JPS63218730A - Purification of polycarbonate granules - Google Patents
Purification of polycarbonate granulesInfo
- Publication number
- JPS63218730A JPS63218730A JP5205087A JP5205087A JPS63218730A JP S63218730 A JPS63218730 A JP S63218730A JP 5205087 A JP5205087 A JP 5205087A JP 5205087 A JP5205087 A JP 5205087A JP S63218730 A JPS63218730 A JP S63218730A
- Authority
- JP
- Japan
- Prior art keywords
- solvent
- polycarbonate
- granules
- water
- slurry
- 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.)
- Granted
Links
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 40
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 40
- 239000008187 granular material Substances 0.000 title abstract description 26
- 238000000746 purification Methods 0.000 title abstract description 3
- 239000002002 slurry Substances 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 150000004045 organic chlorine compounds Chemical class 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000002904 solvent Substances 0.000 abstract description 39
- 125000001309 chloro group Chemical group Cl* 0.000 abstract description 9
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 abstract description 4
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000001035 drying Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 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 4
- 230000000694 effects Effects 0.000 description 4
- 230000004927 fusion Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- URFNSYWAGGETFK-UHFFFAOYSA-N 1,2-bis(4-hydroxyphenyl)ethane Natural products C1=CC(O)=CC=C1CCC1=CC=C(O)C=C1 URFNSYWAGGETFK-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 description 1
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008202 granule composition Substances 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/16—Auxiliary treatment of granules
- B29B2009/168—Removing undesirable residual components, e.g. solvents, unreacted monomers; Degassing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ポリカーボネートの有機塩素化合物（以下溶
剤という）溶液を濃縮ゲル化又は、非溶剤、貧溶剤と接
触せしめて得られる粉粒体を、要すれば通常の脱溶剤法
例えば、熱水処理、乾燥処理或は、両者組合せによる処
理を行なった後に水スラリー状態で加熱することにより
塩素原子を殆ど含有しないポリカーボネート粉粒体を得
る精製方法に関する。Detailed Description of the Invention (Industrial Field of Application) The present invention is directed to a powder or granular material obtained by concentrating a polycarbonate organic chlorine compound (hereinafter referred to as a solvent) solution or contacting it with a non-solvent or a poor solvent. A purification method for obtaining polycarbonate powder containing almost no chlorine atoms by carrying out a conventional solvent removal method, if necessary, such as hot water treatment, drying treatment, or a combination of both, followed by heating in a water slurry state. Regarding.
（従来技術）
溶液法により得られたポリカーボネート溶液から溶剤を
除去してポリカーボネート粉粒体などを得る方法は種々
提案されている。例えば、熱水又は水蒸気と接触させて
フレーク状又は粒状化せしめる方法（特公昭３６−１１
２３１．同４０−９８４３．同４５−９８７５、特開昭
４８−４３７５２．同５４−１２．２３９３号公報）。(Prior Art) Various methods have been proposed for obtaining polycarbonate powder by removing the solvent from a polycarbonate solution obtained by a solution method. For example, a method of forming flakes or granules by contacting with hot water or steam (Japanese Patent Publication No. 36-11
231. 40-9843. 45-9875, Japanese Unexamined Patent Publication No. 48-43752. Publication No. 54-12.2393).
濃縮或は冷却によってゲル化粒状体とする方法（特公昭
３６−２１０３３．同３８−２２４９７．同４０−１２
３７９゜同４５−９８７５．同４７−４１４２１．特開
昭５１−４１０４８号公報）、非溶剤、貧溶剤によるゲ
ル化又は特殊な押出機に供給して溶剤を蒸発、乾燥させ
最終的には溶融物にする方法（特公昭４８−２２８４０
．同５５−１２９８号公報）等が知られている。Method of forming gelled granules by concentration or cooling (Japanese Patent Publications No. 36-21033, No. 38-22497, No. 40-12)
379゜45-9875. 47-41421. JP-A No. 51-41048), gelation using a non-solvent or poor solvent, or feeding to a special extruder to evaporate the solvent, dry it, and finally form a melt (Japanese Patent Publication No. 48-22840)
．． Publication No. 55-1298) and the like are known.
