JP6110491B2 - Fiber manufacturing method, fiber and fiber spinning pack - Google Patents

Description

  The present invention generally relates to a fiber, a fiber manufacturing system, a fiber manufacturing method, and a fiber manufacturing apparatus. More specifically, the present invention relates to fine denier amorphous polymer fibers, such as fine denier polyetherimide fibers, and systems, methods and apparatus for producing such fibers without melt spinning and stretching the polymer.

  Synthetic fibers have been manufactured for many years in highly established processes and process equipment optimized for the melt properties and physical properties of semi-crystalline materials, namely low melt viscosity, excellent thermal stability and crystallization. Synthetic fibers have traditionally been manufactured using semi-crystalline materials that require a process or die design process that is very low viscosity in the dissolved state and that can provide uniform melt distribution across the spinneret hole pattern. The spinneret is designed to facilitate such uniform distribution of the melt. However, these designs are not preferred for use with amorphous polymers including thermoplastics such as polyetherimide. The processing of amorphous thermoplastics into fibers using a melt spinning process is a novel process that has limited success in conventional melt spinning lines. Some of these challenges are due to processing equipment designs that are not suitable for amorphous materials. Despite the need, specifically for the production of fibers from amorphous thermoplastics by melt spinning amorphous thermoplastics and reducing the denier without drawing the resulting fibers There is no designed melt spinning line or spinneret.

  Synthetic fibers have traditionally been produced using semi-crystalline materials that crystallize upon drawing from a spinneret and are easily melt spun into fine denier fibers with a denier per filament (dpf) of 2 or less. Amorphous materials do not form crystals when stretched, and therefore do not have sufficient elongation and strength during the stretching process in a process that draws below 2 dpf using conventional melt spinning methods. Due to the limited fineness of the fibers produced in conventional processes, the protocol is the conversion of certain amorphous engineering thermoplastic compositions such as polyetherimide (PEI) pellets into fine denier fibers. Not suitable for. There is a demand for polyetherimide fibers having a dpf of 2 or less. Methods and processing techniques that enable the production of sub-2dpf fibers from amorphous engineering thermoplastics such as PEI must be developed. Current attempts to produce fine denier fibers have been made with conventional methods, either stretching by the stretching operation after the conversion process or not stretching below 2 dpf.

  An embodiment includes the steps of producing a spun fiber by extruding a polymer melt through a spinneret under a pressure of 400-1500 psi and collecting the spun fiber on a transfer roll (also referred to as a supply roll) to coagulate from the spun fiber. And a method of collecting the coagulated fibers on a spool without subjecting to a drawing step. The melt may contain an amorphous polymer composition such as polyetherimide. The coagulated fiber may have a dpf of more than 0 to 2.5 and a shrinkage rate of 2% or less.

  Another embodiment relates to unstretched amorphous polymer fibers having a denier of less than 2.5 dpf and a shrinkage of greater than 0 to 2%.

  Yet another embodiment relates to a spinneret for producing amorphous unstretched polyetherimide fibers having a dpf of at most 2.5 from a composition comprising an amorphous polyetherimide, such as polyetherimide. The spinneret eliminates the need for a distribution plate and can operate at a pressure that is at least 40% lower than the operating pressure of the spinneret with the distribution plate. The spinneret may comprise a screen pack filter that is connected to the die and distributes the composition to the die. The dies may have a plurality of circular melt channels, each having a length and a diameter, and a ratio of the length to the diameter of 2: 1 to 6: 1.

These and other features, aspects and advantages will be better understood with reference to the following description, claims and appended drawings.
1 is a schematic illustration of a prior art spinneret design with two distribution plates that are not present in the design of various embodiments of the present invention. FIG. FIG. 4 is a schematic diagram of a 72-hole spinneret design with three capillary concentric rings for center core distribution delivery according to various embodiments of the present invention. FIG. 6 is a schematic diagram of a 144-hole spinneret design with a screen pack filter having six capillary concentric rings for dispensing according to various embodiments of the present invention. 1 is a schematic diagram of a prior art fiber manufacturing process that may be improved using spinnerets according to various embodiments of the present invention. FIG.

  It should be understood that the various embodiments are not limited to the arrangements and instrumentality shown in the figures.

  In the following detailed description and the claims that follow, reference will be made to a number of terms that shall be defined to have the following meanings:

  “Denier” is a unit of measurement of the linear mass density of a fiber. In this application and claims, denier is defined as the mass (g) per 9,000 meters.

  In this application and claims, a “spinneret” is a porous device that extrudes a plastic polymer melt to form fibers.

  All numerical values herein are considered modified with “about”, whether or not explicitly indicated. “About” generally refers to a numerical range that is considered equivalent (ie, has the same function or result) to those skilled in the art. In many cases, “about” may include numbers that are rounded to the nearest significant figure.

  One embodiment of the invention relates to a process for producing fine denier fibers from engineering thermoplastics such as polyetherimide.

  In the conventional fiber forming process by melt extrusion, in order to maintain a uniform distribution of the melt throughout the spinneret hole, the cooling rate is controlled by using a quenching device, and thus when the fiber is drawn from the spinneret. High pressure (1000-2000 psi) is important when controlling the crystallinity of the material. In various embodiments of the present invention, these conditions that are undesirable for the processing of amorphous engineering thermoplastics into fine denier fibers are avoided. According to embodiments of the present invention, the pressure can be reduced (400-2000 psi) to reduce shear to the molten material, thereby reducing the adverse effects of excessive shear, i.e., dropping or cutting of fiber strands. . It has been found that when the viscosity of the molten amorphous thermoplastic is high, the back pressure of the system can be made sufficiently high and the melt can be evenly distributed over the entire spinneret. Upon exiting the spinneret, the material is not cooled in the quench cabinet, and in fact uses heat in this space to slow down the cooling rate of the amorphous material and reduce the quenching effect on the spun material. This provides unexpected benefits. In the method according to the present invention using the above method, the polyetherimide fiber can be melt-spun well to 2 dpf or less.

  An embodiment relates to a method comprising a series of steps. The step may be sequential or non-sequential. The method may comprise the step of producing a spun fiber by extruding the melt through a spinneret.

  The melt may be extruded through a spinneret under pressure within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower limit value and / or the upper limit value are 100, 150, 200, 250, 300, 350, 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900, 950, 1000, 1050, 1100, 1150, 1200, 1250, 1300, 1350, 1400, 1450, 1500, 1550, 1600, 1650, 1700, 1750, 1800, 1850, 1900, 1950 and 2000 psi can be selected. According to certain preferred embodiments, the melt can be extruded through a spinneret, for example under a pressure of 400-1500 psi.

  The melt may contain an amorphous polymer composition. The melt flow rate of the amorphous polymer composition may be within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower limit value and / or the upper limit value are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, It can be selected from 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 and 60 g / 10 minutes. According to certain preferred embodiments, the melt flow rate of the amorphous polymer composition may be, for example, 4-18 g / 10 min.

  The melt may include one or more crystalline materials. The amorphous polymer composition may contain polyimide. Polyimides include polyetherimide and polyetherimide copolymers. The polyetherimide may be selected from (i) a polyetherimide homopolymer such as polyetherimide, (ii) a polyetherimide copolymer such as polyetherimide sulfone, and (iii) combinations thereof. Polyetherimide is a known polymer and is sold by SABIC Innovative Plastics under the ULTEM®, EXTEM® and Siltem brands (trademark of SABIC Innovative Plastics IP BV).

