JPH06842B2 - Low molecular weight polyester - Google Patents
Low molecular weight polyesterInfo
- Publication number
- JPH06842B2 JPH06842B2 JP60271701A JP27170185A JPH06842B2 JP H06842 B2 JPH06842 B2 JP H06842B2 JP 60271701 A JP60271701 A JP 60271701A JP 27170185 A JP27170185 A JP 27170185A JP H06842 B2 JPH06842 B2 JP H06842B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- low molecular
- polyester
- organic liquid
- phase
- 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 - Lifetime
Links
- 229920000728 polyester Polymers 0.000 title claims description 31
- 239000002904 solvent Substances 0.000 claims description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 description 19
- 239000007791 liquid phase Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000006068 polycondensation reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000003444 phase transfer catalyst Substances 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical group OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 4
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 150000002118 epoxides Chemical class 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 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
- YWFPGFJLYRKYJZ-UHFFFAOYSA-N 9,9-bis(4-hydroxyphenyl)fluorene Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C2=CC=CC=C21 YWFPGFJLYRKYJZ-UHFFFAOYSA-N 0.000 description 1
- VOWWYDCFAISREI-UHFFFAOYSA-N Bisphenol AP Chemical compound C=1C=C(O)C=CC=1C(C=1C=CC(O)=CC=1)(C)C1=CC=CC=C1 VOWWYDCFAISREI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VBQDSLGFSUGBBE-UHFFFAOYSA-N benzyl(triethyl)azanium Chemical compound CC[N+](CC)(CC)CC1=CC=CC=C1 VBQDSLGFSUGBBE-UHFFFAOYSA-N 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Description
【発明の詳細な説明】 技術分野 本発明は、式 の鎖構成員から本質同になる低分子量ポリエステルであ
つて、該鎖構成員中構成員Ｘとして本質的に構造 又は を有し、構成員Ｙとして本質的に構造 式中、 Ｒは二官能性脂肪族炭化水素基又は二官能 性の、少くとも１個の芳香環もしくは脂環 式環を含有する炭化水素基である、 を有する低分子量ポリエステル並びに該低分子量ポリエ
ステルを製造するための有利な方法に関する。TECHNICAL FIELD The present invention relates to a formula A low molecular weight polyester having essentially the same structure as the chain member of Or And essentially a structure as member Y In the formula, R is a bifunctional aliphatic hydrocarbon group or a bifunctional hydrocarbon group containing at least one aromatic ring or alicyclic ring, and the low molecular weight polyester To an advantageous method for manufacturing.
従来技術 上記の種類の高分子量ポリエステルは、例えば欧州特許
出願第８１８９００７6.３号（公開番号第００４１４９
６Ａ１号）から公知である。該ポリエステルの平均分子
量に対応するインピーレン トビスコシチーの値ＩＶ＝ηinh（測定条件、温度：３
０℃、濃度：溶液１００ml中ポリエステル0.５ｇ、溶
媒：フエノール６０重量％及び１，１，２，２−テトラ
クロルエタン４０重量％からなる混合溶媒）は、1.５ｄ
ｌ／ｇ以上の範囲にある。PRIOR ART High molecular weight polyesters of the type described above are described, for example, in European Patent Application No. 81890076.3 (Publication No. 004149).
6A1). The value of imperative viscosity corresponding to the average molecular weight of the polyester IV = ηinh (measurement conditions, temperature: 3
0 ° C., concentration: 0.5 g polyester in 100 ml of solution, solvent: 60% by weight of phenol and 40% by weight of 1,1,2,2-tetrachloroethane) is 1.5 d
It is in the range of 1 / g or more.
