JP5779538B2 - Method for producing thermotropic liquid crystal polyester - Google Patents
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- JP5779538B2 JP5779538B2 JP2012099978A JP2012099978A JP5779538B2 JP 5779538 B2 JP5779538 B2 JP 5779538B2 JP 2012099978 A JP2012099978 A JP 2012099978A JP 2012099978 A JP2012099978 A JP 2012099978A JP 5779538 B2 JP5779538 B2 JP 5779538B2
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- 229920000728 polyester Polymers 0.000 title claims description 57
- 239000004974 Thermotropic liquid crystal Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 76
- 239000007790 solid phase Substances 0.000 claims description 21
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000470 constituent Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 23
- 239000002245 particle Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 15
- -1 dicarboxylic acid compound Chemical class 0.000 description 14
- 238000011049 filling Methods 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000012643 polycondensation polymerization Methods 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000006640 acetylation reaction Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 125000003923 ethanoic acid ester group Chemical group 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- MNZMMCVIXORAQL-UHFFFAOYSA-N naphthalene-2,6-diol Chemical compound C1=C(O)C=CC2=CC(O)=CC=C21 MNZMMCVIXORAQL-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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Description
本発明は、サーモトロピック液晶ポリエステルの製造方法に関するものである。 The present invention relates to a method for producing a thermotropic liquid crystal polyester.
近年、繊維、フィルムもしくは成形品用等において、耐熱性、機械的特性、耐薬品性等に優れた材料が求められている。これらに対応する材料として液晶性ポリマーが注目されている。その一種として、芳香族ジカルボン酸を含むジカルボン酸化合物と、芳香族ジオールを含むジヒドロキシ化合物とを縮重合して製造されるサーモトロピック液晶ポリエステルがある。 In recent years, materials excellent in heat resistance, mechanical properties, chemical resistance, and the like have been demanded for fibers, films or molded articles. As a material corresponding to these, liquid crystalline polymers have attracted attention. As one type, there is a thermotropic liquid crystal polyester produced by condensation polymerization of a dicarboxylic acid compound containing an aromatic dicarboxylic acid and a dihydroxy compound containing an aromatic diol.
サーモトロピック液晶ポリエステルの組成については、ポリマー特性の向上を目的とした検討がこれまでにもなされている。例えば、液晶ポリエステルの機械的特性を向上させる目的で、ｐ−ヒドロキシ安息香酸などのヒドロキシカルボン酸化合物や、シクロヘキサンジカルボン酸成分を含有するサーモトロピック液晶ポリエステルが提案されている（例えば、下記特許文献１を参照）。 As for the composition of the thermotropic liquid crystal polyester, studies have been made for the purpose of improving the polymer characteristics. For example, for the purpose of improving the mechanical properties of liquid crystal polyester, a thermotropic liquid crystal polyester containing a hydroxycarboxylic acid compound such as p-hydroxybenzoic acid or a cyclohexanedicarboxylic acid component has been proposed (for example, Patent Document 1 below). See).
ところで、上記のようなサーモトロピック液晶ポリエステルは、通常、原料モノマーを反応容器に仕込んで加熱溶融して攪拌混合しながら縮重合反応を進める溶融縮重合によって製造される。このとき、液晶ポリエステルの重合度が上がるにしたがって溶融温度が上昇するため、低重合度の液晶ポリエステルが得られたところで反応を固相縮重合に変更し、ポリマーの重合度を高めることが行われている。具体的には、溶融縮重合において、その反応槽中の溶融重合体の温度が所定の温度に達したところで、低重合度の液晶ポリエステルを溶融状態のまま重合槽から抜き出し、スチールベルトやドラムクーラー等の冷却機へ供給し、冷却して固化させる。ついで、固化した低重合度の液晶ポリエステルを、後続の固相縮重合反応に適した大きさに粉砕し、粉砕物（プレポリマー）を固相縮重合して目的の液晶ポリエステルを得る（例えば、下記特許文献２を参照）。 By the way, the thermotropic liquid crystal polyester as described above is usually produced by melt-condensation polymerization in which a raw material monomer is charged into a reaction vessel, heated and melted, and a condensation polymerization reaction proceeds while stirring and mixing. At this time, the melting temperature increases as the degree of polymerization of the liquid crystalline polyester increases, so when the liquid crystalline polyester having a low degree of polymerization is obtained, the reaction is changed to solid phase condensation polymerization to increase the degree of polymerization of the polymer. ing. Specifically, in the melt-condensation polymerization, when the temperature of the molten polymer in the reaction tank reaches a predetermined temperature, the liquid crystalline polyester having a low polymerization degree is withdrawn from the polymerization tank in a molten state, and a steel belt or a drum cooler. Etc., cool and solidify. Next, the solidified low polymerization degree liquid crystal polyester is pulverized to a size suitable for the subsequent solid phase condensation polymerization reaction, and the pulverized product (prepolymer) is subjected to solid phase condensation polymerization to obtain the desired liquid crystal polyester (for example, (See Patent Document 2 below).
しかしながら、液晶ポリエステルは熱伝導が悪いため、上記特許文献２のようにロータリーキルンを使用する固相重合では重合時間が長くかかるという問題がある。また、ロータリーキルンは装置の構造上窒素等不活性ガスを流通させる空間を有するために粉体の充填率が高々４０％程度であり、減圧下での運転も困難なため生産効率が低いという問題がある。 However, since liquid crystalline polyester has poor thermal conductivity, there is a problem that solid-state polymerization using a rotary kiln as described in Patent Document 2 takes a long polymerization time. In addition, the rotary kiln has a space through which an inert gas such as nitrogen is circulated due to the structure of the apparatus, so that the powder filling rate is about 40% at most, and the operation under reduced pressure is difficult, so the production efficiency is low. is there.
本発明は、サーモトロピック液晶ポリエステルの生産効率の向上を可能とするサーモトロピック液晶ポリエステルの製造方法を提供することを目的とする。 It is an object of the present invention to provide a method for producing a thermotropic liquid crystal polyester that can improve the production efficiency of the thermotropic liquid crystal polyester.
本発明のサーモトロピック液晶ポリエステルの製造方法は、反応槽から溶融状態で排出し、冷却固化し、粉砕して得られる融点が２４０〜３３０℃である低重合度サーモトロピック液晶ポリエステル粉砕物を、振動させた反応器内で少なくとも上下方向に流動させて固相重合することを特徴とする。 The production method of the thermotropic liquid crystal polyester of the present invention is to vibrate a low polymerization degree thermotropic liquid crystal polyester pulverized product having a melting point of 240 to 330 ° C. discharged from a reaction vessel in a molten state, cooled and solidified, and pulverized. It is characterized in that it is solid-phase polymerized by flowing at least in the vertical direction in the reactor.
本明細書において、重力の作用により粉砕物が流動する方向が上下方向の下方である。 In this specification, the direction in which the pulverized material flows due to the action of gravity is the downward direction in the vertical direction.