式中、ａは２以上であり、例えば１０〜１，０００以上であり、より具体的には１０〜５００である。 In some embodiments, the polyetherimide has the structure of formula (1):

In the formula, a is 2 or more, for example, 10 to 1,000 or more, and more specifically 10 to 500.

  The group V of formula (1) is a tetravalent linker containing an ether group (here “polyetherimide”) or a combination of ether and arylene sulfone groups (“polyetherimide sulfone”). Such linkers include, but are not limited to, (a) a C5-50 substituted or unsubstituted, saturated, unsaturated or aromatic monocycle optionally substituted with an ether group, an arylene sulfone group or a combination thereof. (B) C1-30 substituted or unsubstituted, linear or branched, saturated or unsaturated, optionally substituted with an ether group or a combination of an ether group and an arylene sulfone group A saturated alkyl group; or a combination containing at least one of these. Further suitable substituents include, but are not limited to, ether groups, amide groups, ester groups, and combinations including at least one of these.

｛式中、Ｑ１は、これに限定されないが、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−ＳＯ２−、−ＳＯ−、−ＣｙＨ２ｙ−（ｙは１〜５の整数）および、パーフルオロアルキレン基を含むこれらのハロゲン化誘導体などの二価部分を含む｝が挙げられる。 The R group of the formula (1) is not limited thereto, but (a) a C6-20 aromatic hydrocarbon group and a halogenated derivative thereof, (b) a C2-20 linear or branched alkylene group, (c ) C3-20 cycloalkylene group or (d) a divalent group of formula (2):

{In the formula, Q1 is not limited thereto, but -O-, -S-, -C (O)-, -SO2-, -SO-, -CyH2y- (y is an integer of 1 to 5) and Including a divalent moiety such as a halogenated derivative thereof containing a perfluoroalkylene group.

式中、Ｗは、−Ｏ−、−ＳＯ２−または式−Ｏ−Ｚ−Ｏ−［式中、−Ｏ−または−Ｏ−Ｚ−Ｏ−基の二価結合は、３，３'、３，４'、４，３'または４，４'の位置にあり、Ｚは、これに限定されないが、式（４）

｛式中、Ｑは、これに限定されないが、−Ｏ−、−Ｓ−、−Ｃ（Ｏ）−、−ＳＯ２−、−ＳＯ−、−ＣｙＨ２ｙ−（ｙは１〜５の整数）および、パーフルオロアルキレン基を含むこれらのハロゲン化誘導体を含む｝の二価基を含む］の基の二価部分である。 In certain embodiments, linker V includes, but is not limited to, a tetravalent aromatic group of formula (3):

In the formula, W is —O—, —SO 2 — or a formula —O—Z—O— [wherein the divalent bond of the —O— or —O—Z—O— group is 3, 3 ′, 3 , 4 ′, 4, 3 ′ or 4, 4 ′, and Z is not limited to this,

{In the formula, Q is not limited thereto, but -O-, -S-, -C (O)-, -SO2-, -SO-, -CyH2y- (y is an integer of 1 to 5) and A divalent portion of a group including a halogenated derivative including a perfluoroalkylene group.

式中、Ｔは、−Ｏ−または式−Ｏ−Ｚ−Ｏ−基である。ここで、−Ｏ−または−Ｏ−Ｚ−Ｏ−基の二価結合は３，３'、３，４'、４，３'または４，４'の位置にあり；Ｚは、上記で定義したように式（３）の二価基であり；Ｒは、上記で定義したように式（２）の二価基である。 In certain embodiments, the polyetherimide comprises 2 or more structural units of formula (5), specifically 10 to 1,000, more specifically 10 to 500:

In the formula, T is —O— or a group of formula —O—Z—O—. Where the divalent bond of the —O— or —O—Z—O— group is in the 3,3 ′, 3,4 ′, 4,3 ′ or 4,4 ′ position; Z is as defined above Is a divalent group of formula (3); R is a divalent group of formula (2) as defined above.

  In another specific embodiment, the polyetherimide sulfone is a poly-ether comprising an ether group and a sulfone group, wherein at least 50 mol% of the linker V and R group of formula (1) comprises a divalent arylene sulfone group. Ether imide. For example, all linkers V except for any R group may contain an arylene sulfone group; or, except for any linker V, all R groups may contain an arylene sulfone group; Alternatively, the arylene sulfone may be present in a part of the linker V and R groups, provided that the total molar fraction of the linker V and R group containing an aryl sulfone group is 50 mol% or more.

式中、Ｙは−Ｏ−、−ＳＯ２−あるいは式−Ｏ−Ｚ−Ｏ−の基であり、−Ｏ−、ＳＯ２−または−Ｏ−Ｚ−Ｏ−基の二価結合は３，３'、３，４'、４，３'または４，４'の位置にあり、Ｚは、上記のように式（３）の二価基であり、Ｒは、式（２）のＹモルとＲモルの合計の５０モル％超が−ＳＯ２−基を含むことを条件として、上記のように式（２）の二価基である。 Even more specifically, the polyetherimide sulfone may contain two or more structural units of the formula (6), specifically 10 to 1,000, more specifically 10 to 500. :

In the formula, Y is —O—, —SO 2 — or a group of formula —O—Z—O—, and the divalent bond of —O—, SO 2 — or —O—Z—O— is 3,3 ′. , 3, 4 ', 4, 3' or 4, 4 ', Z is a divalent group of formula (3) as described above, and R is the Y mole of formula (2) and R It is a divalent group of formula (2) as described above, provided that more than 50 mol% of the total moles contain -SO2- groups.

It should be understood that the polyetherimide and polyetherimide sulfone may optionally include a linker V that does not include an ether group or an ether group and a sulfone group, such as, for example, a linker of formula (7):

  Imide units containing such linkers are generally present in an amount of 0 to 10 mol%, specifically 0 to 5 mol% of the total number of units. In certain embodiments, there is no additional linker V in the polyetherimide and polyetherimide sulfone.

  In another specific embodiment, the polyetherimide comprises 10 to 500 structural units of formula (5) and the polyetherimide sulfone comprises 10 to 500 structural units of formula (6).

  Polyetherimide and polyetherimide sulfone can be prepared by any suitable process. In certain embodiments, the polyetherimide and polyetherimide copolymers include polycondensation polymerization methods and halo substitution polymerization methods.

  The polycondensation method may include a method for preparing a polyetherimide having the structure (1) and is referred to as a nitro substitution method (X is nitro in formula (8)). In one example of the nitro substitution method, N-methylphthalimide is nitrated with 99% nitric acid to produce a mixture of N-methyl-4-nitrophthalimide (4-NPI) and N-methyl-3-nitrophthalimide (3-NPI). Generate. After purification, a mixture containing about 95 parts 4-NPI and 5 parts 3-NPI is reacted with the disodium salt of bisphenol A (BPA) in toluene in the presence of a phase transfer catalyst. This reaction, known as the nitro substitution step, produces BPA-bisimide and NaNO2. After purification, BPA-bisimide is reacted with phthalic anhydride by imide exchange reaction to obtain BPA-dianhydride (BPADA), and this is then subjected to imidation polymerization step in orthodichlorobenzene such as metaphenylenediamine (MPD) To obtain a polyetherimide product.