該ポリエステルは好ましくは二相界面（重合）法（Zwei
phasengrenzflchenverfahren）により製造される。こ
の二相界面重合法では水性相又は、水又は場合により水
及び可溶化剤としての有機溶媒からなる混合物中のジフ
エノール、ジフエノラート基を生成させるための化学量
論比又は少し過剰の水性アルカリ並びに相間移動触媒
（Phasentransferkatalysator）例えばベンジルトリエ
チルアンモニウムクロライド、テトラブチルアンモニウ
ムヨーダイド又はクラウンエーテルからなる水性相と有
機溶媒中の酸クロライドの溶液からなる有機液体 とか
ら、細かい分散体（Dispersion）をつくる。その際相間
移動触媒の助けで有機液体相に移動したジフエノラート
は酸ハロゲン化物と重縮合反応を起こし、重縮合反応の
後生成したポリエステルが有機液体相から得られる。The polyester is preferably a two-phase interfacial (polymerization) method (Zwei
manufactured by phasengrenzflchenverfahren). In this two-phase interfacial polymerization process, a stoichiometric ratio or a slight excess of aqueous alkali and interphase between the aqueous phase or a mixture of water or optionally water and an organic solvent as solubilizer to form diphenol groups. A fine dispersion is formed from an aqueous phase consisting of a phase transfer catalyst, such as benzyltriethylammonium chloride, tetrabutylammonium iodide or crown ether, and an organic liquid consisting of a solution of the acid chloride in an organic solvent. At that time, the diphenolate transferred to the organic liquid phase with the aid of the phase transfer catalyst undergoes a polycondensation reaction with the acid halide, and the polyester produced after the polycondensation reaction is obtained from the organic liquid phase.
本発明の説明 多くの用途のために、例えば重合体混合物の成分とし
て、又は更に重合反応を行なわせるための出願原料とし
て、低分子量重合体、とくに0.１〜0.５ｄｌ／ｇのイン
ヒーレントビスコシチーの値を有する低分子量ポリエス
テルが現在必要とされている。上記のように更に重合反
応を行なわせる場合、低分子量重合体は、例えばアミ
ン、アミド、イミド等との重縮合反応によりあるいはま
た例えばエポキシド、ノルボルネン等との重付加反応に
より反応することが可能である。DESCRIPTION OF THE INVENTION For many applications, low molecular weight polymers, in particular 0.1-0.5 dl / g of inherent polymer, for example as a component of polymer mixtures or as raw material for further polymerization reactions. There is currently a need for low molecular weight polyesters with biscocity values. When the polymerization reaction is further carried out as described above, the low molecular weight polymer can be reacted by a polycondensation reaction with, for example, an amine, an amide, an imide or the like or by a polyaddition reaction with, for example, an epoxide, norbornene or the like. is there.
本発明の課題はまず第一に、良好なインヒーレントビス
コシチーの値の再現性を得つつ製造することができる上
述の種類の低分子量ポリエステルを提供することであ
る。The object of the present invention is, first of all, to provide a low-molecular-weight polyester of the abovementioned type which can be produced with good reproducibility of the value of the inherent viscocity.
本課題は、0.０８〜0.３５ｄｌ／ｇ、好ましくは０．１
〜０．２５ｄｌ／ｇのインヒーレントビスコシチー（測
定条件、温度：３０℃、温度：溶液１００ml中ポリエス
テル０．５ｇ、溶媒：フエノール６０重量％及び１，
１，２，２−テトラクロルエタン４０重量％からなる混
合溶媒）を示す本発明に従うポリエステルによつて解決
される。その場合、上記鎖構成員中構成員Ｙにおいて二
官能性基Ｒは 又は であることが有利であることがある。This subject is 0.08 to 0.35 dl / g, preferably 0.1
˜0.25 dl / g inherent viscocity (measurement conditions, temperature: 30 ° C., temperature: 0.5 g polyester in 100 ml of solution, solvent: 60% by weight of phenol and 1,
It is solved by a polyester according to the invention exhibiting a mixed solvent consisting of 40% by weight of 1,2,2-tetrachloroethane). In that case, the bifunctional group R in the member Y among the above-mentioned chain members is Or Can be advantageous.
本発明に従うポリエステルの有利な態様によれば、上記
鎖構成員の３０〜７０％は構成員Ｘとして構造Ｘ１を有
し、上記鎖構成員の７０〜３０％が構成員Ｘとして構造
Ｘ２を有する。According to an advantageous embodiment of the polyester according to the invention, 30-70% of the chain members have the structure X 1 as member X and 70-30% of the chain members have the structure X 2 as member X. Have.
本発明の課題はさらに、本発明に従う低分子量ポリエス
テルを製造するための上で略述した種類の二相界面重合
法を提供することである。It is a further object of the present invention to provide a two phase interfacial polymerization process of the type outlined above for producing the low molecular weight polyester according to the present invention.
本課題は、重縮合反応の初期から反応進行の大部分の期
間に分散体が水性相に含有されているジフエノラートを
有機相に含有されている酸ハロゲン化物に関して不足量
で含有していることを特徴とする本発明に従う方法によ
つて解決される。The object of the present invention is that the dispersion contains the diphenolate contained in the aqueous phase in an insufficient amount with respect to the acid halide contained in the organic phase from the initial stage of the polycondensation reaction to most of the reaction progress. It is solved by a method according to the invention which is characterized.
本発明に従う方法の有利な態様によれば、水性相に加え
て装入した有機液体相もまた相間移動触媒を含有してい
る。According to an advantageous embodiment of the process according to the invention, the charged organic liquid phase in addition to the aqueous phase also contains a phase transfer catalyst.
本発明に従う方法の有利な態様において、容器に装入し
た有機液体相を休まずに激しく撹拌しながら、該有機液
体相に反応すべきジフエノールを、有機液体相に装入し
た酸ハロゲン化物に関して化学量論比又はそれより少量
で含有している水性相を連続的に又は順々に一部分ずつ
加え、その後場合により水性相及び有機液体相からなる
分散体を少くとも重縮合反応が終了するまで更に撹拌す
ることによつて維持する。その際、水性相の添加は、少
くとも添加した水性相が場合によりただちに有機液体相
中で分散される程度にゆつくりと、有利には１〜１５分
間の間に行なう。In an advantageous embodiment of the process according to the invention, the diphenyl which is to react with the organic liquid phase is reacted chemically with respect to the acid halide charged into the organic liquid phase, while vigorously stirring the organic liquid phase charged in the vessel. The aqueous phase, containing it in stoichiometric proportion or less, is added continuously or sequentially in portions, and then a dispersion of an aqueous phase and an organic liquid phase is further added at least until the polycondensation reaction is complete. Maintained by stirring. The aqueous phase is then added at least to such an extent that the added aqueous phase is immediately dispersed in the organic liquid phase, preferably between 1 and 15 minutes.
本発明に従う方法の別の有利な態様に従えば、有機液体
相と、装入した酸ハロゲン化物に関してジフエノールを
不足量で含有している水性相を連続的に混合し、その後
該混合物を順に１個又は複数個の分散装置及び／又は静
的ミキサー（statische Mixer）に流入させる。According to another advantageous embodiment of the process according to the invention, the organic liquid phase and the aqueous phase containing a deficient amount of diphenol with respect to the acid halide charged are continuously mixed, after which the mixture is successively mixed with 1 Flow into one or more dispersers and / or a static mixer.
他の有利な態様に従うと、有機液体相を導管の形状につ
くつた反応器の入口に供給し、該反応器は中に流動方向
に順々に１個又は複数個の分散装置及び／又は静的ミキ
サーを備えており、その際水性相は、反応器へ流動方向
に順に配置された複数個の供給場所で複数の部分流とし
て場合により連続的に導入する。According to another advantageous embodiment, the organic liquid phase is fed to the inlet of a reactor in the form of a conduit, through which one or more dispersing devices and / or statics are arranged one after the other in the flow direction. A dynamic mixer is provided, in which case the aqueous phase is continuously introduced into the reactor as a plurality of partial streams at a plurality of feed stations arranged one after the other in the flow direction.
図面の説明 図面は本発明に従う方法の好ましい態様の実施をするた
めの装置の流れ図を示す。DESCRIPTION OF THE DRAWINGS The drawing shows a flow chart of an apparatus for carrying out the preferred embodiments of the method according to the invention.
