JPS6142004B2 - - Google Patents
Info
- Publication number
- JPS6142004B2 JPS6142004B2 JP22420484A JP22420484A JPS6142004B2 JP S6142004 B2 JPS6142004 B2 JP S6142004B2 JP 22420484 A JP22420484 A JP 22420484A JP 22420484 A JP22420484 A JP 22420484A JP S6142004 B2 JPS6142004 B2 JP S6142004B2
- Authority
- JP
- Japan
- Prior art keywords
- solution
- composition
- orientation
- force
- aromatic polyamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000002245 particle Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 239000004760 aramid Substances 0.000 claims description 11
- 229920003235 aromatic polyamide Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 9
- 238000011033 desalting Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 description 10
- 239000000835 fiber Substances 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 6
- 239000002783 friction material Substances 0.000 description 5
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 4
- 230000015271 coagulation Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- 206010061592 cardiac fibrillation Diseases 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004807 desolvation Methods 0.000 description 3
- 230000002600 fibrillogenic effect Effects 0.000 description 3
- QZUPTXGVPYNUIT-UHFFFAOYSA-N isophthalamide Chemical compound NC(=O)C1=CC=CC(C(N)=O)=C1 QZUPTXGVPYNUIT-UHFFFAOYSA-N 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 polyparaphenylene terephthalamide Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000000710 polymer precipitation Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Paper (AREA)
- Artificial Filaments (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐熱性、機械的性質等の優れたパル
プ粒子を製造する方法に関する。さらに詳しく
は、合成紙原料、樹脂補強材、摩擦材等の用途に
好適な、フイブリル化したパルプ粒子を工業的に
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing pulp particles having excellent heat resistance, mechanical properties, etc. More specifically, the present invention relates to a method for industrially producing fibrillated pulp particles suitable for use as synthetic paper raw materials, resin reinforcing materials, friction materials, and the like.
従来、全芳香族ポリアミド、例えばポリ（パラ
フエニレンテレフタルアミド）、ポリ（メタフエ
ニレンイソフタルアミド）は耐熱性、機械的特
性、電気的特性等の優れたパルプ粒子（フイブリ
ツド）、繊維、フイルム、シート状物、樹脂、積
層材の原料として有用であることが知られてい
る。
Conventionally, fully aromatic polyamides, such as poly(paraphenylene terephthalamide) and poly(metaphenylene isophthalamide), have been used to make pulp particles (fibrids), fibers, films, and other materials with excellent heat resistance, mechanical properties, and electrical properties. It is known to be useful as a raw material for sheet materials, resins, and laminates.
例えば、特公昭47−2489号公報にはポリ（パラ
フエニレンテレフタルアミド）又はそのコポリマ
ーから得られる高強度、高モジユラス繊維につい
て記載されており、また、特開昭47−23602号公
報には、ポリ（メタフエニレンイソフタルアミ
ド）等の非融解性全芳香族ポリアミドのフイブリ
ツドを用いた合成紙が記載されている。 For example, Japanese Patent Publication No. 47-2489 describes high strength and high modulus fibers obtained from poly(paraphenylene terephthalamide) or its copolymer, and Japanese Patent Publication No. 47-23602 describes Synthetic papers using fibrils of non-fusible wholly aromatic polyamides such as poly(metaphenylene isophthalamide) have been described.
しかしながら、前述の高強度、高モジユラス繊
維は、短繊維に切断するのに特別の工夫・装置を
要し、またそのままでは合成紙原料、摩擦材等の
パルプ粒子の用途分野には使用し難い。一方、ポ
リ（メタフエニレンイソフタルアミド）のフイブ
リツドは、耐熱性合成紙の原料として適当なもの
とされているが、実質的に分子配向していないた
め強度に劣るという問題があり、また、樹脂補強
材、摩擦材等の分野には不適当であるという問題
がある。 However, the aforementioned high-strength, high-modulus fibers require special measures and equipment to be cut into short fibers, and are difficult to use as they are in pulp particle applications such as synthetic paper raw materials and friction materials. On the other hand, poly(metaphenylene isophthalamide) fibrils are considered to be suitable as raw materials for heat-resistant synthetic paper, but there is a problem that they are inferior in strength because they are not substantially oriented, and resin There is a problem in that it is unsuitable for fields such as reinforcing materials and friction materials.