  Other diamines can also be used. Suitable diamines include m-phenylenediamine; p-phenylenediamine; 2,4-diaminotoluene; 2,6-diaminotoluene; m-xylylenediamine; p-xylylenediamine; benzidine, 3,3′-dimethyl. 3,3′-dimethoxybenzidine; 1,5-diaminonaphthalene; bis (4-aminophenyl) methane; bis (4-aminophenyl) propane; bis (4-aminophenyl) sulfide; bis (4-aminophenyl) ) Sulfone; bis (4-aminophenyl) ether; 4,4′-diaminodiphenylpropane; 4,4′-diaminodiphenylmethane (4,4′-methylenedianiline); 4,4′-diaminodiphenyl sulfide; 4′-diaminodiphenyl sulfone; 4,4′-diaminodiphenyl ether ( , 4'-oxydianiline); 1,5-diaminonaphthalene; 3,3 'dimethylbenzidine; 3-methylheptamethylenediamine; 4,4-dimethylheptamethylenediamine; 2,2', 3,3'-tetrahydro -3,3,3 ', 3'-tetramethyl-1,1'-spirobi [1H-indene] -6,6'-diamine; 3,3', 4,4'-tetrahydro-4,4,4 ', 4'-tetramethyl-2,2'-spirobi [2H-1-benzo-pyran] -7,7'-diamine; 1,1'-bis [1-amino-2-methyl-4-phenyl] And cyclohexane, and isomers thereof, and blends containing at least one of them. In certain embodiments, the diamine is specifically an aromatic diamine, in particular m- and p-phenylene diamine, and mixtures comprising at least one of these.

  Suitable dianhydrides that can be used with diamines include, but are not limited to, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride; 4,4′-bis (3 , 4-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4′-bis (3,4-dicarboxyphenoxy) benzophenone 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride; 4′-bis (2,3-dicarboxyphenoxy) diphenyl ether dianhydride; 4,4′-bis (2,3-dicarboxyphenoxy) diphenylsulfi Dianhydride; 4,4′-bis (2,3-dicarboxyphenoxy) benzophenone dianhydride; 4,4′-bis (2,3-dicarboxyphenoxy) diphenylsulfone dianhydride; 4- (2, 3-dicarboxyphenoxy) -4 '-(3,4-dicarboxyphenoxy) diphenyl-2,2-propane dianhydride; 4- (2,3-dicarboxyphenoxy) -4'-(3,4 Dicarboxyphenoxy) diphenyl ether dianhydride; 4- (2,3-dicarboxyphenoxy) -4 ′-(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4- (2,3-dicarboxyphenoxy) -4 '-(3,4-dicarboxyphenoxy) benzophenone dianhydride; 4- (2,3-dicarboxyphenoxy) -4'-(3,4-dicarboxyphenoxy) ) Diphenylsulfone dianhydride; 1,3-bis (2,3-dicarboxyphenoxy) benzene dianhydride; 1,4-bis (2,3-dicarboxyphenoxy) benzene dianhydride; 1,3-bis (3,4-dicarboxyphenoxy) benzene dianhydride; 1,4-bis (3,4-dicarboxyphenoxy) benzene dianhydride; 3,3 ′, 4,4′-diphenyltetracarboxylic dianhydride 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride; naphthalic dianhydrides such as 2,3,6,7-naphthalic dianhydride; 3,3', 4,4'- Biphenyl sulfonic acid tetracarboxylic dianhydride; 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride; 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride; 4 , 4'-bis (3 , 4-dicarboxyphenoxy) diphenyl sulfide dianhydride; 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride; 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl Propane dianhydride; 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; bis (phthalic acid) phenylsulfine oxide dianhydride; p-phenylene-bis (triphenylphthalic acid) dianhydride; m-phenylene-bis (triphenylphthalic acid) dianhydride; bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride; bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride 2,2′-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride; 4,4′-oxydiphthalic dianhydride; Lomellitic dianhydride; 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride; 4 ′, 4′-bisphenol A dianhydride; hydroquinone diphthalic dianhydride; 6,6′- Bis (3,4-dicarboxyphenoxy) -2,2 ′, 3,3′-tetrahydro-3,3,3 ′, 3′-tetramethyl-1,1′-spirobi [1H-indene] dianhydride 7,7′-bis (3,4-dicarboxyphenoxy) -3,3 ′, 4,4′-tetrahydro-4,4,4 ′, 4′-tetramethyl-2,2′-spirobi [2H -1-benzopyran] dianhydride; 1,1′-bis [1- (3,4-dicarboxyphenoxy) -2-methyl-4-phenyl] cyclohexane dianhydride; 3,3 ′, 4,4 ′ -Diphenylsulfone tetracarboxylic dianhydride; 3,3 ', 4,4'-diphenyls Rufidotetracarboxylic dianhydride; 3,3 ′, 4,4′-diphenyl sulfoxide tetracarboxylic dianhydride; 4,4′-oxydiphthalic dianhydride; 3,4′-oxydiphthalic dianhydride; 3,3′-oxydiphthalic dianhydride; 3,3′-benzophenonetetracarboxylic dianhydride; 4,4′-carbonyldiphthalic dianhydride; 3,3 ′, 4,4′-diphenylmethanetetracarboxylic Acid dianhydride; 2,2-bis (4- (3,3-dicarboxyphenyl) propane dianhydride; 2,2-bis (4- (3,3-dicarboxyphenyl) hexafluoropropane dianhydride (3,3 ′, 4,4′-diphenyl) phenylphosphine tetracarboxylic dianhydride; (3,3 ′, 4,4′-diphenyl) phenylphosphine oxide tetracarboxylic dianhydride; 2,2 ′ Dichloro-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2′-dimethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2′- Dicyano-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2′-dibromo-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2′- Diiodo-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2′-ditrifluoromethyl-3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2 '-Bis (1-methyl-4-phenyl) -3,3', 4,4'-biphenyltetracarboxylic dianhydride; 2,2'-bis (1-trifluoromethyl-2-phenyl) -3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis (1-trifluoro Olomethyl-3-phenyl) -3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride; 2,2′-bis (1-trifluoromethyl-4-phenyl) -3,3 ′, 4 4'-biphenyltetracarboxylic dianhydride; 2,2'-bis (1-phenyl-4-phenyl) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride; 4,4'- Bisphenol A dianhydride; 3,4'-bisphenol A dianhydride; 3,3'-bisphenol A dianhydride; 3,3 ', 4,4'-diphenyl sulfoxide tetracarboxylic dianhydride; '-Carbonyldiphthalic dianhydride; 3,3', 4,4'-diphenylmethanetetracarboxylic dianhydride; 2,2'-bis (1,3-trifluoromethyl-4-phenyl) -3, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, And combinations of these isomers and these isomers.

式中、Ｒは上記のものであり、Ｘは、ニトロ基またはハロゲンである。式（８）のビスフタルイミドは、例えば、式（９）の対応する無水物の縮合で形成できる：

式中、Ｘは、式（１０）の有機ジアミンを有するニトロ基またはハロゲンである：

式中、Ｒは上記のものである。 The halo-substituted polymerization process for producing polyetherimide and polyetherimide sulfone includes, but is not limited to, the reaction of bis (phthalimide) of formula (8):

In the formula, R is as described above, and X is a nitro group or halogen. The bisphthalimide of formula (8) can be formed, for example, by condensation of the corresponding anhydride of formula (9):

Where X is a nitro group or halogen having an organic diamine of formula (10):

In the formula, R is as described above.