容器１及び２は計量ポンプ５，５′及び流量計６，６′
を備えた導管３，４を経て、分散装置７の入口と連結さ
れており、分散装置７の出口は導管９を経て静的ミキサ
ー１０の入口と連結されている。静的ミキサー１０の出
口１１は導管１２を経て撹拌機１３を備えた容器１４に
通じている。Containers 1 and 2 are metering pumps 5 and 5'and flow meters 6 and 6 '.
Is connected to the inlet of the dispersing device 7 via the conduits 3 and 4, and the outlet of the dispersing device 7 is connected to the inlet of the static mixer 10 via the conduit 9. The outlet 11 of the static mixer 10 leads via a conduit 12 to a vessel 14 equipped with a stirrer 13.
本発明を実施するための最良の方法 低分子量ポリエステルを製造するための本発明に従う重
縮合方法を以下において若干の実施例に基き詳しく説明
する。BEST MODE FOR CARRYING OUT THE INVENTION The polycondensation process according to the present invention for producing low molecular weight polyesters is described in detail below based on some examples.
実施例 １ 水性相を調製するために、水４００ml中にまずNaOH8.８
ｇ（0.２２モル）を、次いで１，１−ビス（４−ヒドロ
キシフエニル）−１−フエニルエタン２９ｇ（0.１モ
ル）を暖めて溶解させ、生成した溶液を冷却しイソプロ
パノール７０mlと混合する。次にこの溶液に相間移動触
媒として少量の水に溶解したベンジルトリエチルアンモ
ニウムクロライド1.１４ｇ（0.００５モル）を加える。Example 1 To prepare an aqueous phase, first add NaOH 8.8 in 400 ml of water.
g (0.22 mol), then 29 g (0.1 mol) of 1,1-bis (4-hydroxyphenyl) -1-phenylethane are dissolved by warming, the resulting solution is cooled and mixed with 70 ml of isopropanol. . Next, 1.14 g (0.005 mol) of benzyltriethylammonium chloride dissolved in a small amount of water is added to this solution as a phase transfer catalyst.
無水１，２−ジクロルエタン２５０ml中のイソフタル酸
クロライド１3.２ｇ（0.０６５モル）及びテレフタル酸
クロライド１3.２ｇ（0.０６５モル）の溶液からなる有
機液体相を窒素雰囲気下において、分散機として作用す
る高速回転撹拌機を備えた2.５のフラスコに導入し、
まず冷却浴中で１７℃に冷却する。An organic liquid phase consisting of a solution of 13.2 g (0.065 mol) of isophthalic acid chloride and 13.2 g (0.065 mol) of terephthalic acid chloride in 250 ml of anhydrous 1,2-dichloroethane was used as a disperser under a nitrogen atmosphere. Introduced into a 2.5 flask equipped with a working high speed rotary stirrer,
First, it cools to 17 degreeC in a cooling bath.
撹拌機のスイツチを入れた後、導入した有機液体相に６
分間の間に水性相を流入させる。そのとき激しい撹拌の
ために流入する水相は有機液体相中で場合によりただち
に分散される。水性相の添加の間に、反応混合物を生成
する分散体の温度は１７℃から約２６℃に上昇する。添
加終了後、分散体を維持するため６分間の後反応時間の
間もさらに撹拌を続ける。After adding the switch of the stirrer, add 6 to the introduced organic liquid phase.
Allow the aqueous phase to flow in between the minutes. The inflowing aqueous phase is then immediately dispersed in the organic liquid phase, if necessary, due to vigorous stirring. During the addition of the aqueous phase, the temperature of the dispersion forming the reaction mixture rises from 17 ° C to about 26 ° C. After the addition is complete, stirring is continued during the 6 minute post-reaction time to maintain the dispersion.
撹拌機のスイツチを切り放置すると短時間のうちに相が
分離してくる。分離した相のうち弱アルカリ性の水性相
はすてる。次いで生成した低分子量ポリエステルを含有
する有機液体相を水で３回洗浄し、最後にイソプロパノ
ールを添加して撹拌することによつてポリエステルを細
かい粒子の形態で沈殿させる。沈殿した物質を吸引別
し、８０℃で真空乾燥中で乾燥する。インヒーレントビ
スコシチーＩＶ＝0.１３ｄｌ／ｇ及び融解範囲２００〜
２２０℃のポリエステル４０ｇ（収率９５％）が得られ
る。If the switch of the stirrer is cut off and left to stand, the phases will separate in a short time. Of the separated phases, the weakly alkaline aqueous phase is drained. The resulting organic liquid phase containing the low molecular weight polyester is then washed 3 times with water and finally the polyester is precipitated in the form of fine particles by adding isopropanol and stirring. The precipitated substance is suctioned off and dried in vacuum drying at 80 ° C. Inherent Viscosity IV = 0.13 dl / g and melting range 200-
40 g of polyester at 220 ° C. (95% yield) are obtained.
その際インヒーレントビスコシチーＩＶ＝ηinhの測定
は、温度：３０℃、濃度：溶液１００ml中ポリエステル
0.５ｇ、溶媒：フエノール６０重量％及び１，１，２，
２−テトラクロルエタン４０重量％からなる混合溶媒の
条件で行なう。In that case, the measurement of inherent viscocity IV = η inh was as follows: temperature: 30 ° C., concentration: polyester in 100 ml of solution
0.5 g, solvent: 60% by weight of phenol and 1,1,2,
It is carried out under the condition of a mixed solvent consisting of 40% by weight of 2-tetrachloroethane.
実施例 ２ ジフエノールとして９，９−ビス（４−ヒドロキシフエ
ニル）−フルオレン３５ｇ（0.1モル）及びその溶解性
が悪いため溶媒としてイソプロパノール１４０mlを導入
した点を除き、実施例１の方法を繰り返した。Example 2 The method of Example 1 was repeated except that 35 g (0.1 mol) of 9,9-bis (4-hydroxyphenyl) -fluorene was used as the diphenol and 140 ml of isopropanol was introduced as the solvent due to its poor solubility. .
インヒーレントビスコシチーＩＶ＝0.１５ｄｌ／ｇ及び
融解範囲２００〜２２０℃の低分子量ポリエステル４７
ｇ（収率９7.９％）が得られた。Inherent Viscosity IV = 0.15 dl / g and melting range 200-220 ° C. low molecular weight polyester 47
g (yield 97.9%) was obtained.
実施例 ３ ジフエノールとして２，２−ビス（４−ヒドロキシフエ
ニル）−プロパン２３ｇ（0.１モル）を導入した点を除
き、実施例２の方法を繰り返した。Example 3 The method of Example 2 was repeated except that 23 g (0.1 mol) of 2,2-bis (4-hydroxyphenyl) -propane was introduced as the diphenol.
インヒーレントビスコシチーＩＶ＝0.１４ｄｌ／ｇ及び
融解範囲１４０〜１６０℃の低分子量ポリエステル３４
ｇ（収率９4.７％）が得られた。Inherent Viscosity IV = 0.14 dl / g and melting range 140-160 ° C. low molecular weight polyester 34
g (yield 94.7%) was obtained.
実施例 ４ 実施例１に記載されているのと同様にして、水性相とし
て溶液Ａを１，１−ビス（４−ヒドロキシフエ ２３2.
４ｇ ニル）−１−フエニルエタン （0.８モル） ＮａＯＨ ７0.４ｇ （1.７６モル） 水 9.６０ イソプロパノール 1.０６ 及び ベンジルトリエチルアンモニウム 4.８ｇ クロライド （0.０２１モル） から、そして有機液体相として溶液Ｂを、イソフタル酸
クロライドとテレフタ １６2.４ｇ （0.８モル） ル酸クロライドの５０：５０の混合物 １，２−ジクロルエタン 4.４ 及び １０モル％の酸クロライドの過剰分 としてのイソフタル酸クロライドと １6.２ｇ テレフタル酸クロライドの５０： （0.０８モル） ５０の混合物 から調製する。Example 4 Solution A was used as an aqueous phase in the same manner as described in Example 1 with 1,1-bis (4-hydroxyphene 232.