本発明のサーモトロピック液晶ポリエステルの製造方法によれば、低重合度サーモトロピック液晶ポリエステル粉砕物の重合時間の短縮を図ることができる。また、本発明の方法によれば、反応器に粉砕物を高充填した場合であっても重合を十分進行させることができる。 According to the method for producing the thermotropic liquid crystal polyester of the present invention, it is possible to shorten the polymerization time of the low polymerization degree thermotropic liquid crystal polyester. Moreover, according to the method of the present invention, the polymerization can be sufficiently advanced even when the reactor is highly filled with the pulverized product.
本発明の方法が上記の効果を奏する理由としては、上記特定の低重合度サーモトロピック液晶ポリエステル粉砕物と、振動させた反応器による上下方向の流動が含まれる流動パターンとの組合せにより、高充填時であっても十分な攪拌が可能となり、粉砕物への伝熱効率を向上させることができること、反応器内における重合温度のムラを抑制できること、並びに、融点が２４０〜３３０℃である低重合度サーモトロピック液晶ポリエステル粉砕物は結晶化によって適度に硬い表面を有しており、攪拌効率が非常に高い流動パターンの中にあっても、粉砕物同士が融着して重合が阻害されることを防止できること、などが考えられる。 The reason why the method of the present invention has the above-described effect is that the specific low polymerization degree thermotropic liquid crystal polyester pulverized product and the flow pattern including the vertical flow by the vibrated reactor are combined to provide a high packing. Even when it is possible, sufficient stirring is possible, heat transfer efficiency to the pulverized product can be improved, unevenness of polymerization temperature in the reactor can be suppressed, and a low polymerization degree having a melting point of 240 to 330 ° C. The thermotropic liquid crystal polyester pulverized product has a moderately hard surface by crystallization, and even in a flow pattern with a very high stirring efficiency, the pulverized product is fused with each other to inhibit polymerization. What can be prevented is considered.
本発明のサーモトロピック液晶ポリエステルの製造方法において、上記反応器は、円筒形状の内面を有し、円筒軸線が略水平となるように配されており、当該反応器に、円筒軸線回りの円振動又は楕円振動を付与することが好ましい。この場合、振動により、反応器の円周方向に粉砕物が下方から上方へせり上がる流動を発生させることができ、上下方向の流動による粉砕物の攪拌効率を更に向上させることができる。また、粉砕物と反応器内部壁面との接触頻度が多くなるため、粉砕物への伝熱効率を更に向上させることができる。 In the method for producing the thermotropic liquid crystal polyester of the present invention, the reactor has a cylindrical inner surface and is arranged so that the cylinder axis is substantially horizontal, and the reactor is subjected to circular vibration around the cylinder axis. Or it is preferable to provide elliptical vibration. In this case, the vibration can generate a flow in which the pulverized product rises from the lower side to the upper side in the circumferential direction of the reactor, and the stirring efficiency of the pulverized product by the vertical flow can be further improved. Further, since the contact frequency between the pulverized product and the inner wall surface of the reactor increases, the heat transfer efficiency to the pulverized product can be further improved.
また、耐熱性、成形加工性の観点から、上記低重合度サーモトロピック液晶ポリエステル粉砕物が、ポリエステルの構成成分としてｐ−ヒドロキシ安息香酸を４０〜７５モル％含有するものであることが好ましい。 Moreover, it is preferable that the said low polymerization degree thermotropic liquid crystal polyester ground material contains 40-75 mol% of p-hydroxybenzoic acid as a structural component of polyester from a viewpoint of heat resistance and moldability.
本発明によれば、サーモトロピック液晶ポリエステルの生産効率の向上を可能とするサーモトロピック液晶ポリエステルの製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the thermotropic liquid crystal polyester which can improve the production efficiency of the thermotropic liquid crystal polyester can be provided.
本実施形態のサーモトロピック液晶ポリエステルの製造方法は、反応槽から溶融状態で排出し、冷却固化し、粉砕して得られる融点が２４０〜３３０℃である低重合度サーモトロピック液晶ポリエステル粉砕物を、振動させた反応器内で少なくとも上下方向に流動させて固相重合する。 The production method of the thermotropic liquid crystal polyester of the present embodiment is a low polymerization degree thermotropic liquid crystal polyester pulverized product having a melting point of 240 to 330 ° C., which is discharged in a molten state from a reaction vessel, cooled and solidified, and pulverized. In the vibrated reactor, it is allowed to flow at least in the vertical direction and undergo solid phase polymerization.
本実施形態の方法で製造されるサーモトロピック液晶ポリエステルとしては、例えば、芳香族ジカルボン酸と芳香族ジオールと芳香族ヒドロキシカルボン酸との組み合わせからなるもの、異種の芳香族ヒドロキシカルボン酸からなるもの、芳香族ジカルボン酸と芳香族ジオールとの組み合わせからなるもの、脂環式ジカルボン酸と芳香族ジカルボン酸と芳香族ジオールと芳香族ヒドロキシカルボン酸との組み合わせからなるもの、ポリエチレンテレフタレートなどのポリエステルに芳香族ヒドロキシカルボン酸を反応させたもの、等が挙げられる。 As the thermotropic liquid crystal polyester produced by the method of the present embodiment, for example, those composed of a combination of aromatic dicarboxylic acid, aromatic diol and aromatic hydroxycarboxylic acid, those composed of different aromatic hydroxycarboxylic acids, A combination of an aromatic dicarboxylic acid and an aromatic diol, a combination of an alicyclic dicarboxylic acid, an aromatic dicarboxylic acid, an aromatic diol and an aromatic hydroxycarboxylic acid, or an aromatic polyester such as polyethylene terephthalate What reacted with hydroxycarboxylic acid etc. are mentioned.
サーモトロピック液晶ポリエステルの具体的な構造単位としては、例えば下記のものが挙げられる。 Specific examples of the structural unit of the thermotropic liquid crystal polyester include the following.
芳香族ヒドロキシカルボン酸に由来する構造単位としては、下記式（Ａ−１）〜（Ａ−５）で示される構造単位が挙げられる。 Examples of the structural unit derived from the aromatic hydroxycarboxylic acid include structural units represented by the following formulas (A-1) to (A-5).
式（Ａ−１）及び（Ａ−２）中、Ｘ１及びＸ２はハロゲン原子又はアルキル基を示し、ｎ及びｍは０〜４の整数を示す。 In formulas (A-1) and (A-2), X 1 and X 2 represent a halogen atom or an alkyl group, and n and m represent an integer of 0 to 4.
芳香族ジカルボン酸に由来する構造単位としては、下記式（Ｂ−１）〜（Ｂ−６）で示される構造単位が挙げられる。 Examples of the structural unit derived from the aromatic dicarboxylic acid include structural units represented by the following formulas (B-1) to (B-6).