これらの方法の中で、押出機によって溶融物にする以外
の方法によって得られる粉粒体（フレークも含む）は、
なお、多くの溶剤を含有しているので、約１００℃の熱
水に接触させたり、更には溶剤の沸点以上の熱風乾燥な
どの方法によって、溶剤を除去することが行なわれてい
る。Among these methods, powders (including flakes) obtained by methods other than melting with an extruder are
Since it contains a large amount of solvent, the solvent is removed by contacting it with hot water at about 100°C or drying with hot air at a temperature higher than the boiling point of the solvent.
しかしながら、得られる粉粒体は、なお数百〜数千ｐｐ
ｍの塩素原子に相当する溶剤を含有するので、減圧ベン
ト付押出機によってペレット化すると同時に溶剤の除去
が行なわれているが、それでもなお、ペレット中に数＋
ｐｐ−の塩素原子に相当する溶剤を含有することが多い
。このように多量の溶剤を含有するポリカーボネートを
、空気の存在下で１００℃以上に加熱する方法では、溶
剤が分解して装置を腐食し、その除虫ずる重金属の塩化
物がポリカーボネートの分解を促進したり、ポリカーボ
ネート中に微粒子状に分散して品質の低下をもたらす。However, the obtained powder and granules still contain several hundred to several thousand pp.
Since the solvent contains a number of chlorine atoms in the pellets, the solvent is removed at the same time as pelletizing using an extruder with a vacuum vent.
It often contains a solvent corresponding to pp- chlorine atoms. In this method of heating polycarbonate containing a large amount of solvent to over 100°C in the presence of air, the solvent decomposes and corrodes the equipment, and the heavy metal chloride that removes insects accelerates the decomposition of the polycarbonate. or dispersed in the form of fine particles in polycarbonate, resulting in a decrease in quality.
また、数＋００１以上の塩素原子に相当する溶剤を含有
するポリカーボネートは、染顔料による着色の際に色ぶ
れをもたらし、種々の添加剤による改質や、繊維による
補強の際に、それらの効果を削減することがある。更に
溶融成形に於ては、金型の寿命を短縮する怖れがあり、
成形品のメタライジングやコーティングにおいてもトラ
ブルを惹起することがある。かくして、ポリカーボネー
ト中に残留する溶剤の除去が強く要望されている。In addition, polycarbonate containing a solvent equivalent to +001 or more chlorine atoms causes color blurring when colored with dyes and pigments, and when modified with various additives or reinforced with fibers, these effects are May be reduced. Furthermore, in melt molding, there is a risk of shortening the life of the mold.
It can also cause trouble in metallizing and coating molded products. Thus, there is a strong need to remove residual solvents from polycarbonate.
ポリカーボネート粉粒体に含有される溶剤を低減せしめ
る方法としては、０．１〜３０重量％の溶剤を含有する
ポリカーボネート粉粒体を容器中で直接水蒸気に接触せ
しめ、溶剤蒸気を含有する混合蒸気を排出することによ
って、ポリカーボネート粉粒体の溶剤を低下せしめる方
法（特開昭５４−１０１７７１号公報参照）が知られて
いるが、その低下限度は１００１）Ｉ）−程度であって
まだ充分とはいい難い。As a method for reducing the amount of solvent contained in polycarbonate powder, polycarbonate powder containing 0.1 to 30% by weight of solvent is brought into direct contact with water vapor in a container, and a mixed vapor containing solvent vapor is removed. A method is known in which the amount of solvent in polycarbonate powder is reduced by discharging it (see Japanese Patent Application Laid-Open No. 101771/1984), but the limit of the reduction is approximately 1001)I)-, which is still not sufficient. Good and difficult.
（発明の目的）
本発明の目的は、溶剤含有ポリカーボネート粉粒体から
溶剤を除去して、その含有量を塩素原子として約１０
Ｅｌｆ）−以下に低減せしめる方法を提供することにあ
る。(Object of the Invention) The object of the present invention is to remove the solvent from the solvent-containing polycarbonate powder and reduce the content to about 10% in terms of chlorine atoms.