4 g nil) -1-phenylethane (0.8 mol) NaOH 70.4 g (1.76 mol) water 9.60 isopropanol 1.06 and benzyltriethylammonium 4.8 g chloride (0.021 mol) and then an organic liquid Solution B as the phase, isophthalic acid chloride and terephthale 162.4 g (0.8 mol) 50:50 mixture of acid chlorides 1,2-dichloroethane 4.4 and isophthalic acid as excess of 10 mol% acid chloride Prepared from a 50: (0.08 mole) 50 mixture of acid chloride and 16.2 g terephthalic acid chloride.
図に示した装置を用いて低分子量ポリエステルを連続的
に製造するために、約１７℃で冷却した溶液Ａ及びＢを
容器１及び２にみたす。計量ポンプ５，５′を使用して
水性相として溶液Ａを０．３４４／分の量で、有機液
体相として溶液Ｂを0.２６５／分の量で共に連続的に
分散装置７に供給する。分散装置７の中で上記の二つの
相は温度が約２６℃となり細かい分散体に変化する。次
いでこの分散体を、重縮合反応の進行の間に分散状態を
維持する静的ミキサー１０へ通し、最後に水が入れてあ
る容器１４の中へ激しく撹拌しながら導入する。用意し
た溶液Ａ及びＢがなくなつた後、容器１４中で放置して
二つの相を分離させ、弱アルカリ性の水性相をすてる。For continuous production of low molecular weight polyesters using the apparatus shown, solutions A and B cooled at about 17 ° C. are filled in vessels 1 and 2. Solution A as an aqueous phase in an amount of 0.344 / min and solution B as an organic liquid phase in an amount of 0.265 / min are continuously supplied to a dispersion device 7 using metering pumps 5, 5 '. . In the disperser 7, the above two phases have a temperature of about 26 ° C. and change into a fine dispersion. The dispersion is then passed through a static mixer 10 which maintains the dispersion during the course of the polycondensation reaction and is finally introduced with vigorous stirring into a vessel 14 containing water. After the prepared solutions A and B have disappeared, the solution is left in the container 14 to separate the two phases, and the weakly alkaline aqueous phase is rinsed.
次いで有機液体相中に生成した低分子量ポリエステルの
沈殿及び処理を実施例１に記載したのと同様にして行な
つた。得られたポリエステルはインヒーレントビスコシ
チーＩＶ＝0.１８ｄｌ／ｇ及び融解範囲２１０〜２２５
℃を有する。The low molecular weight polyester formed in the organic liquid phase was then precipitated and treated as described in Example 1. The resulting polyester has an inherent viscocity IV of 0.18 dl / g and a melting range of 210-225.
Having a ° C.
本製造方法の実施例の変法においては、酸クロライドの
過剰量は溶液Ａ及びＢ相対的流量を変化させることによ
り変化させた。その際酸クロライドの過剰量が増大する
につれてインヒーレントビスコシチーは減少し逆行する
ことが明らかになつた。さらに、約0.６〜0.７ｄ／ｇ
よりも小さいインヒーレントビスコシチー（ＩＶ）範囲
においてポリエステルの融解温度は広い範囲でＩＶ値の
増加と比例して増加することがわかつた。従つてＩＶ値
の対応する調節により例えば低分子量ポリエステルの特
定の応用に対しと最適の融解温度値を得ることができ
る。In a modification of the example of the present production method, the excess amount of acid chloride was changed by changing the relative flow rates of solutions A and B. It was revealed that as the excess amount of acid chloride increased, the inherent viscocity decreased and went backward. Furthermore, about 0.6-0.7 d / g
It has been found that in the smaller incoherent viscosity (IV) range, the melting temperature of polyesters increases over a wide range in proportion to increasing IV values. Therefore, by correspondingly adjusting the IV value, optimum melting temperature values can be obtained, for example for specific applications of low molecular weight polyesters.
一般に本発明に従う方法においては、インヒーレントビ
スコシチーの変化は、温度、水性相の添加速度、可溶化
剤及び／又は相間移動触媒の濃度を変化させることによ
り及び場合により補足的に有機液体相へもまた相間移動
触媒を添加することにより達成される。Generally, in the process according to the invention, the change in inherent viscosity is brought about by changing the temperature, the rate of addition of the aqueous phase, the concentration of the solubilizer and / or the phase transfer catalyst and optionally additionally to the organic liquid phase. Is also achieved by adding a phase transfer catalyst.