  Specific examples of the amine compound of the formula (10) include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexa Methylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1 2-bis (3-aminopropoxy) ethane, bis (3-aminopropyl) sulfide, 1,4-cyclohexanediamine, bis- (4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2,4 -Diaminotoluene, 2,6-diaminotoluene, m-xylylenediamine, p-xylylenediamine, 2-methyl-4,6-diethyl-1,3-phenylenediamine, 5-methyl-4,6-diethyl- 1,3-phenylene-diamine, benzidine, 3,3′-dimethylbenzidine, 3,3′-dimethoxybenzidine, 1,5-diaminonaphthalene, bis (4-aminophenyl) methane, bis (2-chloro-4- Amino-3,5-diethylphenyl) methane, bis (4-aminophenyl) propane, 2,4-bis ( b-amino-t-butyl) toluene, bis (p-b-amino-t-butylphenyl) ether, bis (p-b-methyl-o-aminophenyl) benzene, bis (p-b-methyl-o-) Aminopentyl) benzene, 1,3-diamino-4-isopropylbenzene, bis (4-aminophenyl) ether and 1,3-bis (3-aminopropyl) tetramethyldisiloxane. Mixtures of these amines can also be used. Specific examples of amine compounds of formula (10) containing a sulfone group include, but are not limited to, diaminodiphenyl sulfone (DDS) and bis (aminophenoxyphenyl) sulfone (BAPS). Combinations containing any of these amines can also be used.

  The polyetherimide is prepared by the presence or absence of a phase transfer catalyst between a bis (phthalimide) of formula (8) and an alkali metal salt of a dihydroxy-substituted aromatic hydrocarbon of formula HO-V-OH where V is as described above. It can be synthesized in any reaction. Suitable phase transfer catalysts are disclosed in US Pat. No. 5,229,482. Specifically, dihydroxy substituted aromatic hydrocarbons such as bisphenol A, or a combination of an alkali metal salt of bisphenol and an alkali metal salt of another dihydroxy substituted aromatic hydrocarbon can be used.

  In certain embodiments, the polyetherimide comprises structural units of formula (5). Wherein each R is independently p-phenylene, m-phenylene or a mixture comprising at least one of these; T is a group of the formula —O—Z—O — {— O—Z—O— The divalent bond is in the 3,3 ′ position, and Z is a 2,2-diphenylene ruene propane group (bisphenol A group) group. Further, the polyetherimide sulfone is a structural unit of the formula (6), wherein at least 50 mol% of the R groups are of the formula (4) (Q is —SO 2 —), and the remaining R groups are independently , P-phenylene, m-phenylene, or a combination comprising at least one of these}; T represents a group of the formula —O—Z—O— wherein the —O—Z—O— group The divalent bond is in the 3,3 ′ position, and Z is a 2,2-diphenylenepropane group.

  Polyetherimide and polyetherimide sulfone may be used alone or in combination with each other, or may be used in combination with other polymeric materials disclosed in the polymer component manufacture described herein. In some embodiments, only polyetherimide is used. In another embodiment, the mass ratio of polyetherimide to polyetherimide sulfone may be 99: 1 to 50:50.

  The weight average molecular weight (Mw) of the polyetherimide can be 5,000 to 100,000 g / mol as measured by gel permeation chromatography (GPC). In some embodiments, the Mw can be 10,000 to 80,000. Molecular weight in this specification refers to absolute mass average molecular weight (Mw).

  The intrinsic viscosity of the polyetherimide can be 0.2 dl / g or more as measured in m-cresol at a temperature of 25 ° C. Within this range, the intrinsic viscosity can be 0.35 to 1.0 dl / g measured in m-cresol at a temperature of 25 ° C.

  The glass transition temperature of the polyetherimide may be greater than 180 ° C., specifically 200 ° C. to 500 ° C., as measured by differential scanning calorimetry (DSC) according to ASTM D3418. In some embodiments, the polyetherimide, particularly a general polyetherimide, has a glass transition temperature of 240 ° C to 350 ° C.

  The melt index of the polyetherimide may be 0.1-10 g / min as measured at a temperature of 340-370 ° C. and a load of 6.7 kg in accordance with ASTM D1238.

  An alternative halo-substituted polymerization method for producing polyetherimide (eg, polyetherimide having the structure of formula (1)) is a process called chlorine substitution method (X is chlorine in formula (8)). The chlorine substitution method is illustrated as follows: 4-chlorophthalic anhydride and metaphenylenediamine are reacted in the presence of sodium phenylphosphinate catalyst to give metaphenylenediamine (CAS Registry Number 148935-94-8). ) Bischlorophthalimide. Thereafter, bischlorophthalimide is polymerized with the disodium salt of BPA in a chlorine substitution reaction in the presence of a catalyst in orthodichlorobenzene or anisole solvent. Alternatively, 3-chloro- and 4-chlorophthalic anhydride can be used to obtain a mixture of bischlorophthalimide isomers, which can be polymerized with BPA disodium salt by chlorine substitution as described above.

式中、Ｒ１−６はそれぞれ独立に、Ｃ５−３０の置換または未置換、飽和、不飽和または芳香族単環式基、Ｃ５−３０の置換または未置換、飽和、不飽和または芳香族多環式基、Ｃ１−３０の置換または未置換アルキル基、およびＣ２−３０の置換または未置換アルケニル基から構成される群から選択され；Ｖは、Ｃ５−５０の置換または未置換、飽和、不飽和または芳香族単環式および多環式基、Ｃ１−３０の置換または未置換アルキル基、Ｃ２−３０の置換または未置換アルケニル基およびこれらのリンカーの少なくとも１つを含む組み合わせから構成される群から選択された四価リンカーであり；ｇは１〜３０であり；ｄは２〜２０である。市販のシロキサンポリエーテルイミドは、ＳＡＢＩＣ Ｉｎｎｏｖａｔｉｖｅ Ｐｌａｓｔｉｃｓ社からブランド名ＳＩＬＴＥＭ＊（＊ＳＡＢＩＣ Ｉｎｎｏｖａｔｉｖｅ Ｐｌａｓｔｉｃｓ ＩＰ Ｂ．Ｖ．社の商標）で入手できる。 The siloxane polyetherimide may comprise a polysiloxane / polyetherimide block copolymer having a siloxane content of greater than 0 to less than 40% by weight relative to the total weight of the block copolymer. The block copolymer comprises a siloxane block of formula (11):

In the formula, each R1-6 is independently a C5-30 substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic group, a C5-30 substituted or unsubstituted, saturated, unsaturated or aromatic polycycle. Selected from the group consisting of a formula group, a C1-30 substituted or unsubstituted alkyl group, and a C2-30 substituted or unsubstituted alkenyl group; V is a C5-50 substituted or unsubstituted, saturated, unsaturated Or from a group consisting of aromatic monocyclic and polycyclic groups, C1-30 substituted or unsubstituted alkyl groups, C2-30 substituted or unsubstituted alkenyl groups and combinations comprising at least one of these linkers Selected tetravalent linker; g is 1-30; d is 2-20. A commercially available siloxane polyetherimide is available from SABIC Innovative Plastics under the brand name SILTEM * (* Trademark of SABIC Innovative Plastics IP BV).