式（Ｂ−１）及び（Ｂ−２）中、Ｘ３及びＸ４はそれぞれ、ハロゲン原子、アルキル基又はアリール基を示し、ｓ及びｔはそれぞれ、０〜４の整数を示す。式（Ｂ−６）中、Ｌ１は、２価の炭化水素基、−Ｏ−、−Ｏ−ＣＨ２ＣＨ２−Ｏ−、−ＳＯ−、−ＳＯ２−、−ＣＯ−、又は−Ｓ−を示す。 In formulas (B-1) and (B-2), X 3 and X 4 each represent a halogen atom, an alkyl group or an aryl group, and s and t each represent an integer of 0 to 4. In formula (B-6), L 1 represents a divalent hydrocarbon group, —O—, —O—CH 2 CH 2 —O—, —SO—, —SO 2 —, —CO—, or —S. -Is shown.
脂環式ジカルボン酸に由来する構造単位としては、下記式（Ｂ−７）で示される構造単位が挙げられる。
式（Ｂ−７）で表されるシクロヘキシル基の２つの結合手はメタ位またはパラ位である。
Examples of the structural unit derived from the alicyclic dicarboxylic acid include a structural unit represented by the following formula (B-7).
Two bonds of the cyclohexyl group represented by the formula (B-7) are in the meta position or the para position.
芳香族ジオールに由来する構造単位としては、下記式（Ｃ−１）〜（Ｃ−６）で示される構造単位が挙げられる。 Examples of the structural unit derived from the aromatic diol include structural units represented by the following formulas (C-1) to (C-6).
式（Ｃ−１）及び（Ｃ−２）中、Ｘ５及びＸ６はそれぞれ、ハロゲン原子、アルキル基又は無置換若しくは置換基を有するアリール基を示し、ｕ及びｖはそれぞれ、０〜４の整数を示す。置換基を有するアリール基の置換基としては、ハロゲン原子又はアルキル基が挙げられる。式（Ｃ−６）中、Ｌ２は、２価の炭化水素基、−Ｏ−、−Ｓ−、−ＳＯ−、−ＣＯ−、又は−ＳＯ２−を示す。 In formulas (C-1) and (C-2), X 5 and X 6 each represent a halogen atom, an alkyl group, or an aryl group having an unsubstituted or substituted group, and u and v are each 0-4. Indicates an integer. Examples of the substituent of the aryl group having a substituent include a halogen atom or an alkyl group. In formula (C-6), L 2 represents a divalent hydrocarbon group, —O—, —S—, —SO—, —CO—, or —SO 2 —.
本実施形態において、好ましいサーモトロピック液晶ポリエステルは、融点が２８０℃以上のものであり、特に、ｐ−ヒドロキシ安息香酸（Ｉ）、テレフタル酸及び／又はイソフタル酸（ＩＩ）、４，４’−ジヒドロキシビフェニル（ＩＩＩ）（これらの誘導体を含む。）を８０〜１００モル％（但し、（Ｉ）と（ＩＩ）の合計を６０モル％以上とする。）、および、（Ｉ）、（ＩＩ）、（ＩＩＩ）のいずれかと縮合反応可能な他の芳香族化合物０〜２０モル％を重縮合してなる融点２８０℃以上の液晶ポリエステルである。 In the present embodiment, a preferred thermotropic liquid crystal polyester has a melting point of 280 ° C. or more, and in particular, p-hydroxybenzoic acid (I), terephthalic acid and / or isophthalic acid (II), 4,4′-dihydroxy Biphenyl (III) (including these derivatives) in an amount of 80 to 100 mol% (provided that the total of (I) and (II) is 60 mol% or more), and (I), (II), A liquid crystal polyester having a melting point of 280 ° C. or higher obtained by polycondensation of 0 to 20 mol% of another aromatic compound capable of undergoing a condensation reaction with any of (III).
さらに好ましくは、ｐ−ヒドロキシ安息香酸や２−ヒドロキシ−６−ナフトエ酸などの芳香族ヒドロキシカルボン酸から得られるポリエステル、さらにこれらとテレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸などの芳香族ジカルボン酸とハイドロキノン、レゾルシン、４，４’−ジヒドロキシジフェニル、２，６−ジヒドロキシナフタレンなどの芳香族ジヒドロキシ化合物とから得られる液晶性ポリエステルなどが挙げられる。 More preferably, polyesters obtained from aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid, and aromatics such as terephthalic acid, isophthalic acid and 2,6-naphthalenedicarboxylic acid. Examples thereof include liquid crystalline polyesters obtained from dicarboxylic acids and aromatic dihydroxy compounds such as hydroquinone, resorcin, 4,4′-dihydroxydiphenyl, and 2,6-dihydroxynaphthalene.
また、サーモトロピック液晶ポリエステルは、ｐ−ヒドロキシ安息香酸を４０〜７５モル％含有するものであることが好ましい。この場合、後述する低重合度サーモトロピック液晶ポリエステル粉砕物にｐ−ヒドロキシ安息香酸を４０〜７５モル％含有させることにより、適度な結晶化により表面が硬い粒子となって固相重合が安定に効率よく進行し、優れた耐熱性、成形加工性を得ることができる。 Further, the thermotropic liquid crystal polyester preferably contains 40 to 75 mol% of p-hydroxybenzoic acid. In this case, by adding 40 to 75 mol% of p-hydroxybenzoic acid in the low polymerization degree thermotropic liquid crystal polyester pulverized product, which will be described later, the surface becomes hard particles by appropriate crystallization, and solid phase polymerization is stably and efficiently performed. It progresses well and can obtain excellent heat resistance and molding processability.
次に、低重合度サーモトロピック液晶ポリエステル粉砕物の製造について説明する。 Next, production of a low polymerization degree thermotropic liquid crystal polyester pulverized product will be described.
上述の芳香族ジカルボン酸及び／又は脂環式ジカルボン酸、芳香族ジオール及び芳香族ヒドロキシカルボン酸などのモノマーから通常の重縮合反応によって低重合度のサーモトロピック液晶ポリエステルを得ることができる。その際、モノマーの水酸基の少なくとも一部が酢酸エステル（アセチル化モノマー）であるものを使用して脱酢酸反応を伴いながら重縮合反応を行うのが好ましい。重合装置はモノマー供給手段、酢酸排出手段、溶融ポリマー取り出し手段および攪拌手段を備えた重合槽を用いて行うのが好ましい。このような重合装置は公知のものから適宜選択することができる。重合温度は好ましくは１５０℃〜３５０℃である。重合温度は１５０℃から、０．１℃／分〜２℃／分の範囲で昇温して、最終温度として２８０〜３５０℃まで上昇させるのが好ましい。重合の進行により生成重合体の溶融温度が上昇するのに対応して重合温度も上昇する。 A thermotropic liquid crystal polyester having a low degree of polymerization can be obtained from monomers such as the above-mentioned aromatic dicarboxylic acids and / or alicyclic dicarboxylic acids, aromatic diols and aromatic hydroxycarboxylic acids by an ordinary polycondensation reaction. At that time, it is preferable to carry out the polycondensation reaction using a monomer in which at least a part of the hydroxyl groups of the monomer is an acetic acid ester (acetylated monomer) with a deacetic acid reaction. The polymerization apparatus is preferably carried out using a polymerization tank equipped with monomer supply means, acetic acid discharge means, molten polymer take-out means and stirring means. Such a polymerization apparatus can be appropriately selected from known ones. The polymerization temperature is preferably 150 ° C to 350 ° C. The polymerization temperature is preferably raised from 150 ° C. in the range of 0.1 ° C./min to 2 ° C./min and raised to 280 to 350 ° C. as the final temperature. The polymerization temperature rises corresponding to the melting temperature of the produced polymer rising as the polymerization proceeds.