産業上の利用性 本発明に従う低分子量ポリエステルは重合方法、例えば
アミン、アミド、イミド等との一般的重縮合反応におい
て、また例えばエポキシド、ノルボルネン等との重付加
反応において出発原料として有利に利用することができ
る。INDUSTRIAL APPLICABILITY The low molecular weight polyester according to the present invention is advantageously used as a starting material in a polymerization method, for example, general polycondensation reaction with amines, amides, imides and the like, and also in polyaddition reaction with epoxides, norbornenes and the like. be able to.
図面は本発明に従う方法の好ましい態様を実施するため
の装置の流れ図を示す。 １…容器 ７…分散装置 ２…容器 ８…出口 ３…導管 ９…導管 ４…導管 １０…静的ミキサー ５…計量ポンプ １１…出口 ５′…計量ポンプ １２…導管 ６…流量計 １３…撹拌機 ６′…流量計 １４…容器The drawing shows a flow chart of an apparatus for carrying out a preferred embodiment of the method according to the invention. DESCRIPTION OF SYMBOLS 1 ... Container 7 ... Dispersion device 2 ... Container 8 ... Outlet 3 ... Conduit 9 ... Conduit 4 ... Conduit 10 ... Static mixer 5 ... Metering pump 11 ... Outlet 5 '... Metering pump 12 ... Conduit 6 ... Flow meter 13 ... Stirrer 6 '... Flowmeter 14 ... Container
Claims (2)
って、該鎖構成員中構成員Ｘとして本質的に構造 又は を有し、構成員Ｙとして本質的に構造 式中、Ｒは 又は である、 を有し、0.08〜0.35ｄｌ／ｇ、好ましくは0.1〜0.25ｄ
ｌ／ｇのインヒーレントビスコシチー（測定条件、温
度：３０℃、濃度：溶液１００ｍｌ中ポリエステル０．
５ｇ、溶媒：フエノール６０重量％及び１，１，２，２
−テトラクロルエタン４０重量％からなる混合溶媒）を
有する低分子量ポリエステル。1. A formula A low molecular weight polyester consisting essentially of the chain members of Or And essentially a structure as member Y In the formula, R is Or And has 0.08 to 0.35 dl / g, preferably 0.1 to 0.25 d
Inherent viscocity of 1 / g (measurement conditions, temperature: 30 ° C., concentration: polyester in 100 ml of solution:
5 g, solvent: 60% by weight of phenol and 1,1,2,2
A low molecular weight polyester with a mixed solvent of 40% by weight of tetrachloroethane).
構造Ｘ１を有し、鎖構成員の７０〜３０％が構成員Ｘと
して構造Ｘ２を有する特許請求の範囲第１項記載の低分
子量ポリエステル。2. 30 to 70% of the chain members have the structure X 1 as member X and 70 to 30% of the chain members have the structure X 2 as member X. The low molecular weight polyester described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60271701A JPH06842B2 (en) | 1985-12-04 | 1985-12-04 | Low molecular weight polyester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60271701A JPH06842B2 (en) | 1985-12-04 | 1985-12-04 | Low molecular weight polyester |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19774793A Division JPH06256487A (en) | 1993-07-16 | 1993-07-16 | Preparation of low-molecular-weight polyester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62132917A JPS62132917A (en) | 1987-06-16 |
| JPH06842B2 true JPH06842B2 (en) | 1994-01-05 |
Family
ID=17503639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60271701A Expired - Lifetime JPH06842B2 (en) | 1985-12-04 | 1985-12-04 | Low molecular weight polyester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06842B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5614526A (en) * | 1979-07-17 | 1981-02-12 | Mitsubishi Gas Chem Co Inc | Production of low-molecular aromatic dihydroxy ester |
| US4314051A (en) * | 1980-05-05 | 1982-02-02 | Union Carbide Corporation | Process for preparing polyarylates |
-
1985
- 1985-12-04 JP JP60271701A patent/JPH06842B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62132917A (en) | 1987-06-16 |
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