted that, extruder 7 is same except the two ends of the second boosting section have sealing ring with extruder 3.
By relatively confirming of embodiment 4 and embodiment 2, by sealing ring is set, can improve effect of the present invention.
< evaluates 5 >
Comparative example 8 is described.Except using, the water filling port of the extruder 3 using in embodiment 2 is changed into by C10 the extruder 8 of C7, by method similarly to Example 2, made extrudate, measure the content of paracide contained in extrudate.Measurement result is 0.9ppm.
By relatively confirming of embodiment 2 and comparative example 8, though beyond the boosting section of resin injected water, the effect of amount that reduces p-DCB is also low.
< evaluates 6 >
In order to study supply ，Wu Ge on the opportunity position of water, extract raw material in plasticizing as sample.By according to each sample of the determination of test method of test standard: ISO11443 at 310 ℃, shear rate 1000sec
-1under melt viscosity.In addition, to each sample by according to test standard: the high temperature GPC of JIS K7252-1 measures weight average molecular weight.As solvent, use 1-chloronaphthalene, molecular weight converts and determines with polystyrene standard.By these measurement results, calculate shear rate 1000sec
-1under melt viscosity, calculate the thickening multiplying power (melt viscosity of sample/calculated by polymer molecular weight melt viscosity) of amino silane.Thickening multiplying power is a timing, can regard polyarylene sulfide resin as and finish with reacting of amino silane.By measuring the react end point of knot confirmation polyarylene sulfide resin with amino silane, confirm the boosting section that water filling port is arranged to the resin in compare Gai Diangeng downstream.
description of reference numerals
1 extruder
10 screw rods
11 machine barrels
111 hoppers
112 first row gas port portions
113 second row gas port portions
114 water filling ports
12 ejection moulds
2 sealing rings
Claims (5)
1. the manufacture method of a poly arylidene thio-ester based resin composition, it uses the extruder that is equipped with screw rod in machine barrel, the poly arylidene thio-ester based resin composition that manufacture comprises the polyarylene sulfide resin of having implemented in advance dry processing, described screw rod from the upstream side as raw material supplying side start to there is supply unit, plasticizing portion, boosting section
Wherein, described machine barrel has the first row gas port portion that possesses decompressing unit between described plasticizing portion and described boosting section;
In the more downstream of described boosting section, there is the second row gas port portion that possesses decompressing unit;
In described plasticizing Bu Geng downstream, have for water being injected into the water filling port of machine barrel inside,
From end of downstream side to the length L 1 of upstream-side-end of described boosting section and the ratio of the diameter D of described screw rod of described plasticizing portion, be that L1/D is more than 3.0 and below 25.0,
From end of downstream side to the length L 2 of end of downstream side of described screw rod and the ratio of the diameter D of described screw rod of described boosting section, be that L2/D is more than 5.0 and below 15.0,
From described supply unit, supply with the raw material that comprises polyarylene sulfide resin and amino silane, from described water filling port, to described boosting section, inject described water.
2. the manufacture method of poly arylidene thio-ester based resin composition according to claim 1, wherein, the two ends of described boosting section have sealing ring.
3. the manufacture method of a poly arylidene thio-ester based resin composition, it uses the extruder that is equipped with screw rod in machine barrel, the poly arylidene thio-ester based resin composition that manufacture comprises the polyarylene sulfide resin of having implemented in advance dry processing, described screw rod from the upstream side as raw material supplying side start to there is supply unit, plasticizing portion, the first boosting section, the second boosting section
Wherein, described machine barrel has the first row gas port portion that possesses decompressing unit between described the first boosting section and described the second boosting section;
In the more downstream of described the second boosting section, there is the second row gas port portion that possesses decompressing unit;
In described plasticizing Bu Geng downstream, have for water being injected into the water filling port of machine barrel inside,
From end of downstream side to the length L 3 of upstream-side-end of described the second boosting section and the ratio of the diameter D of described screw rod of described the first boosting section, be that L3/D is more than 3.0 and below 15.0,
From end of downstream side to the length L 2 of end of downstream side of described screw rod and the ratio of the diameter D of described screw rod of described the second boosting section, be that L2/D is more than 5.0 and below 15.0,
From described supply unit, supply with the raw material that comprises polyarylene sulfide resin and amino silane, from described water filling port to described the first boosting section and/or described the second boosting section inject described water.