  The weight average molecular weight (Mw) of the polyetherimide may be within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower limit value and / or the upper limit value are 5000, 6000, 7000, 8000, 9000, 10000, 11000, 12000, 13000, 14000, 15000, 16000, 17000, 18000, 19000, 20000, 21000, 22000, 23000, 24000, 25000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 50000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 9000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 70000, 71000, 72000, 73000, 74000, 75000, 76000, 77000, 78000, 79000, 80000, 81000, 82000, 83000, 84000, 85000, 86000, 87000, 88000, 89000, 90000, 91000, 92000, 93000, 94000, 95000, 96000, 97000, 98000, 99000, 100000, 101000, 102000, 103000, 104000, 105000, 106000, 107000, 108000, Selected from 109000 and 110,000 Daltons Get. The weight average molecular weight (Mw) of the polyetherimide can be, for example, 5,000-100,000 daltons, 5,000-80,000 daltons, or 5,000-70,000 daltons. The primary alkyl amine modified polyetherimide will have a lower molecular weight and higher melt flow than the starting unmodified polyetherimide.

  Polyetherimides include those described in, for example, U.S. Pat. Nos. 3,875,116, 6,919,422, and 6,355,723, such as 4,690,997. Polyether imide sulfone described in US Pat. No. 4,808,686, polyether imide sulfone described in US Pat. No. 7,041,773, and combinations thereof. May be. Each of these patents is incorporated herein in its entirety.

  The glass transition temperature of the polyetherimide can be within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower limit value and / or the upper limit value are 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300 and It can be selected from 310 ° C. The glass transition temperature (Tg) of the polyetherimide can be, for example, greater than about 200 ° C.

  The polyetherimide may be substantially free of benzyl protons (less than 100 ppm). The polyetherimide may be free of benzyl protons. The amount of benzyl protons in the polyetherimide can be less than 100 ppm. In certain embodiments, the amount of benzyl protons is greater than 0 and less than 100 ppm. In another embodiment, the amount of benzyl protons is not detectable.

  The polyetherimide may be substantially free of halogen atoms (less than 100 ppm). The polyetherimide may be free of halogen atoms. The amount of halogen atoms in the polyetherimide can be less than 100 ppm. In certain embodiments, the halogen atom weight is greater than 0 and less than 100 ppm. In another embodiment, the halogen atom weight is not detectable.

  In one embodiment, the polyetherimide comprises a polyetherimide heat comprising: (a) a polyetherimide; and (b) an amount of a phosphorus-containing stabilizer effective to increase the melt stability of the polyetherimide. The low volatility of the phosphorus-containing stabilizer is a plastic composition, wherein an initial amount of the phosphorus-containing stabilizer sample is measured by thermogravimetric analysis, and the sample is heated at a heating rate of 20 ° C./in an inert atmosphere. When heated to 300 ° C. per minute, 10% by mass or more of the initial amount of the sample remains without volatilization. In certain embodiments, the phosphorus-containing stabilizer has the structure of formula P-Ra, wherein R ′ is independently hydrogen, alkyl, alkoxy, aryl, aryloxy, or an oxy substituent; a is 3 or 4 Is). Examples of such suitable stabilized polyetherimides are found in US Pat. No. 6,001,957, which is hereby incorporated by reference in its entirety.

  The method may comprise the step of collecting the spun fibers on a transfer roll or supply roll without drawing. In the typical prior art process shown in FIG. 4, the spun fibers are collected by a converging guide 406, and the fibers are drawn by a series of drawn godets (collectively 409) operating at high speeds while applying tension to the fibers to denier them. Reduce. The final material can be applied to the coagulated fibers 407 with a final applicator in the form of a kiss roll 408. In the apparatus according to the present invention, the use of final and kiss rolls 408 is optional, and in some embodiments, a series of stretched godets 409 may be completely absent. Accordingly, the apparatus according to the invention comprises a spinneret according to FIG. 2 or 3, a transfer roll for collecting spun fibers, a supply roll, and at least one spool on which fine denier undrawn fibers are collected for future use. A bobbin. The method may comprise producing coagulated fibers from a melt spun polymer. Embodiments of the method may comprise collecting the coagulated fibers on a spool without going through a drawing step. Embodiments of the method may produce coagulated fibers without a forced air cooling step. The method may comprise the step of collecting the fibers on a spool without undergoing any annealing step. The method may comprise the step of heating the spun fiber after exiting the spinneret.

  The dpf of the coagulated fiber can be within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower and upper limits are 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1. 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2. 4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3. From 7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 and 5dpf It may be selected. According to certain preferred embodiments, the dpf of the coagulated fiber may be greater than 0 to 2.5.

  The shrinkage of the coagulated fiber can be within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower and upper limits are 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1. 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2. 4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3. 7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 and 5% Can be selected. According to a preferred embodiment, the shrinkage rate of the coagulated fibers can be, for example, 2% or less.

  One embodiment also relates to a novel spinneret design suitable for the production of low denier and low shrinkage fibers using high viscosity amorphous engineering thermoplastics. Unlike known processing of polyetherimide fibers, which require the use of high pressure conditions (eg, 1500-2000 psi) to maintain a uniform distribution of the melt across the spinneret hole, according to various embodiments The spinneret is designed to allow uniform distribution at pressures as low as 400 psi (eg, in the range of 400-1500 psi, preferably in the range of 400-1200 psi, more preferably in the range of 400-1000 psi). Is done. Accordingly, the die design and spinneret enable melt spinning of amorphous thermoplastics such as PEI into fine denier fibers. In these embodiments, a completely circular melt channel is possible across the entire die, where amorphous material collects or swirls, creating a dead space or stagnation that does not flow easily but stagnates and deteriorates. Can be minimized and then the degraded material can be intermittently released into the melt stream. The ratio of melt channel length to diameter can be optimized for amorphous materials, the distribution channel reduces shear to the material, and uses a higher viscosity amorphous material in the molten state It can be designed to obtain a uniform distribution of the melt over the entire spinneret. Using a design similar to the proposed design, it is now possible to spin materials that could not be spun into fibers at all, regardless of denier, and wind them on a spool. Fiber can be achieved.

  One particular embodiment relates to a spin pack comprising a spinneret and / or a spinneret that produces amorphous unstretched polyetherimide fibers of up to 2.5 dpf from a composition comprising an amorphous polyetherimide. The spinneret does not require a distribution plate.

  The spinneret may comprise a die having a plurality of circular melt channels each having a length and a diameter. The ratio of length to diameter of each circular melt channel is 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, It may be 10: 1, 11: 1 or 12: 1. According to certain preferred embodiments, the ratio of the length to the diameter of each circular melt channel may be, for example, 2: 1 to 6: 1.

  According to certain embodiments, the spinneret can operate at a lower pressure compared to the same spinneret with a distribution plate. According to various embodiments, the operating pressure of a spinneret without a distribution plate can be reduced at a rate relative to the same spinneret with a distribution plate. The ratio can be within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower limit value and / or the upper limit value are 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 and 60% may be selected. According to certain preferred embodiments, the working pressure of a spinneret without a distribution plate according to various embodiments can be reduced by at least 40% compared to the same spinneret with a distribution plate.

  The spinneret may further comprise at least one screen pack filter connected to the die for distributing the composition to the die. The mesh size of the screen pack filter may be within a certain range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower limit value and / or the upper limit value are 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 490 and 500 mesh may be selected. According to one preferred embodiment, the screen pack filter mesh size may be 200-400 US mesh.

  Other embodiments relate to amorphous polymer fibers. The fibers can be drawn, but can have excellent properties even in an undrawn state.