本発明の主たる目的は、光学的異方性を有する
溶液に分子配向性を与え、しかる後に機械的剪断
力を加えながら脱溶媒（脱塩）を行つてパルプ粒
子を製造するという、従来の全芳香族ポリアミド
繊維やフイブリツドの製法とは異なつた方法でパ
ルプ粒子を製造する方法を提供するにある。
The main purpose of the present invention is to provide a solution with optical anisotropy with molecular orientation, and then remove the solvent (desalt) while applying mechanical shearing force to produce pulp particles. It is an object of the present invention to provide a method for producing pulp particles by a method different from that for producing aromatic polyamide fibers and fibrids.
本発明の他の目的は、合成紙原料、樹脂強化
材、摩擦材等として好適な剛直な全芳香族ポリア
ミドからなるフイブリル化したパルプ粒子を安価
に製造する方法を提供することにある。 Another object of the present invention is to provide a method for inexpensively producing fibrillated pulp particles made of a rigid wholly aromatic polyamide suitable as a synthetic paper raw material, a resin reinforcement material, a friction material, etc.
本発明は、主として下記反復単位〔〕で構成
される剛直な全芳香族ポリアミドの光学的異方性
溶液からパルプ粒子を製造するにおいて、光学的
異方性溶液に分子配向させるに足る力を与え、配
向緩和し難い高次構造をもつ分子配向性を有する
組成物となし、次いで、この分子配向性を有する
未凝固の組成物に機械的剪断力を与えると同時に
脱溶媒・脱塩することにより、該組成物をフイブ
リル化したパルプ状粒子とすることを特徴とする
パルプ粒子の製造法である。
The present invention applies sufficient force to orient molecules to the optically anisotropic solution in producing pulp particles from an optically anisotropic solution of a rigid wholly aromatic polyamide mainly composed of the following repeating units [ ]. , by forming a composition with molecular orientation that has a higher-order structure that is difficult to relax the orientation, and then applying mechanical shearing force to the unsolidified composition having this molecular orientation, and simultaneously removing solvent and desalting. , a method for producing pulp particles characterized by forming the composition into fibrillated pulp particles.
〔但し式中Ar1及びAr2は、１・４−フエニレン基
をあらわす〕
本発明において用いる剛直な全芳香族ポリアミ
ドとしては、ポリパラフエニレンテレフタルアミ
ド）が好ましいが、繰返し単位の一部（例えば５
モル％以下）が他のポリアミド繰返し単位からな
るものでもよい。この全芳香族ポリアミドは、固
有粘度（ηinh）にして1.5以上の重合度を有する
必要がある。なお、ここで云う固有粘度は、ポリ
マー組成物から当該ポリマーを粉末として取りだ
し、濃硫酸中0.5ｇ／100mlの濃度で測定した値で
ある。 [However, Ar 1 and Ar 2 in the formula represent 1,4-phenylene groups] As the rigid wholly aromatic polyamide used in the present invention, polyparaphenylene terephthalamide) is preferable, but some of the repeating units ( For example 5
mol % or less) may consist of other polyamide repeating units. This wholly aromatic polyamide must have a degree of polymerization of 1.5 or more in terms of intrinsic viscosity (ηinh). The intrinsic viscosity referred to herein is a value obtained by taking out the polymer as a powder from the polymer composition and measuring it in concentrated sulfuric acid at a concentration of 0.5 g/100 ml.
本発明においては、前記の剛直な全芳香族ポリ
アミドとして、所望のポリマー組成に相当する混
合比のモノマー系から溶液重合法によつて調製せ
しめた重合進行系又は重合の終了した混合系をそ
のまま、あるいは副生するHClを中和した系を用
いる。 In the present invention, as the above-mentioned rigid wholly aromatic polyamide, a polymerized system prepared by a solution polymerization method from a monomer system with a mixing ratio corresponding to a desired polymer composition or a mixed system after polymerization is directly used. Alternatively, use a system in which by-produced HCl is neutralized.
かかる剛直なポリマーの一つの属性として、
特定の溶剤系中で、特定の濃度範囲、特定の温
度範囲では光学的異方性の溶液を与えることが知
られている（特公昭47−2489号公報、米国特許第
3671542号明細書参照）。 One attribute of such rigid polymers is that they provide optically anisotropic solutions in specific solvent systems, specific concentration ranges, and specific temperature ranges (Japanese Patent Publication No. 47-2489). , U.S. Patent No.