本実施形態においては、低重合度のサーモトロピック液晶ポリエステルの融点が、２４０〜３３０℃に相当する重合度、好ましくは２４０〜２７０℃に相当する重合度に達したら、低重合度のサーモトロピック液晶ポリマーを溶融状態のまま重合槽からスチールベルトやドラムクーラー等の冷却機へ抜き出し、冷却して固化させる。低重合度の液晶ポリエステルの融点が２４０℃未満では、重合度が低すぎ、固相重合の時間が極めて長くなり工業的に好ましくない。 In this embodiment, when the melting point of the thermotropic liquid crystal polyester having a low polymerization degree reaches a polymerization degree corresponding to 240 to 330 ° C., preferably a polymerization degree corresponding to 240 to 270 ° C., the thermotropic liquid crystal having a low polymerization degree is used. The polymer is withdrawn from the polymerization tank in a molten state to a cooling machine such as a steel belt or a drum cooler, and is cooled and solidified. If the melting point of the liquid crystalline polyester having a low degree of polymerization is less than 240 ° C., the degree of polymerization is too low, and the time for solid phase polymerization becomes extremely long, which is not industrially preferable.
なお、低重合度サーモトロピック液晶ポリエステル粉砕物の融点は、例えばセイコー電子工業（株）製の示差走査熱量計（ＤＳＣ）により、リファレンスとしてα−アルミナを用い、昇温速度２０℃／分で室温から４２０℃まで昇温してポリマーを完全に融解させた後、速度１０℃／分で１５０℃まで降温し、更に２０℃／分の速度で４２０℃まで昇温するＤＳＣ測定を行ったときに得られる吸熱ピークの頂点を指す。 The melting point of the low-polymerization degree thermotropic liquid crystal polyester crushed material is, for example, a differential scanning calorimeter (DSC) manufactured by Seiko Denshi Kogyo Co., Ltd., using α-alumina as a reference, and a room temperature increase rate of 20 ° C./min. When DSC measurement was performed, the temperature was raised to 420 ° C. to completely melt the polymer, then the temperature was lowered to 150 ° C. at a rate of 10 ° C./min, and further raised to 420 ° C. at a rate of 20 ° C./min. It refers to the peak of the endothermic peak obtained.
また、上記低重合度サーモトロピック液晶ポリエステル粉砕物は、ｐ−ヒドロキシ安息香酸を４０〜７５モル％含有することが好ましい。当該低重合度サーモトロピック液晶ポリエステル粉砕物は、ｐ−ヒドロキシ安息香酸以外の成分として、４，４’−ジヒドロキシジフェニルに代表されるジオール成分、テレフタル酸に代表されるジカルボン酸成分を含有することができる。 Moreover, it is preferable that the said low polymerization degree thermotropic liquid crystal polyester ground material contains 40-75 mol% of p-hydroxybenzoic acid. The low polymerization degree thermotropic liquid crystal polyester pulverized product may contain a diol component typified by 4,4′-dihydroxydiphenyl and a dicarboxylic acid component typified by terephthalic acid as components other than p-hydroxybenzoic acid. it can.
固化した低重合度物の粉砕方法は特に限定されないが、例えば、ホソカワミクロン社製のフェザーミル、ビクトミル、コロプレックス、パルベラーザー、コントラプレックス、スクロールミル、ＡＣＭパルベラ−ザー等の衝撃式粉砕機、マツボー社製の架砕式粉砕機であるロールグラニュレーター等が挙げられる。特に好ましくは、ホソカワミクロン社製のフェザーミルである。 The method for pulverizing the solidified low polymerization degree is not particularly limited. For example, Hosokawa Micron's Feather Mill, Victor Mill, Coroplex, Pulverizer, Contraplex, Scroll Mill, ACM Pulverizer, etc. Examples thereof include a roll granulator which is a crushed grinder. Particularly preferred is a feather mill manufactured by Hosokawa Micron.
本実施形態において、固相重合を行う粉砕物の粒径に特に制限はないが、好ましくはＪＩＳ標準工業フルイ（タイラーメッシュ）で４メッシュ通過〜２０００メッシュ不通（粒径で約０．０１〜５ｍｍの範囲にあるものに相当）の範囲である。粒径が４メッシュ以下（５ｍｍ以上）のものが多く含有されると、大小粒子間で固相重合反応の進行に差が生じること、大粒径粒子の表皮部と内部の重合度の差が生じること、また、粒子内に酢酸が残留する等の問題が発生し、固相重合後のポリマー全体の均一性を低下させるので好ましくない。また、粒径が２０００メッシュ以上（０．０１ｍｍ以下）のものが多く含有されることは、ダストの発生、それらが溶融して重合反応器内壁に付着することによる熱伝導効率の低下、それらが滑剤的効果を発生して他の粉砕物の反転攪拌による表面更新の障害等を生じるため好ましくない。これらの点から１５０〜２０００メッシュ（約０．０１〜０．１ｍｍの粒径）の成分を１〜２０質量％、４〜２０メッシュ（約０．８〜５ｍｍの粒径）の成分を１〜２０質量％含有する粒度分布を有するものであることが好ましい。 In the present embodiment, the particle size of the pulverized product to be subjected to solid phase polymerization is not particularly limited, but preferably passes 4 meshes to 2000 meshes with a JIS standard industrial sieve (Tyler mesh) (particle size is about 0.01 to 5 mm). Equivalent to those in the range). If many particles with a particle size of 4 mesh or less (5 mm or more) are contained, there will be a difference in the progress of the solid-state polymerization reaction between the large and small particles, and the difference in the degree of polymerization between the skin part of the large particle and the inside This is not preferable because it causes problems such as acetic acid remaining in the particles and lowers the uniformity of the entire polymer after solid phase polymerization. In addition, the inclusion of many particles having a particle size of 2000 mesh or more (0.01 mm or less) is the generation of dust, a decrease in heat conduction efficiency due to melting and adhering to the inner wall of the polymerization reactor, This is not preferable because a lubricant effect is generated and surface renewal failure is caused by inversion stirring of other pulverized materials. From these points, a component of 150 to 2000 mesh (particle size of about 0.01 to 0.1 mm) is 1 to 20% by mass, a component of 4 to 20 mesh (particle size of about 0.8 to 5 mm) is 1 to 1%. It is preferable to have a particle size distribution containing 20% by mass.