An object of the present invention is to provide a method for reducing
（発明の構成）
本発明は、有機塩素化合物含有ポリカーボネート粉粒体
を、水スラリー状態で１５０″Ｃ以上に加熱することを
特徴とするポリカーボネート粉粒体の精製方法である。(Structure of the Invention) The present invention is a method for purifying polycarbonate powder, which is characterized by heating polycarbonate powder containing an organic chlorine compound to a temperature of 150''C or higher in a water slurry state.
本発明に於て使用されるポリカーボネートは、溶剤の存
在下で二価フェノール類にホスゲン又はジクロロホルメ
ートを常法により反応せしめて重合する溶液法により得
られる。The polycarbonate used in the present invention is obtained by a solution method in which dihydric phenols are reacted with phosgene or dichloroformate in the presence of a solvent and polymerized by a conventional method.
ここで使用される二価フェノールとしては、ハイドロキ
ノン、４．４−ジヒドロキシジフェニル。The dihydric phenol used here is hydroquinone, 4,4-dihydroxydiphenyl.
ビス（４−ヒドロキシフェニル）メタン、 １．１−
ビス（４−ヒドロキシフェニル）エタン、 ２．２−
ビス（４−ヒドロキシフェニル）プロパン（以下ＢＰＡ
という）、２．２−ビス（４−ヒドロキシフェニル）ブ
タン、１．１−ビス（４−ヒドロキシフェニル）シクロ
ヘキサン、１−７エニルー １．１−ビス（４−ヒドロ
キシフェニル）エタン、 ２．２−ビス（４−ヒドロ
キシフェニル）オクタン、ビス（４−ヒト０キシフエニ
ル）エーテル、ビス（４−ヒドロキシフェニル）ケトン
、ビス（４−ヒドロキシフェニル）スルフィド、ビス（
４−ヒドロキシフェニル）スルホン或は、これらの低級
アルキル或はハロゲン置換体などを例示することが出来
る。これら二価フェノールから得られるポリカーボネー
トは、ホモポリマー或はコポリマー更には、２種以上の
ポリカーボネートの混合物であってもよい。Bis(4-hydroxyphenyl)methane, 1.1-
Bis(4-hydroxyphenyl)ethane, 2.2-
Bis(4-hydroxyphenyl)propane (hereinafter referred to as BPA)
), 2.2-bis(4-hydroxyphenyl)butane, 1.1-bis(4-hydroxyphenyl)cyclohexane, 1-7enyl-1.1-bis(4-hydroxyphenyl)ethane, 2.2- Bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)sulfide, bis(
Examples include 4-hydroxyphenyl) sulfone and lower alkyl or halogen substituted products thereof. The polycarbonate obtained from these dihydric phenols may be a homopolymer, a copolymer, or a mixture of two or more types of polycarbonates.
ここでいう有機塩素化合物とは、例えばテトラクロロエ
タン、塩化メチレン、１，２−ジクロロエタン、クロロ
ホルム、 １，１．２− トリクロロエタン等でこれ
らの単独又は混合物である。The organic chlorine compound mentioned here is, for example, tetrachloroethane, methylene chloride, 1,2-dichloroethane, chloroform, 1,1,2-trichloroethane, etc., and these compounds may be used alone or in mixtures thereof.
反応により得られるポリカーボネートの溶剤溶液から、
ポリカーボネート粉粒体等を得るためには、前記のよう
な公知の方法を任意に採用することができる。From the polycarbonate solvent solution obtained by reaction,
In order to obtain polycarbonate powder or the like, any of the known methods described above can be employed.
本発明方法で使用するポリカーボネートの粉粒体（以下
供給粉粒体と称する）の形状および大きさは特に制限さ
れないが、スラリー化の容易さから平均粒径０．１〜１
０ｍの球状又はそれに近い形状であることが望ましく、
溶剤脱離の容易さから多少ポーラスであることが好まし
い。The shape and size of the polycarbonate powder (hereinafter referred to as supplied powder) used in the method of the present invention are not particularly limited, but from the viewpoint of ease of slurry formation, the average particle size is 0.1 to 1.
It is desirable to have a spherical shape of 0 m or a shape close to it,
It is preferable that the material be somewhat porous for ease of solvent removal.