3671542).
ここで云う光学的異方性溶液は、例えば特開昭
47−39458号にも述べられているが、簡便な判定
法の一つは溶液が肉眼では乳濁状にみえ、かつ偏
光顕微鏡で偏光子を回転させて観察した場合、完
全に視野が暗くなる角度の無いものである。上述
の光学的異方性はポリ（パラフエニレンテレフタ
ルアミド）の溶液重合系でも出現することは、特
公昭47−2489号公報及び／米国特許第3673143号
明細書にも報告されている通りである。 The optically anisotropic solution referred to here is, for example,
As stated in No. 47-39458, one simple method for determining this is that the solution appears milky to the naked eye, and when observed with a polarizing microscope by rotating the polarizer, the field of view becomes completely dark. It has no angle. The above-mentioned optical anisotropy also appears in solution polymerization systems of poly(paraphenylene terephthalamide), as reported in Japanese Patent Publication No. 47-2489 and US Pat. No. 3,673,143. be.
例えば、パラフエニレンジアミン等のジアミン
をヘキサメチルホスホルアミド（又はこれとＮ−
メチルピロリドン、Ｎ・Ｎ−ジメチルアセトアミ
ドとの混合系）等の極性溶媒に溶解させ、この溶
液に通常はテレフタル酸クロライド等のジ酸クロ
ライドを撹拌し且つ冷却しながら加えることによ
つて重合反応が開始する。仕込みポリマー濃度、
溶媒の組成（混合比、LiCl・CaCl2等の添加無機
塩の存在）等の重合条件の差異によつて、重合系
は２、３分以内にポリマーの沈澱が生じたり、反
応混合物がカンテン状等にゲル化する。重合反応
が未だ完了していない重合反応進行中の系がすで
に光学的異方性を呈することも上記特許等によつ
て明らかにされている。 For example, diamine such as paraphenylene diamine is mixed with hexamethylphosphoramide (or with N-
The polymerization reaction is usually carried out by dissolving diacid chloride such as terephthalic acid chloride into this solution with stirring and cooling. Start. Charged polymer concentration,
Due to differences in polymerization conditions such as solvent composition (mixing ratio, presence of added inorganic salts such as LiCl/ CaCl2 ), polymer precipitation may occur within a few minutes in the polymerization system, or the reaction mixture may become agar-like. etc. to gel. It has also been clarified by the above-mentioned patents and the like that a system in which the polymerization reaction is not yet completed but is in progress already exhibits optical anisotropy.
本発明はポリ（パラフエニレンテレフタルアミ
ド）の溶液重合進行系又は重合の終了した混合系
あるいは重合反応によつて副生した塩化水素の一
部あるいは全部を中和した混合系からなる上述の
ような光学的異方性溶液に分子配向性せしめるに
足る力を与え、配向緩和しにくい高次組織をもつ
分子配向性を有する組成物とすることが必要であ
る。 The present invention comprises a solution polymerization system of poly(paraphenylene terephthalamide), a mixed system after polymerization, or a mixed system in which part or all of the hydrogen chloride by-produced by the polymerization reaction is neutralized. It is necessary to apply sufficient force to the optically anisotropic solution to cause the molecules to become oriented, thereby creating a composition that has molecular orientation and has a higher-order structure that is difficult to relax.
光学的異方性溶液は、すでにその溶液構造から
して、分子配向の状態又はより分子配向をし易い
状態にある。本発明者等の研究によれば、前述の
ごときポリ（パラフエニレンテレフタルアミド）
からなる系では、一旦、分子配向した後は極めて
配向緩和しにくい高次組織をつくり易いので、配
向方向に沿つて分子鎖密度の低い横方向結合力の
弱い部分を生じるため、これに脱溶媒・脱塩（成
形）と同時に適度の機械的剪断力を加えると極め
て容易にフイブリル化することができ、目的とす
るパルプ粒子を形成することが判つた。 The optically anisotropic solution is already in a state of molecular orientation or a state where molecular orientation is more likely to occur due to its solution structure. According to the research of the present inventors, the above-mentioned poly(paraphenylene terephthalamide)
In systems consisting of, once the molecules are oriented, it is easy to form a higher-order structure that is extremely difficult to relax, and this creates areas along the orientation direction where the molecular chain density is low and the lateral bonding force is weak. - It was found that by applying appropriate mechanical shearing force at the same time as desalting (molding), fibrillation can be made extremely easily and the desired pulp particles can be formed.