本実施形態においては、粉砕物の粒径分布が、５メッシュ〜２０００メッシュ（０．０１〜４ｍｍの粒径）にあればさらに好ましく、９メッシュ〜１４５０メッシュ（０．０２〜２ｍｍの粒径）にあればさらに好ましい。また、いずれの分布状態においても重量平均粒径が、０．２〜２ｍｍにあればさらに好ましい。 In the present embodiment, the particle size distribution of the pulverized product is more preferably 5 mesh to 2000 mesh (0.01 to 4 mm particle size), and 9 mesh to 1450 mesh (0.02 to 2 mm particle size). If it is in, it is still more preferable. Further, in any distribution state, it is more preferable that the weight average particle diameter is 0.2 to 2 mm.
また、固相重縮合反応の進行の均一性、昇温効率と固相重縮合反応時の低分子量成分の除去の効率の観点から、粉砕物の粒径は、ＪＩＳ標準工業フルイで５メッシュ（呼び径４．００ｍｍ）通過〜２７０メッシュ（呼び径５３μｍ）不通の範囲にあることが好ましい。５メッシュ（呼び径４．００ｍｍ）通過〜１００メッシュ（呼び径１５０μｍ）不通の範囲にあればさらに好ましく、９メッシュ（呼び径２．００ｍｍ）〜３２メッシュ（呼び径５００μｍ）不通の範囲にあればさらに好ましい。 In addition, from the viewpoint of the uniformity of the progress of the solid phase polycondensation reaction, the temperature elevating efficiency, and the efficiency of removing low molecular weight components during the solid phase polycondensation reaction, the particle size of the pulverized product is 5 mesh ( It is preferable that the nominal diameter is in the range of 4.00 mm) through 270 mesh (nominal diameter of 53 μm). 5 mesh (nominal diameter 4.00 mm) passage to 100 mesh (nominal diameter 150 μm) is more preferable, and 9 mesh (nominal diameter 2.00 mm) to 32 mesh (nominal diameter 500 μm) is not preferable. Further preferred.
次に、粉砕物の固相重合について説明する。 Next, solid phase polymerization of the pulverized product will be described.
本実施形態において、粉砕物は振動させた反応器内で少なくとも上下方向に流動させることが必要である。粉砕物の流動パターンは、水平方向から反応器をみたときに、上下方向の流動を含むものであればよい。特に、反応器が円筒形状の内面を有し、円周方向に粉砕物が下方から上方にせり上がる流動を発生させることで、上下方向の流動が生じるものが好ましい。より具体的には、反応器が円筒形状の内面を有し、円筒軸線が略水平となるように配されており、当該反応器に円筒軸線回りの円振動又は楕円振動を付与することが好ましい。この場合、振動により、円周方向に粉砕物が下方から上方へせり上がる流動を容易に発生させることができ、上下方向の流動による粉砕物の攪拌効率を更に向上させることができる。また、粉砕物と反応器内部壁面との接触頻度を多くすることができるため、伝熱効率を向上させることができる。 In this embodiment, the pulverized product needs to flow at least in the vertical direction in the vibrated reactor. The flow pattern of the pulverized material is not particularly limited as long as it includes flow in the vertical direction when the reactor is viewed from the horizontal direction. In particular, it is preferable that the reactor has a cylindrical inner surface and the flow in the vertical direction is generated by generating a flow in which the pulverized material rises from below to above in the circumferential direction. More specifically, the reactor has a cylindrical inner surface, and is arranged so that the cylinder axis is substantially horizontal, and it is preferable to impart circular vibration or elliptic vibration around the cylinder axis to the reactor. . In this case, the vibration can easily generate a flow in which the pulverized product rises from below to above in the circumferential direction, and the stirring efficiency of the pulverized product by the upward and downward flow can be further improved. Further, since the contact frequency between the pulverized product and the inner wall surface of the reactor can be increased, the heat transfer efficiency can be improved.
また、重合したポリマー粉体を反応器から排出する際の利便性を高めるために、上記反応器は、重合終了後に水平軸から３〜１０度傾斜できる構造を有することが好ましい。 Moreover, in order to improve the convenience at the time of discharging | emitting the polymer powder which superposed | polymerized from a reactor, it is preferable that the said reactor has a structure which can incline 3-10 degree | times from a horizontal axis after completion | finish of superposition | polymerization.
本実施形態においては、反応器として粉粒体用振動処理装置を用いることができる。図１の（ａ）及び（ｂ）は、本実施形態の方法で用いられる反応器の一例を説明するための模式図である。 In this embodiment, a vibration treatment apparatus for granular materials can be used as a reactor. FIGS. 1A and 1B are schematic diagrams for explaining an example of a reactor used in the method of the present embodiment.
図１に示される粉粒体用振動処理装置１００は、支持柱１４と、支持柱１４上に設けられた弾性体１２と、弾性体１２上に配された反応器１０と、反応器１０に設けられた発振機１６と、を有する。反応器１０は、円筒形状の内面を有し、円筒軸線が略水平となるように弾性体１２上に配されている。
1 is a
弾性体１２は、コイルばねであるが、反応器１０に付与される振動を吸収できる弾性体であれば、板ばね、エアばね、ゴム状弾性体等であってもよい。
The
反応器１０には、粉粒体として本発明に係る上記の低重合度サーモトロピック液晶ポリエステル粉砕物を投入するための投入口２２と、重合後に得られるサーモトロピック液晶ポリエステルを取り出すための排出口２４とが設けられている。投入口や排出口の配置は適宜変更することが可能である。また、反応器１０は、気体導入口及び排気口を備え、密閉することができる構造を有している。これにより、減圧或いは真空下、又は不活性ガス流通下で固相重合反応を行うことができる。
The
反応器１０の容量としては、特に限定されないが、０．０２〜１０ｍ３が好ましい。
The volume of the
発振機１６は、不平衡錘を有する発振部を原動機（モータ）で回転させる機械式であるが、電磁石方式、振動モータ方式などに適宜変更が可能である。発振機１６は反応器１０の下部に連結されており、発振機１６によって反応器１０に円筒軸線回りの円振動又は楕円振動を付与することができる。
The
本実施形態においては、例えば、発振機１６の発振部を楕円振動（図１（ｂ）中の破線矢印Ａ）させることにより、反応器１０の上部の中央において上下振動（図１（ｂ）中の破線矢印Ｂ１）、反応器の下部の中央において円振動（図１（ｂ）中の破線矢印Ｂ２）を発生させることができる。このときの振動数（発振機モータ回転数）は、１０００〜２０００ｒｐｍが好ましく、１２００〜１５００ｒｐｍがより好ましい。また、反応容器の振動中心（図１（ｂ）中の破線矢印Ｂ２）における振幅（円振動の直径）は、２〜５ｍｍが好ましく、３〜４ｍｍがより好ましい。
In the present embodiment, for example, by causing the oscillation part of the
図２の（ａ）及び（ｂ）は粉砕物の流動パターンの一例を示す模式図である。上記の振動によって反応器１０内の粉砕物２０は、円周上下方向への動きが主体の流動パターンで流動する。図２中、矢印Ｃが重力方向を示し、重力の作用により粉砕物が流動する方向が上下方向の下方である。
2A and 2B are schematic views showing an example of the flow pattern of the pulverized product. Due to the above vibration, the pulverized
反応器１０には温調手段が設けられており、粉砕物を加熱及び冷却することができる。温調手段としては、例えば、温水、水蒸気、冷水、熱媒油などの熱媒体を通過可能に配管されたジャケットなどが挙げられる。
The
粉粒体用振動処理装置としては、例えば、ＶＨ２５型、ＶＨ１２０型（以上、中央化工機株式会社製）などの振動式乾燥機を用いることができる。 As the vibration treatment apparatus for powder particles, for example, a vibratory dryer such as a VH25 type, a VH120 type (manufactured by Chuo Kako Co., Ltd.) can be used.