4. the manufacture method of a poly arylidene thio-ester based resin composition, it uses the extruder that is equipped with screw rod in machine barrel, the poly arylidene thio-ester based resin composition that manufacture comprises the polyarylene sulfide resin of having implemented in advance dry processing, described screw rod from the upstream side as raw material supplying side start to there is supply unit, plasticizing portion, the first boosting section, the second boosting section
Wherein, described machine barrel has the first row gas port portion that possesses decompressing unit between described plasticizing portion and described the first boosting section;
In the more downstream of described the second boosting section, there is the second row gas port portion that possesses decompressing unit;
In described plasticizing Bu Geng downstream, have for water being injected into the water filling port of machine barrel inside,
From end of downstream side to the length L 4 of upstream-side-end of described the first boosting section and the ratio of the diameter D of described screw rod of described plasticizing portion, be that L4/D is more than 3.0 and below 15.0,
From end of downstream side to the length L 2 of end of downstream side of described screw rod and the ratio of the diameter D of described screw rod of described the second boosting section, be that L2/D is more than 5.0 and below 15.0,
From described supply unit, supply with the raw material that comprises polyarylene sulfide resin and amino silane, from described water filling port to described the first boosting section and/or described the second boosting section inject described water.
5. according to the manufacture method of the poly arylidene thio-ester based resin composition described in claim 3 or 4, wherein, the two ends of described the first boosting section and/or described the second boosting section have sealing ring.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2011/060313 WO2012147185A1 (en) | 2011-04-27 | 2011-04-27 | Method for producing polyarylene sulfide resin compositions |
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| CN103522517A (en) * | 2013-09-30 | 2014-01-22 | 昆山市华浦塑业有限公司 | Extrusion device with impurity removing functions |
| JP2019104107A (en) * | 2016-04-15 | 2019-06-27 | 住友化学株式会社 | Method for producing resin composition and twin screw kneading extruder |
| CN115066459B (en) * | 2020-02-10 | 2023-02-28 | 宝理塑料株式会社 | Method for producing polyarylene sulfide resin composition |
| WO2021161995A1 (en) * | 2020-02-10 | 2021-08-19 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1890075A (en) * | 2003-12-12 | 2007-01-03 | 宝理塑料株式会社 | Resin composition hardly staining metal mold and method of manufacturing the same |
| CN102007184A (en) * | 2008-04-17 | 2011-04-06 | 宝理塑料株式会社 | Method for producing polyarylene sulfide resin composition |
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| JPH06306171A (en) * | 1993-04-27 | 1994-11-01 | Dainippon Ink & Chem Inc | Production of high-purity polyarylene sulfide resin |
| JPH08207118A (en) * | 1995-02-06 | 1996-08-13 | Japan Steel Works Ltd:The | Removal of volatile substance from thermoplastic resin and vent type twin-screw extruder |
| JP3989075B2 (en) * | 1997-02-18 | 2007-10-10 | 旭化成ケミカルズ株式会社 | Method for producing resin composition |
| JP2000135713A (en) * | 1998-10-30 | 2000-05-16 | Toray Ind Inc | Preparation of thermoplastic resin composition |
| JP2000318001A (en) * | 1999-05-07 | 2000-11-21 | Teijin Ltd | Resin molding method and production of molded article |
| WO2007108384A1 (en) * | 2006-03-16 | 2007-09-27 | Toray Industries, Inc. | Polyphenylene sulfide resin composition, process for producing the same, and molded article |
| JP2008238626A (en) * | 2007-03-28 | 2008-10-09 | Toray Ind Inc | Manufacturing method for thermoplastic resin composition |
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| CN1890075A (en) * | 2003-12-12 | 2007-01-03 | 宝理塑料株式会社 | Resin composition hardly staining metal mold and method of manufacturing the same |
| CN102007184A (en) * | 2008-04-17 | 2011-04-06 | 宝理塑料株式会社 | Method for producing polyarylene sulfide resin composition |
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| WO2012147185A1 (en) | 2012-11-01 |
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