供給粉粒体に含まれる溶剤層は塩素原子として約ｉｏ
ｐｐｍ〜約３重量％であることが望ましい。溶剤の含有
量が高過ぎるときは、予め８０〜９５℃の熱水に接触せ
しめて、溶剤の含有量を下げておくことが望ましい。少
量の貧溶剤或は非溶剤を同時に含有することは差支えな
い。The solvent layer contained in the supplied powder and granules contains about io as chlorine atoms.
ppm to about 3% by weight is desirable. When the content of the solvent is too high, it is desirable to lower the content of the solvent by bringing it into contact with hot water of 80 to 95°C in advance. There is no problem in containing a small amount of poor solvent or non-solvent at the same time.
本発明方法では、ポリカーボネートの供給粉粒体は水ス
ラリー状態で加熱される。従って、該粉粒体は溶剤から
分離されたままの未乾燥状態であってもよく、また、前
記のように熱水に接触させたままの状態であってもよい
。もちろん、乾燥状態であっても差支えない。これらの
粉粒体は、水と撹拌されたスラリー状にされる。この場
合、スラリー中の該粉粒体の濃度は取扱の容易さから約
２０〜４０重量％であることが望ましいが、この範囲に
限定されるものではない。スラリーは固液分離を避ける
ために、撹拌下におくことが望ましい。In the method of the present invention, the supplied polycarbonate powder is heated in a water slurry state. Therefore, the granular material may be in an undried state separated from the solvent, or may be kept in contact with hot water as described above. Of course, there is no problem even if it is in a dry state. These powders are stirred with water to form a slurry. In this case, the concentration of the granular material in the slurry is preferably about 20 to 40% by weight for ease of handling, but is not limited to this range. It is desirable to keep the slurry under agitation to avoid solid-liquid separation.
スラリーの加熱方法は、特に限定されず例えば、水蒸気
の直接吸込、ジャケットによる加熱等適宜採用すること
ができる。The method of heating the slurry is not particularly limited, and for example, direct suction of water vapor, heating using a jacket, etc. can be employed as appropriate.
ス°ラリ−の温度は１５０℃以上にすることが必要であ
る。 １５０℃未満では、目的を達成するのに長時間
を要するので実用的でない。また、設備およびエネルギ
ーのコストを考慮すると１８０℃以上の温度は得策では
ない。スラリーを１５０℃以上の温度に保持する時間は
、スラリー中の粉粒体の濃度。It is necessary that the temperature of the slurry be 150°C or higher. If the temperature is less than 150°C, it will take a long time to achieve the objective, so it is not practical. Further, in consideration of equipment and energy costs, a temperature of 180° C. or higher is not a good idea. The time the slurry is kept at a temperature of 150°C or higher depends on the concentration of the powder in the slurry.
粉粒体の溶剤含有量、スラリ一温度等によって変わるが
、一般的には約３時間で充分である。０．５時間以下で
は、本発明の効果を轡られないことが多い。Although it varies depending on the solvent content of the powder, slurry temperature, etc., approximately 3 hours is generally sufficient. When the time is 0.5 hours or less, the effects of the present invention are often not achieved.
以上に述べたように、本発明方法においてはポリカーボ
ネートの粉粒体は、耐圧容器中でスラリー状態で加熱さ
れる。粉粒体から排出される溶剤は、耐圧のコンデンサ
ーを通って、受器に貯留される。As described above, in the method of the present invention, polycarbonate powder is heated in a slurry state in a pressure-resistant container. The solvent discharged from the powder passes through a pressure-resistant condenser and is stored in a receiver.
加熱処理を終ったスラリーは、１００℃以下に冷却され
、水分と分離された後乾燥されるか、或は冷却せずにフ
ラッシュさせてもよい。The slurry that has undergone heat treatment may be cooled to 100° C. or lower, separated from moisture, and then dried, or may be flashed without cooling.
これらの一連の操作は、回分式でも連続式でも実施する
ことができる。These series of operations can be performed either batchwise or continuously.