上述した粉粒体用振動処理装置によれば、振動だけで粉砕物を十分流動させることができるため、（ｉ）粉砕物の破壊が少なく微粉の発生を抑制できる、（ｉｉ）局部加熱による重合ムラを抑制できる、（ｉｉｉ）粉砕物の充填率を高くしても重合ムラを抑制できる、（ｉｖ）振動させながら重合後のポリエステルを容易に排出することができる、などの効果が奏される。 According to the above-described vibration treatment apparatus for granular materials, since the pulverized product can be sufficiently flowed only by vibration, (i) the pulverized product is less destroyed and the generation of fine powder can be suppressed. (Ii) Polymerization by local heating Unevenness can be suppressed, (iii) Polymerization unevenness can be suppressed even when the pulverized product has a high filling rate, and (iv) Polyester after polymerization can be easily discharged while being vibrated. .
固相重合は、上述した振動を付与しながら、不活性ガス気流下又は真空若しくは減圧下、粉砕物（粉体）の最終到達温度２５０℃〜３３０℃、重合時間５時間〜２４時間の条件で行うことができる。昇温の速度は、粉砕物の溶融付着を抑制する点で、０．０５℃／分〜２℃／分の範囲が好ましい。 The solid-phase polymerization is performed under the conditions that the final reached temperature of the pulverized product (powder) is 250 ° C. to 330 ° C. and the polymerization time is 5 hours to 24 hours under an inert gas stream or under vacuum or reduced pressure while applying the vibration described above. It can be carried out. The rate of temperature rise is preferably in the range of 0.05 ° C./min to 2 ° C./min in terms of suppressing melt adhesion of the pulverized product.
減圧下で行う場合、１０Ｔｏｒｒ以下が好ましい。この場合、窒素などの不活性ガスを流通させる費用を低減させることができる。 When carried out under reduced pressure, 10 Torr or less is preferable. In this case, the cost of circulating an inert gas such as nitrogen can be reduced.
反応器における粉砕物の充填率は、３０〜７０％が好ましく、生産効率の観点から、５０〜７０％がより好ましい。ここでいう充填率は、下記式で定義されるものである。
充填率（％）＝［反応器内における粉砕物のかさ体積（ｍ３）］／［反応器の体積（容積）（ｍ３）］×１００
なお、上記粉砕物のかさ体積は、（充填質量）／（粉砕物のかさ比重）から求めることができる。
The filling rate of the pulverized product in the reactor is preferably 30 to 70%, and more preferably 50 to 70% from the viewpoint of production efficiency. The filling rate here is defined by the following formula.
Filling rate (%) = [bulk volume of pulverized material in reactor (m 3 )] / [volume (volume) of reactor (m 3 )] × 100
The bulk volume of the pulverized product can be obtained from (filling mass) / (bulk specific gravity of the pulverized product).
以上、本発明の好適な実施形態について説明したが、本発明は上記実施形態に限定されるものではない。例えば、発振機の取付位置を変更したり、振動のタイプを上下振動、斜め直線振動又は半楕円振動に変更したりしてもよい。また、反応器の形状についても、振動によって粉砕物を少なくとも上下方向に流動させることができるものであれば、種々の形状を選択することができる。 The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment. For example, the mounting position of the oscillator may be changed, or the vibration type may be changed to vertical vibration, oblique linear vibration, or semi-elliptical vibration. As for the shape of the reactor, various shapes can be selected as long as the pulverized material can flow at least in the vertical direction by vibration.
以下、実施例により本発明をさらに具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.
＜低重合度サーモトロピック液晶ポリエステル粉砕物の作製＞
ＳＵＳ３１６を材質とし、ダブルヘリカル攪拌翼を有する１７００Ｌ重合槽（神戸製鋼社製）にｐ−ヒドロキシ安息香酸（上野製薬株式会社製）２９８ｋｇ（２．２キロモル）、４，４’−ジヒドロキシジフェニル（本州化学工業株式会社製）１３４ｋｇ（０．７キロモル）、テレフタル酸（三井化学株式会社製）９０ｋｇ（０．５キロモル）、イソフタル酸（エイ・ジイ・インターナショナルケミカル株式会社製）３０ｋｇ（０．２キロモル）、触媒として酢酸カリウム（キシダ化学株式会社製）０．０４ｋｇ、酢酸マグネシウム（キシダ化学株式会社製）０．１０ｋｇを仕込み、重合槽の減圧−窒素注入を２回行って窒素置換した後、無水酢酸３９０ｋｇ（３．８キロモル）を添加し、攪拌翼の回転数４５ｒｐｍで１５０℃まで１．５時間で昇温して還流状態で２時間アセチル化反応を行った。アセチル化終了後、酢酸留出状態にして０．５℃／分で昇温して、３０５℃において重合物をリアクター下部の抜き出し口から取り出した。取り出した重合体を冷却固化した後、ホソカワミクロン株式会社製の粉砕機により概ね５ｍｍ以下に粉砕し、ＪＩＳ標準工業フルイにて、５メッシュ（呼び径４ｍｍ）通過〜２７０メッシュ（呼び径５３μｍ）不通の範囲にある粉砕物を選別し、固相重合に供するプレポリマーとした。ＤＳＣによって測定したプレポリマーの融点は２４７℃であった。またプレポリマーのＪＩＳ Ｚ ８８０７に準じて測定したかさ比重は０．７ｇ／ｃｍ３であった。
<Preparation of pulverized product of low polymerization degree thermotropic liquid crystal polyester>
P-hydroxybenzoic acid (manufactured by Ueno Pharmaceutical Co., Ltd.) 298 kg (2.2 kgol), 4,4′-dihydroxydiphenyl (Honshu) in a 1700 L polymerization tank (manufactured by Kobe Steel Co., Ltd.) made of SUS316 and having a double helical stirring blade Chemical Industry Co., Ltd.) 134 kg (0.7 kgol), terephthalic acid (Mitsui Chemicals Co., Ltd.) 90 kg (0.5 kgol), Isophthalic acid (Aji International Chemical Co., Ltd.) 30 kg (0.2 kgol) ), 0.04 kg of potassium acetate (manufactured by Kishida Chemical Co., Ltd.) and 0.10 kg of magnesium acetate (manufactured by Kishida Chemical Co., Ltd.) were charged as catalysts, and after depressurizing and injecting nitrogen into the polymerization tank twice to replace the nitrogen, anhydrous 390 kg (3.8 kgol) of acetic acid was added, and the stirring blade rotation speed was 45 rpm to 150 ° C. for 1.5 hours. The acetylation reaction was carried out at reflux for 2 hours. After completion of acetylation, acetic acid was distilled off, the temperature was raised at 0.5 ° C./min, and the polymer was taken out from the outlet at the bottom of the reactor at 305 ° C. The polymer taken out was cooled and solidified, and then pulverized to approximately 5 mm or less by a pulverizer manufactured by Hosokawa Micron Co., Ltd. and passed through 5 mesh (nominal diameter 4 mm) to 270 mesh (nominal diameter 53 μm) through JIS standard industrial sieve. The pulverized product in the range was selected and used as a prepolymer for solid phase polymerization. The melting point of the prepolymer measured by DSC was 247 ° C. The bulk specific gravity of the prepolymer measured according to JIS Z 8807 was 0.7 g / cm 3 .
＜サーモトロピック液晶ポリエステルの製造＞
（実施例１）
振動乾燥機（中央化工機製 ＶＨ−２５型、容量２５Ｌ）に、上記で得られたプレポリマーを１０ｋｇ仕込み（充填率６８％）、反応容器の振動中心の振幅４ｍｍ、振動数１２００ｒｐｍ、１０Ｔｏｒｒの減圧下の運転条件で、固相重合を行った。なお、重合は、熱媒油の温度を室温（２０℃）から１８０℃まで３０分で昇温、１８０℃で１時間保持、１８０℃から２７０℃まで４時間で昇温、２７０℃で１時間保持して行った。最終的な粉体の温度は２５０℃であった。その後、３時間かけて室温まで冷却した。
<Manufacture of thermotropic liquid crystal polyester>
Example 1
Into a vibration dryer (VH-25 model, Chuo Kakoki, capacity 25 L), 10 kg of the prepolymer obtained above was charged (filling rate 68%), the vibration center amplitude of the reaction vessel was 4 mm, the pressure was 1200 rpm, and the pressure was reduced to 10 Torr. Solid state polymerization was performed under the following operating conditions. In the polymerization, the temperature of the heat transfer oil is raised from room temperature (20 ° C.) to 180 ° C. in 30 minutes, held at 180 ° C. for 1 hour, heated from 180 ° C. to 270 ° C. in 4 hours, and heated at 270 ° C. for 1 hour. Held. The final powder temperature was 250 ° C. Then, it cooled to room temperature over 3 hours.
乾燥機内の粉砕物層の上側（以下、「中央部サンプル」という。）および下側（以下、「壁面部サンプル」という。）から、それぞれ、約３００ｇの粉砕物をサンプリングした後、残りの粉砕物をタンブラーミキサーに入れて混合し、全体を均一化したものからも約３００ｇの粉砕物をサンプリングした（以下、「全体サンプル」という。）。 About 300 g of pulverized material was sampled from the upper side (hereinafter referred to as “center portion sample”) and the lower side (hereinafter referred to as “wall surface portion sample”) of the pulverized material layer in the dryer, and then the remaining pulverized material About 300 g of the pulverized material was sampled from what was mixed in a tumbler mixer and homogenized as a whole (hereinafter referred to as “whole sample”).
中央部サンプル、壁面部サンプル及び全体サンプルの融点はそれぞれ、３０２℃、２９９℃及び３００℃であった。 The melting points of the center sample, the wall surface sample, and the whole sample were 302 ° C., 299 ° C., and 300 ° C., respectively.
（比較例１）
上記で得られたプレポリマーを入江商会製のロータリーキルン型（容量１０Ｌ）固相重合装置に１ｋｇ（充填率２５％）充填し、窒素を０．２Ｎｍ３／ｈｒの流速にて流通し、回転速度５ｒｐｍでヒーター温度を室温から２７０℃まで１時間かけて昇温した後、１０時間保持した。粉砕物の温度が２５０℃に到達したことを確認し、加熱を停止して、キルンを回転しながら、８時間かけて室温まで冷却した。ロータリーキルン内の粉砕物層の上側（以下、「中央部サンプル」という。）および下側（以下、「壁面部サンプル」という。）から、それぞれ、約５０ｇの粉砕物をサンプリングした後、残りの粉砕物をタンブラーミキサーに入れて混合し、全体を均一化したものからも約５０ｇの粉砕物をサンプリングした（以下、「全体サンプル」という。）。
(Comparative Example 1)
The prepolymer obtained above was charged into a rotary kiln type (capacity 10 L) solid phase polymerization apparatus manufactured by Irie Shokai Co., Ltd. in a quantity of 1 kg (filling rate 25%), and nitrogen was circulated at a flow rate of 0.2 Nm 3 / hr. The heater temperature was raised from room temperature to 270 ° C. over 1 hour at 5 rpm, and then maintained for 10 hours. After confirming that the temperature of the pulverized product reached 250 ° C., the heating was stopped, and the kiln was rotated, and then cooled to room temperature over 8 hours. About 50 g of pulverized material was sampled from the upper side (hereinafter referred to as “center portion sample”) and the lower side (hereinafter referred to as “wall surface portion sample”) of the pulverized material layer in the rotary kiln, and then the remaining pulverized material. About 50 g of the pulverized material was sampled from the homogenized whole (hereinafter referred to as “whole sample”).
中央部サンプル、壁面部サンプル及び全体サンプルの融点はそれぞれ、２９９℃、３０１℃及び３００℃であった。 The melting points of the center sample, the wall surface sample, and the whole sample were 299 ° C., 301 ° C., and 300 ° C., respectively.
（比較例２）
上記で得られたプレポリマーを入江商会製のロータリーキルン型（容量１０Ｌ）固相重合装置に１ｋｇ（充填率２５％）充填し、窒素を０．２Ｎｍ３／ｈｒの流速にて流通し、回転速度５ｒｐｍでヒーター温度を室温（２０℃）から１８０℃まで３０分かけて昇温、１８０℃で１時間保持、１８０℃から２７０℃まで４時間かけて昇温、２７０℃で１時間保持した。最終的な粉体の温度は２３０℃であった。その後、８時間かけて室温まで冷却した。中央部サンプル、壁面部サンプル及び全体サンプルの融点はそれぞれ、２７４℃、２７７℃及び２７５℃であった。
(Comparative Example 2)
The prepolymer obtained above was charged into a rotary kiln type (capacity 10 L) solid phase polymerization apparatus manufactured by Irie Shokai Co., Ltd. in a quantity of 1 kg (filling rate 25%), and nitrogen was circulated at a flow rate of 0.2 Nm 3 / hr. The heater temperature was raised from room temperature (20 ° C.) to 180 ° C. over 30 minutes at 5 rpm, held at 180 ° C. for 1 hour, heated from 180 ° C. to 270 ° C. over 4 hours, and held at 270 ° C. for 1 hour. The final powder temperature was 230 ° C. Then, it cooled to room temperature over 8 hours. The melting points of the center sample, the wall surface sample, and the entire sample were 274 ° C., 277 ° C., and 275 ° C., respectively.