The denier of unstretched amorphous polymer fibers according to various embodiments can be within a range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower and upper limits are 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1. 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2. 4, 2.5, 2.6, 2.7, 2.8, 2.9 and 3 can be selected. According to certain preferred embodiments, the denier of unstretched amorphous polymer fibers can be less than 2.5.
The shrinkage of unstretched amorphous polymer fibers according to various embodiments can be within a range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower and upper limits are 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1. 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2. 4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3. 7, 3.8, 3.9 and 4% may be selected. According to certain preferred embodiments, the shrinkage of the unstretched amorphous polymer fiber can be greater than 0 to 2%.

  The polydispersity (Mw / Mn) of unstretched amorphous polymer fibers according to various embodiments may be within a range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower and upper limit values are 1, 1.25, 1.5, 1.75, 2, 2.25, 2.5, 2.75, 3, 3.25, 3.5, 3.75, Can be selected from 4, 4.25, 4.5, 4.75, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 and 100. According to certain preferred embodiments, the polydispersity (Mw / Mn) of unstretched amorphous polymer fibers according to various embodiments can be 2.5 or greater.

  The denier of unstretched amorphous polymer fibers according to various embodiments can be within a range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower and upper limits are 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1. 1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2. 4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3. 7, 3.8, 3.9 and 4 can be selected. According to certain preferred embodiments, the denier of unstretched amorphous polymer fibers according to various embodiments can be less than 2.2.

  The strength of unstretched amorphous polymer fibers according to various embodiments can be within a range having a lower limit and / or an upper limit. The range may or may not include the lower limit value and / or the upper limit value. The lower limit value and / or the upper limit value are 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2. 1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3. 4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4. 7, 4.8, 4.9, 5, 10, 15, 20, 25, 30, 35, 40, 45 and 50 cN / dtex. According to certain preferred embodiments, the strength of unstretched amorphous polymer fibers according to various embodiments can be at least 2.6 cN / dtex.

  Unstretched amorphous polymer fibers according to various embodiments may have the above properties without annealing.

  Another embodiment relates to an article comprising the unstretched amorphous polyetherimide fiber. The article includes, but is not limited to, one or more of the polyetherimide fibers (eg, optionally wound, knitted, woven, spun, or otherwise associated with different types of fibers. Yarns made from unstretched amorphous polyetherimide fibers), fabrics made from unstretched amorphous fibers and / or yarns, and fabrics made from unstretched amorphous fibers, or A composite material based on this can be mentioned. Examples of suitable composites include, but are not limited to, paper (eg, electric paper, honeycomb paper, woven special paper, non-woven special paper); structural composites; and semi-structural composites.

  In summary, a process for producing unstretched amorphous polymer fibers can be obtained at pressures of 400-1500 psi (e.g., 400-1000 psi) with a melt flow rate optionally between 4-18 g / 10 min, such as polyetherimide. Extruding a melt containing the amorphous polymer composition through a spinneret to produce a spun fiber; collecting the spun fiber on a supply roll without drawing, and from the spun fiber, a dpf of greater than 0 to 2 .5, producing a coagulated fiber having a shrinkage rate of 2% or less; and winding the coagulated fiber on a spool without being subjected to a drawing step. In any of the foregoing embodiments, one or more of the following conditions may be applied: The method may further optionally comprise collecting the fibers on a spool without an annealing step. The method may further comprise heating the spun fiber after exiting the spinneret to produce a solidified fiber without a forced air cooling step; the melt may be one or more crystalline Contains materials.

  The denier of the amorphous polymer fibers (e.g., fibers produced by the method described above) is less than 2.5, less than 2.2 or less than 2.0, and the shrinkage is greater than 0 to 2%; The fibers further optionally have a melt flow rate of 4-18 g / 10 min, optionally a polydispersity (Mw / Mn) of greater than 0 to 2.5, and optionally a strength of at least 2.6 cN / dtex. For example, a polyetherimide fiber such as polyetherimide may be used. The fiber may not be annealed. Articles containing the aforementioned fibers include yarns, fabrics, and composites.

Spinnerets useful for the above production method of amorphous unstretched polyetherimide fibers of up to 2.5 dpf (eg, melt flow rate 4-18 g / 10 min) do not have a distribution plate; Identical spinning with a die having a plurality of circular melt channels having a length and a diameter, the ratio of 2: 1 to 6: 1, the spinneret optionally comprising a distribution plate At least one screen pack filter (eg, a filter having a 200-400 US mesh size) that operates at a pressure that is at least 40% lower than the working pressure of the base and optionally connects to the die and distributes the composition to the die. Prepare.
The invention is further described in the following specific examples (unless otherwise indicated, all parts and percentages are parts by weight,% by weight).

Examples Table 1 shows the materials used in the examples.

  In the examples, two spinneret designs were used. The first is the α spinneret design (see FIG. 1). Hereinafter, this type of spinneret design will be described in more detail. The second is a β-pack spinneret design (see FIGS. 2 and 3) according to various embodiments of the present invention.

1. 1. Description of α Spinneret Design As shown in FIG. 1, a spin pack 100 according to the prior art is a capillary spinneret that is a rectangular block that is fitted in a heater jacket portion of an extruder with a gap of about 0.25 inches around the periphery. A plate 102 is provided. The prior art spin pack 100 requires a series of distribution plates 103 that are incorporated between the base plate 101 and the capillary spinneret plate 102. The distribution plate 103 is designed to provide a pressure block to evenly distribute the melt into a rectangular array of 144 capillaries. The plates may have different sizes and shapes depending on the extruder used.

  Distributing plate 103 has a very thin melt channel of only about 0.02 inches, a melt channel for material that is only 0.01 inches in diameter and 3/16 inch in length. The limited size of the melt channel results in severe flow conditions for the amorphous material and high internal pack pressure. The internal pack pressure provides a limited processing window for the material. This also causes the material to cover or accumulate the capillary spinneret plate 102 during manufacture. This residue increases with time and must be scraped off the surface. This is undesirable because the process is interrupted.

  The temperature of the spin pack 100 is controlled by convection heating of the surrounding air gap in the extruder. In a system using the spin pack 100, the response to changes in operating conditions such as temperature and pressure is slow. Also, typically, a large temperature loss is observed from the set point to the spin pack, so the operator must adjust the set point temperature to about 20 ° C. above the desired temperature.

2. Description of the Novel Spinneret Design (“β Pack Design”) According to various embodiments, a capillary spinneret that produces melt spun fibers from polyetherimide has a capillary array that is uniformly distributed around a circular pack surface. It may be similar to the showerhead design in that it may have.

  FIG. 2 is a schematic diagram illustrating a spin pack 200 according to various embodiments having a capillary spinneret 201. The specific capillary spinneret 201 shown in FIG. 2 has 72 capillaries 202, but the number of capillaries may be any suitable one. The capillary spinneret 201 may be sandwiched with the distribution block 203 between the base plate 204 and the end cap 205. The distribution block 203 may have a plurality of distribution holes 206 that distribute the molten material to the capillary spinneret 201. The end cap 205 may have a plurality of through-holes 207 aligned with corresponding holes 208 on the base plate 204 for securing and compressing the spin pack 200 with bolts or other securing means.

  FIG. 3 is a schematic diagram illustrating a spin pack 300 according to various embodiments having a capillary spinneret 301. Although the specific capillary spinneret 301 shown in FIG. 3 has 144 capillaries 315, the number of capillaries 315 may be any appropriate one. The capillary spinneret 301 may be sandwiched between the end cap 305 and one or more base plates together with the screen pack filter 302, the first gasket 303, and the second gasket 304. As shown in FIG. 3, a first base plate 306 and a second base plate 307 may be used.

  The end cap 305 has a plurality of through holes 308 aligned with corresponding holes 309 on the base plate 306 for securing and compressing the components of the spin pack 200 with bolts or other securing means. Also good. The first base plate 306 may be fixed to the second base plate 307 with bolts or other fixing means inserted into the receiving holes 311 on the second base plate 307 through the through holes 310 thereabove.

  The second base plate 307 is, for example, an injection port 312 that can inject molten material into the pack 300 from an extruder to which the spinning pack 300 is fixed by bolts or other fixing means inserted through fixing holes 313 thereover. May be provided. The first base plate 306 may include one or more distribution ports 314 that allow the molten material to flow continuously through the spin pack 300.

  Since the capillary spinneret 301 having 144 capillaries has the same throughput as that of the conventional “α” pack design, the spin pack 300 shown in FIG. 3 was used in the examples described below.

  In this design, the melt was easily and efficiently delivered to the pack surface. Since the distribution plate is omitted, the melt is distributed only by the screen pack filter 302. Distributing port 314 provides a complete circular runner system and carries the melt flow from the extruder outlet to the center of the back of the screen pack filter. The gaskets 303 and 304 provide sufficient cavities at the rear of the filter 302 (ie, on the first base plate 306 side), and a uniform flow of material can be formed at the rear of the screen. Once sufficient pressure is formed at the rear of the screen pack filter, the melt passes through it and flows into the spinneret. As shown in FIG. 4, the melt is then extruded through the capillary 315 with the formed pressure, drawn onto a take-up roll, and taken up on one or more bobbins 410.

  FIG. 4 is a schematic diagram of a fiber process 400. Melt stream 401 from the extruder may be fed through metering pump 402, filter 403 and spinneret 404. The melt stream 401 after exiting the spinneret 404 may be passed through the air cooling 405. The convergence guide 406 directs the fiber 407 to the final applicator 408 and winds it onto one or more bobbins 410 via a series of drawn godets 409.

  Various spinnerets were designed and manufactured, and the effect was investigated by changing the ratio of the capillary hole length to diameter (L / D) to 1-6 and the diameter from 0.2 mm to 1.0 mm. . The mesh size of the screen pack filter was also changed from 200 to 400 mesh depending on the viscosity of the material.

  This spin pack design was mounted on a Hills GHP Bi-component melt spinning extrusion line. The spin pack design is designed to fit the same pack envelope as for the α design. This new design is configured to provide sufficient space around the head of the pack to allow temperature control by direct contact of the high watt heater band. With this new design, the spin pack surface, an important part in the melt spinning process, is temperature controlled much more strictly and rapidly.

Description of PEI production using a novel β spinneret design The material was dried at 300 ° F. × 4-8 hours to remove any water that could cause the polymer to degrade in the molten state.

  The spin pack is assembled and placed in a preheat oven, and its temperature is raised to the operating temperature prior to incorporation into the extruder and melt flow.

  After switching on the extruder and preheating for several hours, any material is introduced into the extruder. When the predetermined temperature is reached, the pellets are fed to the extruder using an automatic loader on the hopper above the extruder. Switch on the melt pump, then switch on the extruder. The melt pump and the extruder are controlled manually until the melt flow exits the extruder and a reasonable melt pressure and speed is obtained. During the remainder of the subsequent process, the melt pressure is automatically controlled.

  When the temperature and pressure reach the desired equilibrium, the pump and extruder are stopped and the spinneret is removed from the oven and incorporated into the extruder. An external heater band is mounted on the spin pack along with its control thermocouple. The unit is then switched on and set to the desired set point.

  Then switch on the melt pump and the extruder again. Collect the extruded fibers in the waste barrel until the spinneret is raised to operating temperature. During this time, a melt sample is taken for each fiber in order to determine the specific gravity of the melt.

  After the temperature and pressure have stabilized, the fibers are sucked into a suction gun and collected on a supply roll or transfer roll under any spin final kiss roll. The speed of the pump and transfer roll determines the resulting fiber diameter, ie denier per filament (dpf). After the desired dpf is obtained, the fiber is mounted on a winder. The winder winds the fiber bundles onto at least one spool or bobbins for subsequent use in downstream processes.

  In the case of PEI fibers of 2 dpf or less, the pump is operated at 4 to 6 rpm and the transfer roll is operated at 1500 m / min to 2500 m / min. This process configuration does not require further stretching on any stretching roll, or does not require annealing on any relaxation roll.

Description of PEI manufacturing using a conventional α spinneret design The steps for the α spinneret design are the same with respect to the start-up and operational procedure steps. The steps are different when obtaining fine fibers of 2 dpf or less. In this case, it is necessary to draw the fiber on the drawing roll, and it is necessary to control the shrinkage rate on the relaxing roll.

  In the case of 2 dpf PEI fibers using this configuration, the melt pump is operated at 5-7 rpm and the supply roll is operated at 1500 m / min to 2500 m / min. The supply roll maintains a speed of 1500 m / min to 2500 m / min at a temperature of 200 ° C., the stretching roll maintains a speed of 2250 m / min to 3000 m / min at the same temperature, and the relaxing roll has a speed of 2250 m / min at the same temperature. Maintain ~ 3000 m / min. Fiber annealing and the resulting shrinkage can be controlled by increasing the number of laps on the godet and the temperature of the godet.

Fiber Denier Measurement Technology Fiber denier, or linear density, is measured according to ASTM D1907-07 test method. The fiber was wound with a specified number of revolutions on a reel having a circumference of 1 m and weighed. Depending on the mass and length of the sample, the linear density, or denier, of the individual fiber filaments is determined.

Fiber Shrinkage Measurement Technique A fiber shrinkage test was conducted in accordance with ASTM D2559 dry heating method. A 1 m long fiber sample was placed in an oven and exposed to the appropriate temperature for a predetermined time. The sample is then removed from the oven and the subsequent length is measured. From the deviation from the initial length of 1 m, the rate of change, that is, the shrinkage rate is obtained.

Example 1
The purpose of this example is to produce PEI fibers according to the present invention. Fibers were produced according to the above procedure except that a (1 + 1/4) inch extruder and a β pack design were used. A 0.6 mm capillary spinneret with an L / D of 4 and a 325 mesh screen pack filter were used.

  A fiber having a dpf of 2 and a shrinkage rate of less than 2% was produced. When manufactured directly from a spinneret without the need for drawing or annealing the first wound fiber, the fiber unexpectedly exhibited a combination of low denier and low shrinkage. The fiber could be produced at a speed of 1500 m / min to 2250 m / min for at least 2 hours without breaking. This example thus shows that low denier fibers can be conveniently produced from polyetherimides having a molecular weight distribution of at least 2.5.

Example 2
The purpose of this example is to repeat the process performance of Example 1 to produce polyetherimide fibers according to various embodiments of the present invention. Fibers were produced according to the above procedure. A 0.6 mm capillary spinneret with an L / D of 4 and a 325 mesh screen pack filter were used. The obtained fiber had a dpf of 1.8 and a shrinkage rate of less than 2%.
When produced directly from a spinneret under low shear conditions and without the need for fiber drawing or annealing, the resulting fibers exhibited a combination of low denier and low shrinkage. The fiber could be produced at a speed of 1500 m / min to 2250 m / min for at least 2 hours without breaking. This example shows that low denier fibers can be conveniently made from polyetherimide with a molecular weight distribution of at least 2.5.

Example 3
The purpose of this example is to incorporate a lower mesh screen pack filter to produce a polyetherimide fiber according to an embodiment of the present invention. Fibers were produced according to the procedures of Examples 1 and 2 except that a 200 US mesh screen pack filter was used.

  When produced directly from a spinneret under low shear conditions and without the need for fiber drawing or annealing, the resulting fibers exhibited a combination of low denier and low shrinkage. A fiber having a dpf of 2 and a shrinkage of 1.9% could be produced. These fibers were produced without breaking at a speed of 1500 m / min to 2250 m / min for at least 2 hours. This example shows that low denier fibers can be conveniently made from polyetherimide having a molecular weight distribution of at least 2.5.

Example 4
The purpose of this example is to incorporate a lower mesh screen pack filter to produce a polyetherimide fiber according to an embodiment of the present invention. Fibers were made according to the procedures of Examples 1 and 2 except that a 400 mesh screen pack filter was used.

  When produced directly from a spinneret under low shear conditions and without the need for fiber drawing or annealing, the resulting fibers exhibited a combination of low denier and low shrinkage. A fiber having a dpf of 2 and a shrinkage of 1.8% could be produced. These fibers were produced without breaking at a speed of 1500 m / min to 2250 m / min for at least 2 hours. This example shows that low denier fibers can be conveniently made from polyetherimide having a molecular weight distribution of at least 2.5.

Example 5
The purpose of this example is to produce a polyetherimide fiber according to an embodiment of the present invention. Fibers were produced according to the procedure described in Example 4 except that a spinneret with an L / D of 2 was used.

  When produced directly from a spinneret without the need for fiber drawing or annealing, the resulting fibers exhibited a combination of low denier and low shrinkage. A fiber having a dpf of 2 and a shrinkage of less than 2% could be produced. These fibers were produced without breaking at a speed of 1500 m / min to 2250 m / min for at least 2 hours. This example shows that low denier fibers can be conveniently made from polyetherimide having a molecular weight distribution of at least 2.5.

Example 6
The purpose of this example is to repeat the performance of Example 5 to produce PEI fibers according to certain embodiments of the present invention.

  When produced directly from a spinneret under low shear conditions and without the need for fiber drawing or annealing, the resulting fibers exhibited a combination of low denier and low shrinkage. A fiber having a dpf of 2 and a shrinkage of less than 2% could be produced. These fibers were produced without breaking at a speed of 1500 m / min to 2250 m / min for at least 2 hours. This example shows that low denier fibers can be conveniently produced from PEI having a molecular weight distribution of at least 2.5.

Example 7
The purpose of this example is to produce a polyetherimide fiber according to an embodiment of the present invention. Fibers were produced according to the procedure described above except that this example was performed on a 1 inch screw with a β pack design. In this configuration, a 0.2 mm capillary with a L / D of 4 and a 200 mesh screen pack filter were used.

  When produced directly from a spinneret under low shear conditions and without the need for fiber drawing or annealing, the resulting fibers exhibited a combination of low denier and low shrinkage. A fiber having a dpf of 1.7 and a shrinkage rate of 1.1% could be produced. These fibers were produced without breaking at a speed of 1500 m / min to 2250 m / min for at least 2 hours. Due to the small capillary size, the pack pressure increased to 1400 psi in this example. This example shows that low denier fibers can be conveniently produced from PEI having a molecular weight distribution of at least 2.5.

Example 8
The purpose of this example is to produce a polyetherimide fiber according to an embodiment of the present invention. Fibers were produced according to the procedure described above except that this example was performed on a 1 inch extruder using a β pack design. The spinneret was a 0.4 mm diameter capillary with an L / D ratio of 4. In this scenario, a 200 mesh screen pack filter was also used.

  When produced directly from a spinneret under low shear conditions and without the need for fiber drawing or annealing, the resulting fibers exhibited a combination of low denier and low shrinkage. A fiber having a dpf of 2 and a shrinkage of 1.5% could be produced. These fibers were produced without breaking at a speed of 1500 m / min to 2250 m / min for at least 2 hours. This example shows that low denier fibers can be conveniently produced from PEI having a molecular weight distribution of at least 2.5.

Comparative Example 9
The purpose of this example is to produce polyetherimide fibers according to the prior art “α” spin pack design (with distribution plate) shown in FIG. Fibers were produced according to the above procedure and the following results were obtained. PEI fibers were produced using ULTEM® 9011 PEI. This example was performed on a 1 inch extruder. A 0.6 mm capillary spinneret with an L / D of 4 and a 325 mesh screen pack filter were used.

  The result is that unstretched, unannealed, low shrinkage PEI fibers exhibited by the fibers produced according to various embodiments of the present invention when PEI fibers are produced under high shear conditions (eg, conditions where the pressure is 1400 psi or greater). Indicates that it cannot be manufactured. More specifically, in this example, a fiber with a dpf of 2.2 and a shrinkage of 4% was produced. Furthermore, in order to obtain 2 dpf fibers using the α spin pack, the fibers had to be drawn and then annealed. Subsequent shrinkage rates in this process were higher than processes according to various embodiments of the present invention. Also, the pack pressure in this example was 1500 psi or higher, which was higher than the pressure (400-600 psi) in most of the previous examples.

A summary of the results obtained in Examples 1-9 is shown in Table 2.

  Although the present invention has been described in considerable detail with reference to preferred embodiments, other variations are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.

  The contents of all the articles and documents submitted simultaneously with this specification and made public are incorporated herein by reference.

  Unless otherwise stated, all features disclosed in this specification (including the appended claims, abstract and drawings) may be replaced by alternative features serving the same, equivalent or similar purpose. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.

Claims (11)

Extruding a melt comprising an amorphous polymer composition through a spinneret under a pressure of 400-1500 psi to produce a spun fiber;
Collecting the spun fiber on a supply roll without drawing, and producing a solidified fiber having a dpf of more than 0 to 2.5 and a shrinkage of 2% or less from the spun fiber;
Winding the coagulated fiber on a spool without subjecting it to a drawing step.   The method according to claim 1, wherein the melt flow rate of the amorphous polymer composition is 4 to 18 g / 10 min.   3. The method of claim 1, further comprising collecting the fibers on the spool without being subjected to an annealing step, without being subjected to a forced air cooling step, or without being subjected to an annealing step and a forced air cooling step. the method of.   4. A method according to any preceding claim, wherein the process further comprises heating the spun fiber after exiting the spinneret.   The method according to any one of claims 1 to 4, wherein the melt contains one or more crystalline materials.   The method according to claim 1, wherein the amorphous polymer composition comprises a polyetherimide.   Unstretched amorphous polymer fiber having a denier of less than 2.5 and a shrinkage ratio of more than 0 to 2%.   The unstretched amorphous material according to claim 7, wherein the polymer fiber is a polyetherimide fiber having a polydispersity (Mw / Mn) of 2.5 or more and a strength of at least 2.6 cN / dtex. Quality polymer fiber. A spinning pack for producing amorphous unstretched polyetherimide fibers having a dpf of at most 2.5 from a composition comprising amorphous polyetherimide,
Without a distribution plate,
A spin pack comprising a die having a plurality of circular melt channels, each having a length and a diameter, the ratio of the length to the diameter being 2: 1 to 6: 1. The spin pack, the spin pack of claim 9, further comprising at least one screen pack filter to distribute the composition into the die is connected to the die. The spinning pack according to claim 10, wherein the screen pack filter has a mesh size of 200 to 400 US mesh size.

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