（発明の効果）
ポリカーボネート粉粒体中の溶剤は、高温、長時間の乾
燥によっても低減せしめることができるが、本発明方法
のように溶剤に係る塩素原子を１゜ｐｐｍ以下に低減せ
しめるには、１５０℃以上の温度に数時間以上保持する
ことが必要である。しかしながら、かかる条件下でポリ
カーボネート粉粒体をそのまま処理すると、撹拌下でも
粉粒体間の融着や粉粒体と容器内壁の融着が生じて種々
のトラブルの原因になるのみならず、空気酸化によるポ
リカーボネートの劣化による品質の低下を惹起する。し
かるに、本発明方法によるときは、ポリカーボネート粉
粒体は水スラリー状態にあるため、１５０℃以上に加熱
しても相互融着や器壁との融着は起らず、また空気酸化
による劣化も生じない。(Effect of the invention) The amount of solvent in the polycarbonate powder can be reduced by drying at high temperature for a long time, but it is difficult to reduce the chlorine atoms in the solvent to 1 ppm or less as in the method of the present invention. , it is necessary to maintain the temperature at 150° C. or higher for several hours or more. However, if polycarbonate powder is processed as it is under such conditions, it will not only cause various troubles such as fusion between the powder and the inner wall of the container even under stirring, but also cause air leakage. This causes a decrease in quality due to deterioration of polycarbonate due to oxidation. However, when using the method of the present invention, since the polycarbonate powder is in a water slurry state, even when heated to 150°C or higher, there is no mutual fusion or fusion with the vessel wall, and there is no deterioration due to air oxidation. Does not occur.
更に驚くべきことに、ポリカーボネート中に残存した未
反応の二価フェノール、末端停止剤、Ｎａイオン、（Ｊ
イオンが水層に移行してポリカーボネートの精製が行な
われるなどは、全く予想しえない効果である。かくして
、本発明方法によって得られ°るポリカーボネート粉粒
体は、塩素原子の濃度が１０ ｐｐｍ以下に低下してい
るので（従来技術）の項で述べた問題は殆ど解消され、
―れた材料として情報記録用ディスク材料、レンズなど
の光学的用途を始め広範囲の用途に使用することができ
る。Even more surprisingly, unreacted dihydric phenol, terminal capping agent, Na ion, (J
The fact that ions move into the water layer and purify the polycarbonate is a completely unexpected effect. Thus, in the polycarbonate powder obtained by the method of the present invention, the concentration of chlorine atoms is reduced to 10 ppm or less, so the problems described in the section (prior art) are almost eliminated.
It can be used in a wide range of applications, including optical applications such as disc materials for information recording and lenses.
以下に溶剤として塩化メチレンを使用した場合の実施例
を挙げて本発明方法を詳述する。The method of the present invention will be described in detail below with reference to examples in which methylene chloride is used as the solvent.
実施例１
約７０℃の温水１旦の入ったニーダ−に、ビスフェノー
ルＡ（ＳＰＡ）とホスゲンから通常の溶剤法により得た
ポリカーボネート（平均分子量２５．０００） ２０重
量％の精製された塩化メチレン溶液３ｆを、３ Ｋｇ／
ｄ蒸気と共に徐々に往側し約４０分でゲル化粗砕し粒状
体とした。この粒状体混合物は、ポリカーボネート３６
重量％、塩化メチレン３０重量％、水２４重量％であっ
た。この粒状体混合物を撹拌機付き蒸留槽に入れ、水を
加えてポリカーボネートと水の合計量を基準にして、ポ
リカーボネートが約３０重量％の水スラリーとして蒸気
を吹込みながら９０〜９５℃に保ち、塩化メチレンを留
出させながら１時間処理後脱水した。榊られた粒状体は
、ポリカーボネート９０重量％、水Ｓｔ量％。Example 1 A 20% by weight purified methylene chloride solution of polycarbonate (average molecular weight 25,000) obtained from bisphenol A (SPA) and phosgene by a conventional solvent method was placed in a kneader containing hot water at about 70°C. 3f, 3 kg/
The mixture was gradually sent out together with steam and gelled and crushed into granules in about 40 minutes. This granule mixture is made of polycarbonate 36
The content was 30% by weight of methylene chloride and 24% by weight of water. This granular mixture is placed in a distillation tank equipped with a stirrer, water is added to form a water slurry containing approximately 30% by weight of polycarbonate based on the total amount of polycarbonate and water, and maintained at 90 to 95°C while blowing steam. The mixture was treated for 1 hour while distilling off methylene chloride, and then dehydrated. The sanded granules contained 90% by weight of polycarbonate and % of water St.