（比較例３）
上記で得られたプレポリマーを入江商会製のロータリーキルン型（容量１０Ｌ）固相重合装置に２．８ｋｇ（充填率４０％）充填し、窒素を０．２Ｎｍ３／ｈｒの流速にて流通し、回転速度５ｒｐｍでヒーター温度を室温から２７０℃まで１時間かけて昇温した後、１０時間保持したが、粉体が壁面で固化したため、均一な重合体の粉体を得ることができなかった。
(Comparative Example 3)
The prepolymer obtained above was charged in a rotary kiln type (capacity 10 L) solid-state polymerization apparatus manufactured by Irie Shokai Co., Ltd. with 2.8 kg (filling rate 40%), and nitrogen was circulated at a flow rate of 0.2 Nm 3 / hr. The heater temperature was raised from room temperature to 270 ° C. over 1 hour at a rotational speed of 5 rpm, and then maintained for 10 hours. However, since the powder solidified on the wall surface, a uniform polymer powder could not be obtained.
（比較例４）
上記で得られたプレポリマーを入江商会製のロータリーキルン型（容量１０Ｌ）固相重合装置に２．８ｋｇ（充填率４０％）充填し、窒素を０．２Ｎｍ３／ｈｒの流速にて流通し、回転速度５ｒｐｍでヒーター温度を室温（２０℃）から１８０℃まで３０分で昇温、１８０℃で２時間保持、１８０℃から２７０℃まで８時間かけて昇温、２７０℃で６時間保持した。最終的な粉体の温度は２５０℃であった。その後、１０時間かけて室温まで冷却した。中央部サンプル、壁面部サンプル及び全体サンプルの融点はそれぞれ、３００℃、３０１℃及び３００℃であった。
(Comparative Example 4)
The prepolymer obtained above was charged in a rotary kiln type (capacity 10 L) solid-state polymerization apparatus manufactured by Irie Shokai Co., Ltd. with 2.8 kg (filling rate 40%), and nitrogen was circulated at a flow rate of 0.2 Nm 3 / hr. The heater temperature was raised from room temperature (20 ° C.) to 180 ° C. in 30 minutes at a rotational speed of 5 rpm, held at 180 ° C. for 2 hours, heated from 180 ° C. to 270 ° C. over 8 hours, and held at 270 ° C. for 6 hours. The final powder temperature was 250 ° C. Then, it cooled to room temperature over 10 hours. The melting points of the center sample, the wall surface sample, and the whole sample were 300 ° C., 301 ° C., and 300 ° C., respectively.
本願発明の方法を用いた実施例１では、従来法である比較例１よりも容量が大きく且つ充填率が高いにもかかわらず、短い固相重合時間で、中央部及び壁面部でも融点がほぼ同じである均一な重合体を得ることができることが明らかとなった。したがって、本願発明の方法は、サーモトロピック液晶ポリエステルの生産効率が高いことがわかる。 In Example 1 using the method of the present invention, although the capacity and the filling rate are higher than those of Comparative Example 1 which is a conventional method, the melting point is almost equal even at the central part and the wall part in a short solid phase polymerization time. It has been found that uniform polymers can be obtained which are the same. Therefore, it turns out that the method of this invention has high production efficiency of thermotropic liquid crystal polyester.
一方、ロータリーキルンを用いる従来法の比較例１では、粉体の熱伝導が悪いので初期に大きな熱量を与えるような温度設定で固相重合を進めたが、粉体の表面更新速度が遅いため熱伝導の効率が悪く、固相重合時間が長くなった。比較例２では、ロータリーキルンで実施例１と同様の段階的昇温により重合したが、やはり粉体の熱伝導が悪く、最終的な重合体の融点が低く重合度が不足した。比較例３では、ロータリーキルンの充填率を最大にして重合したが、粉体の表面更新が不十分で均一に加熱できず、反応器内壁面に粉体が融着してしまった。比較例４では、比較例３と同様に充填率を最大にし、実施例１に倣って段階的に昇温したところ、比較例３のような粉体の融着は防げたが、重合時間が著しく長く、実施例１の２．５倍にもなった。 On the other hand, in Comparative Example 1 of the conventional method using a rotary kiln, since the thermal conductivity of the powder was poor, solid phase polymerization was advanced at a temperature setting that gave a large amount of heat in the initial stage. The conduction efficiency was poor, and the solid phase polymerization time was long. In Comparative Example 2, polymerization was performed in a rotary kiln by the same stepwise temperature increase as in Example 1, but the heat conduction of the powder was still poor, the final polymer had a low melting point, and the degree of polymerization was insufficient. In Comparative Example 3, the polymerization was performed with the filling rate of the rotary kiln being maximized, but the surface of the powder was not sufficiently renewed and could not be heated uniformly, and the powder was fused to the inner wall surface of the reactor. In Comparative Example 4, the filling rate was maximized in the same manner as in Comparative Example 3, and when the temperature was raised stepwise in accordance with Example 1, powder fusion as in Comparative Example 3 was prevented. It was significantly longer, 2.5 times that of Example 1.
１０…反応器、１２…弾性体、１４…支持柱、１６…発振機、２０…粉砕物、２２…投入口、２４…排出口、１００…粉粒体用振動処理装置。
DESCRIPTION OF
Claims (2)
前記反応器は、円筒形状の内面を有し、円筒軸線が略水平となるように配されており、当該反応器に、円筒軸線回りの円振動又は楕円振動を付与することを特徴とする、サーモトロピック液晶ポリエステルの製造方法。 A low-polymerization degree thermotropic liquid crystal polyester pulverized product having a melting point of 240 to 330 ° C. discharged from the reaction vessel in a molten state, cooled and solidified, and pulverized is caused to flow at least vertically in a vibrated reactor. A method for producing a thermotropic liquid crystalline polyester that undergoes solid phase polymerization ,
The reactor has a cylindrical inner surface and is arranged so that a cylindrical axis is substantially horizontal, and the reactor is subjected to circular vibration or elliptical vibration around the cylindrical axis . A method for producing thermotropic liquid crystal polyester.
The method for producing a thermotropic liquid crystal polyester according to claim 1, wherein the low polymerization degree thermotropic liquid crystal polyester pulverized product contains 40 to 75 mol% of p-hydroxybenzoic acid as a constituent component of the polyester.
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