本発明において、上記光学的異方性溶液のゲル
化過程に置いて、分子配向し得るに足る力を前記
の光学的異方性溶液に与え、配向緩和しにくい高
次組織をもつ分子配向性を有する組成物とする
が、その方法としては、下記の方法がある：
(i) 口金ノズル、スリツト等を通して塊状、粒
状、粉末状、フイラメント状、ヒモ状、膜状、
シート状、スプレー状に押し出す。 In the present invention, during the gelation process of the optically anisotropic solution, a force sufficient to orient the molecules is applied to the optically anisotropic solution, so that the molecular orientation having a higher-order structure that is difficult to relax the orientation is achieved. The method is as follows: (i) Through a nozzle, slit, etc., the composition is formed into a lump, granule, powder, filament, string, film, etc.
Extrude into sheet or spray form.
(ii) 撹拌等の遠心力を利用して重合溶器の壁面に
衝突させる等、機械的な力を作用させる。(ii) Applying mechanical force, such as colliding with the wall of the polymerization vessel using centrifugal force such as stirring.
本発明では、上記溶液を凝固浴中に導入し、溶
液中の溶媒・塩を除去して重合体として凝固させ
ることにより成形が行われる。 In the present invention, molding is performed by introducing the solution into a coagulation bath, removing the solvent and salt in the solution, and coagulating it as a polymer.
脱溶媒・脱塩（成形）は公知の方法により行う
ことができる。一般には、水、塩化カルシウム水
溶液又は有機溶剤を含む水性凝固浴中において、
凝固、脱塩、脱溶媒が行われる。 Solvent removal and desalting (molding) can be performed by known methods. Generally, in an aqueous coagulation bath containing water, an aqueous calcium chloride solution, or an organic solvent,
Coagulation, desalting, and desolvation are performed.
本発明の方法では、成形時のノズル径、スリツ
ト幅、押し出し速度、凝固系の種類及び温度、脱
溶媒、脱塩速度とタイミング等の成形条件を適当
に組み合せることにより、後で該組成物を糸状に
砕いて得られるパルプ粒子の諸特性、とくにその
形状と機械的性質をコントロール出来、さらに適
当な条件ではパルプ粒子の長さ及びその分布につ
いても、ある程度のコントロールが出来る。 In the method of the present invention, by appropriately combining molding conditions such as nozzle diameter, slit width, extrusion speed, type and temperature of coagulation system, desolvation, and desalination speed and timing during molding, the composition is It is possible to control the various properties of the pulp particles obtained by crushing them into threads, especially their shape and mechanical properties, and furthermore, under appropriate conditions, the length of the pulp particles and their distribution can also be controlled to a certain extent.
本発明では上記(i)(ii)のごとき各種方法によつて
得られた分子配向性を有する未凝固の溶液組成物
を成形と同時に、即ち脱溶媒・脱塩と同時に、機
械的剪断力を加えて糸状に砕いてフイブリル化さ
せる。 In the present invention, a mechanical shearing force is applied to an unsolidified solution composition having molecular orientation obtained by various methods (i) and (ii) above at the same time as molding, that is, at the same time as desolvation and desalting. In addition, it is crushed into threads and fibrillated.
本発明において前記組成物を糸状に砕いてフイ
ブリル化させるには、例えば粉砕、すりつぶし、
衝撃、叩解のような機械的剪断力を加えることが
必要である。剪断力を与える手段としては、各種
グラインダー、ミル、粉砕記機を用いることがで
きる。さらに本工程は紙製造における調整とかな
りの類似性を有するので各種のビーター、ジヨル
ダン、リフアイナー等も適用出来る。さらにパル
プ製造における砕木機グラインダーの一部も使用
出来る。 In the present invention, in order to crush the composition into fibrillation, for example, crushing, grinding,
It is necessary to apply mechanical shear forces such as impact and beating. As means for applying shearing force, various grinders, mills, and crushers can be used. Furthermore, since this process has considerable similarities with the adjustments in paper manufacturing, various beaters, dijordans, refiners, etc. can also be applied. Additionally, some of the wood chipping machine grinders in pulp production can also be used.
上述のごとき本発明の方法によればポリマーの
構造及び成形に供するポリマー溶液の組成を選択
することにより、有用なパルプ粒子を簡単な工程
で一挙に製造することが出来る。
According to the method of the present invention as described above, by selecting the structure of the polymer and the composition of the polymer solution used for molding, useful pulp particles can be produced all at once in a simple process.
しかも、光学的異方性溶液を用いるので、光学
的等方性溶液を用いる場合に比して高いポリマー
濃度で成形することが出来、しかも配向し易い傾
向にあるので、これから得られた組成物は極めて
フイブリル化し易く糸状に砕き易い。さらに大き
な利点は、本発明で特定した剛直な全芳香族ポリ
アミドからなるパルプ粒子は高い剛性を有するも
のが多いので紡糸して得た糸を短く切つて短繊維
を得ることは困難が伴うか、切断機に特殊な工
夫・装置が必要であるのに比し、本発明の方法で
は極めて容易にパルプ粒子を得ることが出来る。 Moreover, since an optically anisotropic solution is used, it is possible to mold the polymer at a higher concentration than when an optically isotropic solution is used, and since it tends to be easily oriented, the composition obtained from this It is extremely easy to fibrillate and break into threads. An even greater advantage is that many of the pulp particles made of the rigid wholly aromatic polyamide specified in the present invention have high rigidity, so it is difficult to obtain short fibers by cutting the spun yarn into short lengths. Unlike cutting machines that require special measures and equipment, the method of the present invention allows pulp particles to be obtained extremely easily.
本発明で得られたパルプ粒子は、そのフイブリ
ル性及び優れた耐熱性、機械的特性を活かして耐
熱性の絶縁紙などの強靭なシート状物に成形する
ことが出来る。また、フイブリル化による大きい
表面積に加えて、高い機械的特性とくに高いモジ
ユラスと強度を有し、さらにガラス繊維、炭素繊
維、金属繊維等に比べて低比重であるので、樹脂
強化用としても有用である。 The pulp particles obtained in the present invention can be formed into a strong sheet-like material such as heat-resistant insulating paper by taking advantage of its fibrillarity, excellent heat resistance, and mechanical properties. In addition to a large surface area due to fibrillation, it has high mechanical properties, especially high modulus and strength, and has a lower specific gravity than glass fiber, carbon fiber, metal fiber, etc., so it is useful for reinforcing resins. be.
また、上述の特性を利用して摩擦材に使用する
ことも出来る。 Moreover, it can also be used as a friction material by utilizing the above-mentioned characteristics.
以下に実施例をもつて本発明を説明する。な
お、実施例中有機極性溶媒はそれぞれヘキサメチ
ルホスホルアミドはHMPA、Ｎ−メチルピロリ
ドンはNMPと略称する。
The present invention will be explained below with reference to Examples. In the Examples, the organic polar solvents are abbreviated as HMPA for hexamethylphosphoramide and NMP for N-methylpyrrolidone.
実施例 １
HMPA50mlとNMP100mlとからなる混合溶媒
に、パラフエニレンジアミン5.661ｇを溶解させ
炭酸リチウム3.868ｇを加えて氷浴で冷却後、テ
レフタル酸クロライドの粉末10.629ｇを添加して
重合反応を行つた。約30分後に光学的異方性溶液
が得られた。このようにして得られたポリ（パラ
フエニレンテレフタルアミド）の固有粘度は2.75
であつた。この溶液は約7.5重量％のポリマーを
含んでおり、重合反応直後からゲル化する性質を
有するものであつた。Example 1 5.661 g of paraphenylenediamine was dissolved in a mixed solvent consisting of 50 ml of HMPA and 100 ml of NMP, 3.868 g of lithium carbonate was added thereto, and after cooling in an ice bath, 10.629 g of terephthalyl chloride powder was added to perform a polymerization reaction. Ivy. An optically anisotropic solution was obtained after about 30 minutes. The intrinsic viscosity of the poly(paraphenylene terephthalamide) thus obtained is 2.75.
It was hot. This solution contained about 7.5% by weight of polymer and had the property of gelling immediately after the polymerization reaction.
このようにして調製した光学的異方性溶液を直
径0.5mmの口金を通して糸状に押出すことにより
分子配向性を与えたのち、未凝固の糸状の溶液組
成物をホモミキサー中に誘導し、水中で脱溶媒・
脱塩すると同時に撹拌粉砕することにより短繊維
状のパルプ粒子を調製した。 The optically anisotropic solution thus prepared was extruded in the form of a thread through a nozzle with a diameter of 0.5 mm to impart molecular orientation, and then the unsolidified thread-like solution composition was introduced into a homomixer and submerged in water. Remove solvent with
Short fibrous pulp particles were prepared by desalting and simultaneously stirring and crushing.
実施例 ２
HMPA50mlとNMP100mlとからなる混合溶媒に
パラフエニレンジアミン5.660ｇを溶解させ氷冷
後、テレフタル酸クロライド10.678ｇを添加して
重合反応を開始し、この重合反応が未だ完了して
いない光学的異方性溶液を遠心力で窒素気流下の
壁面に衝突させて分子配向性を与えた未凝固の膜
状と塊状を呈する溶液組成物を、ホモミキサー中
で水と撹拌して成形（脱溶媒・脱塩）と同時に剪
断力を与えた後、Na2CO3水溶液で洗浄し、水
洗、脱水乾燥して短繊維状のパルプ粒子を得た。Example 2 5.660 g of paraphenylene diamine was dissolved in a mixed solvent consisting of 50 ml of HMPA and 100 ml of NMP, and after cooling on ice, 10.678 g of terephthalic acid chloride was added to start a polymerization reaction. The anisotropic solution is collided with a wall under a nitrogen stream using centrifugal force to impart molecular orientation, and the solution composition, which exhibits an unsolidified film and a lump, is stirred with water in a homomixer and molded (de-molded). After applying shearing force at the same time as (solvent/desalting), the particles were washed with an aqueous Na 2 CO 3 solution, washed with water, and dehydrated and dried to obtain short fibrous pulp particles.
Claims (1)
リアミドの重合進行系又は重合の終了した混合系
あるいは副生する塩化水素の一部又は全部を中和
した混合系からなる、主として下記反復単位
「」で構成される剛直な全芳香族ポリアミドの
光学異方性を有する溶液に、(イ)分子配向せしむる
に足る力を与え、配向緩和しにくい高次組織をも
つ分子配向性を有する組成物となし、次いで、(ロ)
この分子配向性を有する未凝固の組成物に機械的
剪断力を与えると同時に脱溶媒、脱塩することに
より、該組成物をフイブリル化したパルプ状粒子
とすることを特徴とするパルプ粒子の製造法。 （但し式中Ar1及びAr2は、１・４−フエニレン基
を表わす）[Scope of Claims] 1 Consists of a polymerized system of a fully aromatic polyamide prepared by a solution polymerization method, a mixed system after polymerization, or a mixed system in which part or all of by-produced hydrogen chloride is neutralized. (a) Applying sufficient force to force molecular orientation to an optically anisotropic solution of a rigid wholly aromatic polyamide mainly composed of the following repeating units ``'', and molecules having a higher-order structure that is difficult to relax the orientation. A composition having orientation properties, then (b)
Production of pulp particles characterized by applying mechanical shearing force to the unsolidified composition having molecular orientation and simultaneously removing solvent and desalting to form fibrillated pulp-like particles. Law. (However, Ar 1 and Ar 2 in the formula represent a 1,4-phenylene group)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22420484A JPS60126314A (en) | 1984-10-26 | 1984-10-26 | Production of pulp particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22420484A JPS60126314A (en) | 1984-10-26 | 1984-10-26 | Production of pulp particle |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP50005980A Division JPS59603B2 (en) | 1975-01-14 | 1975-01-14 | Method for producing short fibers and/or pulp particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60126314A JPS60126314A (en) | 1985-07-05 |
| JPS6142004B2 true JPS6142004B2 (en) | 1986-09-18 |
Family
ID=16810153
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22420484A Granted JPS60126314A (en) | 1984-10-26 | 1984-10-26 | Production of pulp particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60126314A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62177210A (en) * | 1986-01-30 | 1987-08-04 | Teijin Ltd | Pulp particle made of synthetic polymer |
| US5028372A (en) * | 1988-06-30 | 1991-07-02 | E. I. Du Pont De Nemours And Company | Method for producing para-aramid pulp |
-
1984
- 1984-10-26 JP JP22420484A patent/JPS60126314A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60126314A (en) | 1985-07-05 |
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