塩化メチレン２重量％であった（以下この粒状体を粒状
体Ａという）。粒状体Ａ ０．４Ｋｇと水０．９４１を
２すのオートクレーブに入れ、１００ ｒｌ）Ｉの撹拌
下マントルヒータで１７０℃に加熱した塩化メチレンを
留出させながら２時間処理後取出し、１１０℃１時間常
圧乾燥後、螢光Ｘ線分析計にて塩素原子（以下Ｃｌとい
う）の分析を行なったがＣＩは検出されなかった。The content of methylene chloride was 2% by weight (hereinafter, this granule will be referred to as granule A). 0.4 kg of granular material A and 0.941 kg of water were placed in a 2-cup autoclave, heated to 170°C with a mantle heater under stirring at 100 rl)I, treated for 2 hours while distilling methylene chloride, and then taken out and heated to 110°C. After drying at normal pressure for a period of time, chlorine atoms (hereinafter referred to as Cl) were analyzed using a fluorescent X-ray analyzer, but no CI was detected.
また分離した水を紫外線分光分析計、イオンクロマト分
析計にて分析した結果ＢＰＡ、末端停止剤、Ｎａイオン
、 ＣＩイオンが検出された。粒状体には造塊現象、平
均分子量の低下はみられなかった。Furthermore, as a result of analyzing the separated water using an ultraviolet spectrometer and an ion chromatograph, BPA, terminal stopper, Na ion, and CI ion were detected. No agglomeration phenomenon or decrease in average molecular weight was observed in the granules.
実施例２
粒状体Ａ Ｏ１４に９と水０．８１を２文のオートクレ
ーブに入れ、１００ ｒｐｍの撹拌下１６０℃で３時間
塩化メチレンを留出させながら処理した後粒状体を取出
し、１１０℃で１時間常圧乾燥して螢光Ｘ線分析計にて
ＣＩ分析した結果３ １）ｌ）ｌでありた。水層の分析
結果は実施例１と同様でありた。また、平均分子量の低
下、造塊現象はみられ、なかった。Example 2 Granular material A 9 in O14 and 0.81 ml of water were placed in a 2-liter autoclave, stirred at 100 rpm, and treated at 160°C for 3 hours while distilling methylene chloride.Then, the granular material was taken out and heated at 110°C. After drying under normal pressure for 1 hour, CI analysis was performed using a fluorescent X-ray analyzer, and the result was 31)l)l. The analysis results of the aqueous layer were the same as in Example 1. Further, no decrease in average molecular weight or agglomeration phenomenon was observed.
実施例３
粒状体Ａを１３０℃で５時間減圧乾燥したもののＣＩは
３００ ｐｐｍであった。この粒状体を粒状体Ｂとする
。Example 3 The CI of granules A dried under reduced pressure at 130° C. for 5 hours was 300 ppm. This granular material is referred to as granular material B.
粒状体８０．３Ｋｇと水０．７４２を実施例１のオート
クレーブにて１６０℃１．５時間同様に処理後、同様に
乾燥しＣＩ分析した結果３ ｐｐｍであった。また、
平均分子量の低下、造塊現象はみられなかった。80.3 kg of granules and 0.742 kg of water were treated in the same manner as in Example 1 at 160° C. for 1.5 hours, then dried in the same manner and subjected to CI analysis, and the result was 3 ppm. Also,
No decrease in average molecular weight or agglomeration phenomenon was observed.
更に、水層の分析結果は実施例１と同様であった。Furthermore, the analysis results of the aqueous layer were the same as in Example 1.
実施例４
粒状体０．３Ｋｇ、水０．８１を実施例１のオートクレ
ーブに入れ、１５０℃で２時間同様に処理後乾燥した結
果、ＣＩは５１）Ｉ）ｌであった。平均分子量の低下、
造塊現象はみられなかった。更に水層の分析結果は実施
例１と同様であった。Example 4 0.3 kg of granules and 0.81 g of water were placed in the autoclave of Example 1, treated in the same manner at 150° C. for 2 hours, and then dried. As a result, the CI was 51)I)l. decrease in average molecular weight,
No agglomeration phenomenon was observed. Furthermore, the analysis results of the aqueous layer were the same as in Example 1.
手続補正書 昭和６２年 ４月に 日Procedural amendment In April 1986
Claims (1)
ー状態で１５０℃以上に加熱することを特徴とするポリ
カーボネート粉粒体の精製方法。A method for purifying polycarbonate powder, which comprises heating polycarbonate powder containing an organic chlorine compound to 150° C. or higher in a water slurry state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5205087A JPH0725873B2 (en) | 1987-03-09 | 1987-03-09 | Method for purifying powder of polycarbonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5205087A JPH0725873B2 (en) | 1987-03-09 | 1987-03-09 | Method for purifying powder of polycarbonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63218730A true JPS63218730A (en) | 1988-09-12 |
| JPH0725873B2 JPH0725873B2 (en) | 1995-03-22 |
Family
ID=12903984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5205087A Expired - Fee Related JPH0725873B2 (en) | 1987-03-09 | 1987-03-09 | Method for purifying powder of polycarbonate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725873B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6431690A (en) * | 1987-07-29 | 1989-02-01 | Mitsubishi Gas Chemical Co | Polycarbonate molding material for optical disk |
| EP0489361A2 (en) * | 1990-12-03 | 1992-06-10 | The Dow Chemical Company | Uniform distribution polycarbonate pellets |
| US9340646B2 (en) | 2011-07-12 | 2016-05-17 | Norner Ip As | Process for purifying poly (alkylene carbonate) |
-
1987
- 1987-03-09 JP JP5205087A patent/JPH0725873B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6431690A (en) * | 1987-07-29 | 1989-02-01 | Mitsubishi Gas Chemical Co | Polycarbonate molding material for optical disk |
| EP0489361A2 (en) * | 1990-12-03 | 1992-06-10 | The Dow Chemical Company | Uniform distribution polycarbonate pellets |
| US5187256A (en) * | 1990-12-03 | 1993-02-16 | The Dow Chemical Company | Uniform distribution polycarbonate pellet |
| US5414056A (en) * | 1990-12-03 | 1995-05-09 | The Dow Chemical Company | Uniform distribution polycarbonate pellets |
| US9340646B2 (en) | 2011-07-12 | 2016-05-17 | Norner Ip As | Process for purifying poly (alkylene carbonate) |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0725873B2 (en) | 1995-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4845193A (en) | Process for producing polycarbonate resin molding material having low particle content with vented extruder | |
| US4880896A (en) | Polycarbonate for disc substrate having low bisphenol content | |
| EP0499072B1 (en) | Process for producing granules of polycarbonate and composition thereof | |
| US4631338A (en) | Process for the isolation of thermoplastic polycarbonate from solution with vapor of benzene or alkylbenzene | |
| JPH04305414A (en) | Refining of polycarbonate and polyester carbonate waste | |
| JPS63218730A (en) | Purification of polycarbonate granules | |
| JP3290054B2 (en) | Chemical regeneration of polycarbonate | |
| KR920010145B1 (en) | Process for producing a resin having carbonate bonding | |
| JPS6354011B2 (en) | ||
| JPH07268092A (en) | Production of polycarbonate | |
| JP4567397B2 (en) | Process for obtaining aromatic dihydroxy compounds from waste aromatic polycarbonates | |
| JPS61250026A (en) | Production of water slurry of bead-like polycarbonate solid particles | |
| JP4364747B2 (en) | Process for obtaining aromatic dihydroxy compounds from waste aromatic polycarbonates | |
| JPH05310907A (en) | Method for removing residual solvent | |
| JPH0839551A (en) | Manufacture of polycarbonate resin molding material | |
| JPH06256498A (en) | Preparation of aromatic polycarbonate resin powder and granular body | |
| JP3196274B2 (en) | Method for producing polymer granules | |
| JP2002047350A (en) | Manufacturing method of polycarbonate resin powder | |
| JP2795558B2 (en) | Method for producing polymer granules | |
| JPH0532793A (en) | Production of granular polymer | |
| JP3183951B2 (en) | Method for removing residual solvent from polycarbonate powder | |
| JPH04306227A (en) | Production of molding material for optical molded article | |
| JPS60116412A (en) | Manufacture of polycarbonate resin granular body | |
| JPS6126571B2 (en) | ||
| JPH04189834A (en) | Production of polycarbonate granular substance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |