JPH03247603A - Coagulation of polymer latex and production of granular polymer - Google Patents
Coagulation of polymer latex and production of granular polymerInfo
- Publication number
- JPH03247603A JPH03247603A JP4266390A JP4266390A JPH03247603A JP H03247603 A JPH03247603 A JP H03247603A JP 4266390 A JP4266390 A JP 4266390A JP 4266390 A JP4266390 A JP 4266390A JP H03247603 A JPH03247603 A JP H03247603A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- latex
- screw
- graft
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 126
- 239000004816 latex Substances 0.000 title claims abstract description 48
- 229920000126 latex Polymers 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 238000005345 coagulation Methods 0.000 title description 19
- 230000015271 coagulation Effects 0.000 title description 19
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000000701 coagulant Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 24
- 229920000578 graft copolymer Polymers 0.000 claims description 23
- 230000001112 coagulating effect Effects 0.000 claims description 11
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 abstract description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011780 sodium chloride Substances 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 33
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000007711 solidification Methods 0.000 description 7
- 230000008023 solidification Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000002966 varnish Substances 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical class [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- -1 dimethylsiloxane Chemical class 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical class [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001417494 Sciaenidae Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 235000015115 caffè latte Nutrition 0.000 description 1
- 239000001110 calcium chloride Chemical class 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、重合体ラテックスの凝析方法および粉粒状重
合体の製造法に関し、より詳しくは、グラフト重合体の
ラテックスの凝析を同方向回転−軸部練機で実施し、粒
径か３０−〜５ｍｍ程度の粉粒状重合体を製造する方法
に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a method for coagulating a polymer latex and a method for producing a particulate polymer, and more specifically, the present invention relates to a method for coagulating a latex of a graft polymer in the same direction. This invention relates to a method for producing a powdery polymer having a particle size of about 30 to 5 mm by using a rotating shaft kneader.
乳化重合法などによって得られる重合体ラテックスは、
一般に粒子径か１μ以下の重合体粒子か乳化剤に覆われ
て水に分散浮遊した状態として存在し、粒子径か小さす
ぎるのでそのまま固液分離し、重合体を回収することは
難しい。このような重合体ラテックスから重合体を回収
する従来方法としては、噴霧乾燥機を使用して粉粒体と
して直接分離する方法と、重合体ラテックスに塩または
酸を混合して凝析させ、昇温加熱して固化させた後、脱
水乾燥して粉粒体として回収する方法とが多用されてき
た。Polymer latex obtained by emulsion polymerization method etc.
In general, polymer particles with a particle size of 1 μm or less exist in a suspended state covered with an emulsifier and dispersed in water, and because the particle size is too small, it is difficult to directly separate solid and liquid and recover the polymer. Conventional methods for recovering polymers from such polymer latex include direct separation as powder using a spray dryer, and coagulation by mixing salt or acid with polymer latex. A frequently used method is to heat the material to solidify it, then dehydrate and dry it to collect it as powder.
しかしながら、噴霧乾燥機を使用する方法は、多量の水
を伴なった重合体ラテックスをそのまま乾燥させるため
に蒸発させるへき水の量が多く乾燥エネルキーを多量に
必要とする、噴霧する液滴の大きさにむらか生しやすく
粒度分布が広くなる、粒子の大きさや嵩比重を制御する
ことが難しい、装置コストか高い等の問題点があった。However, the method of using a spray dryer requires a large amount of evaporated water and a large amount of drying energy to dry the polymer latex containing a large amount of water, and the size of the sprayed droplets is large. There are problems such as easy growth of grain size, wide particle size distribution, difficulty in controlling particle size and bulk density, and high equipment cost.
方、凝析剤で凝析し固化させる方法は、従来ラテックス
と凝析剤との混合を、攪拌機を備えた種型または塔型の
凝析固化装置を使用して実施していた。しかしなから、
弾性幹重合体の含有率か６０重量％以上であるグラフト
重合体のラテックスを凝析させる場合には、直径か Ｉ
ｃｍ以上の大きな重合体の固まりか生成しやすいという
問題点かあった。このように大きな凝析粒子か分散した
重合体スラリーは固液分離しやすく、安定性に欠ける。On the other hand, in the method of coagulating and solidifying with a coagulant, the latex and the coagulant have conventionally been mixed using a seed-type or tower-type coagulation and solidification apparatus equipped with a stirrer. However, because
When coagulating a graft polymer latex with an elastic backbone polymer content of 60% by weight or more, the diameter or I
There was a problem in that large polymer lumps of cm or more were likely to form. A polymer slurry in which large coagulated particles are dispersed is likely to undergo solid-liquid separation and lack stability.
特に、オバーフロー型式の種型混合機を用いて連続操作
を行う場合には、重合体スラリーのうち水相のみがオー
バーフローし凝析粒子か種型混合機内に溜り連続操作か
不可能になる。また、ハツチ式て凝析操作を行い凝析粒
子を回収した場合にも、粒子か大き過ぎるために脱水、
洗浄、乾燥なとの後処理工程で取扱いにくい重合体とし
てしか回収できないという欠点があった。In particular, when continuous operation is performed using an overflow type seed mixer, only the aqueous phase of the polymer slurry overflows and the coagulated particles accumulate in the seed mixer, making continuous operation impossible. In addition, even when coagulating particles are collected using a hatch type coagulation operation, the particles are too large and need to be dehydrated.
It has the disadvantage that it can only be recovered as a polymer that is difficult to handle during post-processing steps such as washing and drying.
また、弾性幹重合体の含有率が大きいグラフト重合体ラ
テックスでは、ラテックスと凝析剤を混合した直後、重
合体スラリーの見かけ粘度か一時的に著しく大きくなる
場合かある。このようなりラフト重合体ラテックスを種
型混合機で処理すると、連続操作を行う場合には重合体
スラリーか種型混合機からオーバーフロー排出されす凝
析操作か継続できない。特に、■プロセスの生産性を高
めるために凝析時に重合体スラリーの濃度を高めた場合
、■凝析粒子が粗大化するのを防止するために凝析温度
を下げた場合、あるいは■重合体中に残存する凝析剤量
を低減するために、凝析剤量の使用量を少なくした場合
、なとに重合体スラリーの見かけ粘度か大きくなりやす
い。しかしながら、上述の■〜■の条件設定は、不純物
を含まず取扱いやすい粉粒状重合体を経済的に生産する
ためには望ましいものであった。したがっで、従来用い
られた種型混合機で弾性幹重合体の含有率が高いグラフ
ト共重合体を凝析すると、不純物か多く取扱いにくい粉
粒状重合体しか製造できなかった。Further, in the case of a graft polymer latex having a high content of an elastic backbone polymer, the apparent viscosity of the polymer slurry may temporarily increase significantly immediately after mixing the latex and a coagulant. If such a raft polymer latex is treated in a seed mixer, the coagulation operation cannot be continued because the polymer slurry will be discharged as an overflow from the seed mixer in the case of continuous operation. In particular, ■ if the concentration of the polymer slurry is increased during coagulation to increase the productivity of the process, ■ if the coagulation temperature is lowered to prevent coagulated particles from becoming coarse, or ■ if the polymer slurry is When the amount of coagulant used is reduced in order to reduce the amount of coagulant remaining in the polymer slurry, the apparent viscosity of the polymer slurry tends to increase. However, the above-mentioned conditions (1) to (2) are desirable for economically producing a powdery polymer that does not contain impurities and is easy to handle. Therefore, when a graft copolymer with a high content of an elastic backbone polymer is coagulated using a conventional seed mixer, only a powdery polymer containing many impurities and difficult to handle can be produced.
本発明者等は、上記の問題点を解決するために鋭意検討
した結果、凝析装置として同方向回転軸混練機を使用す
ることにより、上記の問題点が解決されることを見い出
し、本発明を完成するにいたった。As a result of intensive studies to solve the above problems, the present inventors found that the above problems could be solved by using a co-rotating shaft kneader as a coagulation device, and the present invention was completed.
すなわち、本発明の重合体ラテックスの凝析方法は、弾
性幹重合体に硬質重合体を形成する四量体をグラフト重
合することにより得られたグラフト重合体で、その弾性
幹重合体の含有率か６０車量％以上であるグラフト重合
体のラテックスを凝析させるに際しで、該ラテックスと
凝析剤との混合を同方向回転二軸混練機で実施すること
を特徴とする。That is, the method for coagulating the polymer latex of the present invention is to obtain a graft polymer obtained by graft polymerizing a tetramer forming a hard polymer onto an elastic backbone polymer, and to obtain a graft polymer obtained by graft polymerizing a tetramer forming a hard polymer onto an elastic backbone polymer. When coagulating the latex of the graft polymer having a content of 60% or more by weight, the latex and the coagulant are mixed in a co-rotating twin-screw kneader.
また、本発明の粉粒状重合体の製造方法は、弾性幹重合
体に硬質重合体を形成する単量体をグラフト重合するこ
とにより得られたグラフト重合体で、その弾性幹重合体
の含有率か６０重量％以上であるグラフト重合体のラテ
ックスと凝析剤とを同方向回転二軸混練機で混合して凝
析し、得られた重合体スラリーを、該グラフト重合体の
ガラス転移温度（Ｔｇ）より１０℃低い温度（Ｔｇ−１
０） ℃以上て加熱処理する工程を有することを特徴と
する。In addition, the method for producing a powdery polymer of the present invention is a graft polymer obtained by graft polymerizing a monomer that forms a hard polymer to an elastic backbone polymer, and the content of the elastic backbone polymer is The latex of the graft polymer, which is 60% by weight or more, and the coagulant are mixed and coagulated in a co-rotating twin-screw kneader, and the obtained polymer slurry is mixed at the glass transition temperature of the graft polymer ( Tg-1
0) It is characterized by having a step of heat treatment at a temperature of 0.degree. C. or higher.
本発明の重合体ラテックスの凝析方法および粉粒状重合
体の製造方法は、重合体ラテックスと凝析剤との混合を
同方向回転二軸混練機て実施する。In the method for coagulating a polymer latex and the method for producing a powdery polymer of the present invention, a polymer latex and a coagulant are mixed using a co-rotating twin-screw kneader.
第１〜３図に、本発明の方法で使用する同方向回転二軸
混練機の一例を示す。1 to 3 show an example of a co-rotating twin-screw kneader used in the method of the present invention.
本発明の方法においては、バレル断面が８字形てスクリ
ューを二本官する二軸混練機を使用する。スクリューを
一本しか有さない混練機や単軸押出機では、凝析して得
られる重合体スラリーを搬送する能力に乏しく、また重
合体か閉塞しやすいので使用できない。In the method of the present invention, a twin-screw kneader with a barrel cross section of a figure 8 shape and two screws is used. A kneader or a single-screw extruder having only one screw cannot be used because it lacks the ability to convey the polymer slurry obtained by coagulation and the polymer tends to clog.
また、本発明の方法で使用する二軸混練機では、スクリ
ューの回転方向か同一で、スクリューにセルフクリーニ
ンク作用のある同方向回転二軸混練機を使用することか
必要である。スクリュー回転方向が異なる異方向回転二
軸混練機では、スクリューにセルフクリーニンク作用を
持たせるのか難しいため、重合体スラリー中の重合体が
スクリュー表面に付着しやすく、重合体が装置内に閉塞
して安定な運転か困難となる。Further, in the twin-screw kneading machine used in the method of the present invention, it is necessary to use a co-rotating twin-screw kneading machine in which the screws rotate in the same direction and the screws have a self-cleaning action. In a twin-screw kneader that rotates in different directions, it is difficult to make the screws self-cleaning, so the polymer in the polymer slurry tends to adhere to the screw surface, causing the polymer to clog the equipment. This makes stable operation difficult.
混練機に配置されるスクリューとしては、スクリュー断
面が第４図（ａ）のような二条ネジタイプや第４図（ｂ
）のような三条ネジタイプのものを使用することかでき
るか、装置のホールドアツプ量を大きくとれる二条ネジ
タイプの方が好ましい。The screws to be placed in the kneading machine are of the double-thread type with a screw cross section as shown in Figure 4(a), or of the screw type as shown in Figure 4(b).
) can be used, but a double thread type is preferable as it allows for a larger hold up of the device.
スクリューのエレメントは、一般にその機能から、■順
方向搬送、■逆方向搬送、■混練、■前記■と■の機能
を備える順送り混練、および■前記■と■の機能を備え
る逆送り混練の五種類に大別できる。第５図（ａ）〜（
ｅ）にこれら五種類のスクリューエレメントの代表的な
形状を示す。Screw elements generally have five functions based on their functions: ■Forward conveyance, ■Reverse conveyance, ■Kneading, ■Progressive kneading with the functions of ■ and ■ above, and ■Reverse feed kneading with the functions of ■ and ■ above. It can be roughly divided into types. Figure 5(a)-(
Representative shapes of these five types of screw elements are shown in e).
同方向回転二軸混練機内に重合体ラテックスおよび凝析
剤を供給する部分のスクリューエレメントは、順方向の
搬送機能を有する■順方向搬送または■順送り混練のエ
レメントを有することかてき、特に■順方向搬送のエレ
メントか望ましい。The screw element that supplies the polymer latex and coagulant into the co-rotating twin-screw kneader has a forward conveyance function or a forward kneading element, especially in the forward direction. Elements with directional conveyance are preferred.
同方向回転二軸混練機の長さは、重合体ラテックスおよ
び凝析剤の両者か供給された位置から重合体スラリーが
排出される位置まで距離をＬとし、スクリューの外径を
Ｄとすると、比Ｌ／Ｄか２以上であることが好ましい。The length of the co-rotating twin-screw kneader is as follows, where L is the distance from the position where both the polymer latex and coagulant are supplied to the position where the polymer slurry is discharged, and D is the outer diameter of the screw. It is preferable that the ratio L/D is 2 or more.
しかし、あまり長すぎると装置の製作か困難になるので
、比Ｌ／Ｄは４０以下、特に２０以下が望ましい。However, if the length is too long, it becomes difficult to manufacture the device, so the ratio L/D is desirably 40 or less, particularly 20 or less.
滞在時間か１台の二軸混練機だけでは不足する場合には
、２台以上の同方向回転二軸混練機を直列に接続して使
用するのが好ましい。また、二軸混練機の後にオーバー
フロー形式の混合槽を接続して使用することもてきる。If the residence time is insufficient for one twin-screw kneader, it is preferable to use two or more co-rotating twin-screw kneaders connected in series. It is also possible to use an overflow type mixing tank connected after the twin-screw kneader.
同方向回転二軸混練機としては、同方向回転二軸押出機
を使用することかできる。As the co-rotating twin-screw kneader, a co-rotating twin-screw extruder can be used.
スクリューの回転数は、スクリューによる混合効果を高
めるために、スクリューがバレル内面と接している部分
の速度か５ｃｍ／秒以上となるようにするのか望ましい
。スクリュー回転数の上限は装置の機械的強度から決定
されるか、通常２０００回転／分以Ｊとするのが望まし
い。The rotational speed of the screw is desirably set to 5 cm/sec or more at the portion where the screw is in contact with the inner surface of the barrel, in order to enhance the mixing effect of the screw. The upper limit of the screw rotation speed is determined from the mechanical strength of the device, and is preferably 2000 revolutions per minute or more.
製品である粉粒状重合体の粒子径は、同方向回転二軸混
練機の温度をＦげると小さくなる。また、スクリューと
して第５図中の混練機能のスクリューエレメント（（：
）を多くし、１昆錬を弓牟くすると粒子径は小さくなり
、スクリューの回転数を増加させると粒子径は小さくな
る。The particle size of the product powder/grain polymer becomes smaller when the temperature of the co-rotating twin-screw kneader is increased by F. In addition, as a screw, the screw element ((:
) is increased and 1 kunren is reduced, the particle size becomes smaller, and when the number of revolutions of the screw is increased, the particle size becomes smaller.
本発明において使用される重合体ラテックスは、弾性幹
重合体に硬質重合体を形成する単量体をグラフト重合す
ることにより得られたグラフト重合体で、かつその弾性
幹重合体の含有率が６０重量％以上のものである。６０
重量％未満のり′ラフト重合体に対しても本発明の方法
を適用することはり能であるか、凝析時のスラリーの見
がけ粘度の十昇かそれ程でもないので、本発明の方法を
採用する理由が乏しい。この重合体ラテックスは、通常
の乳化重合法によって製造されるものであり、乳化剤、
重合開始剤および他の重合助剤等を含んでもよい。The polymer latex used in the present invention is a graft polymer obtained by graft polymerizing a monomer that forms a hard polymer onto an elastic backbone polymer, and the content of the elastic backbone polymer is 60%. % by weight or more. 60
It is possible to apply the method of the present invention even to raft polymers with less than 10% by weight, and the apparent viscosity of the slurry during coagulation does not increase by more than 10%, so the method of the present invention is adopted. There is little reason to do so. This polymer latex is produced by a normal emulsion polymerization method, and includes an emulsifier,
It may also contain a polymerization initiator and other polymerization aids.
本発明において使用されるグラフト重合体ラテックスを
構成する弾性幹重合体としては、ブタジェン、イソプレ
ン、クロロプレン等のジエン系重合体ニブチルアクリレ
ート、オクチルアクリレート等のアルキル基の炭素数が
４〜１ｏのアク’）ル酸−Ｌステル系重合体：エチレン
ーブロビ１ノンー非共役ジエン共重合体ニジメチルシロ
キサン等を重合して得られるシリコーン系ゴム重合体：
およびそれらと共重合可能な単量体との共重合体か挙げ
られる。共重合可能な単量体としてはスチレン、α−メ
チルスチレン等の芳香族ビニル化合物：メチルメタクリ
レート、エチルメタクリレート等のメタクリル酸アルキ
ルエステル：メチルアクリレート、エチルアクリレート
等のアルキル基の炭素数が１〜３のアクリル酸アルキル
エステル：アクリロニトリル、メタクリロニトリル等の
シアン化ビニル化合物があげられる。Elastic backbone polymers constituting the graft polymer latex used in the present invention include diene polymers such as butadiene, isoprene, and chloroprene; ') Ruric acid-L ster type polymer: Ethylene-brobyl-non-nonconjugated diene copolymer Silicone rubber polymer obtained by polymerizing dimethylsiloxane, etc.:
and copolymers with monomers copolymerizable with them. Copolymerizable monomers include aromatic vinyl compounds such as styrene and α-methylstyrene; methacrylic acid alkyl esters such as methyl methacrylate and ethyl methacrylate; and methyl acrylate and ethyl acrylate in which the alkyl group has 1 to 3 carbon atoms. Acrylic acid alkyl esters include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile.
また、硬質重合体を形成する単量体としては、スチレン
、α−メチルスチレン等の芳香族ビニル化合物、メチル
メタクリレート、エチルメタクリレートおよびブチルメ
タクリレート等のメタクリル酸アルキルエステル；アク
リロニトリル、メタクリロニトリル等のシアン化ビニル
化合物、塩化ビニル、臭化ビニル等のハロゲン化ビニル
化合物等かあげられる。これらの単量体は単独あるいは
２種以上を用いて使用される。なお、硬質重合体の量は
５重量％以上であることか好ましい。５重量％未満ては
、グラフト重合体としての性能の発揮か不十分となりや
すい。In addition, monomers forming the hard polymer include aromatic vinyl compounds such as styrene and α-methylstyrene, methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; cyanogens such as acrylonitrile and methacrylonitrile. Examples include vinyl chloride compounds, vinyl chloride, vinyl bromide, and other halogenated vinyl compounds. These monomers may be used alone or in combination of two or more. Note that the amount of the hard polymer is preferably 5% by weight or more. If it is less than 5% by weight, the performance as a graft polymer is likely to be insufficient.
本発明の方法て使用する凝析剤に関しては何ら制約条件
はなく、通常の凝析剤を使用することかできる。例えば
塩化ナトリウム、塩化カルシウム、塩化マグネシウム、
硫酸ナトリウム、硫酸アルミニウム、硫酸曲鉛、硫酸マ
グネシウム、炭酸ナトリウム、炭酸水素ナトリウム、塩
化アンモニウム、カリミョウバン等の金属塩類、硫酸、
塩酸、リン酸、硝酸、炭酸、酢酸等の酸類、メタノール
、エタノール等のアルコール類かあげられ、それらを単
独または混合して用いることかできる。添加量は特に限
定されず、通常は重合体ラテックスの固形分に対して約
０．０５〜５０重量％となる量である。好ましくは約０
．１〜２０重量％である。There are no restrictions on the coagulant used in the method of the present invention, and any conventional coagulant may be used. For example, sodium chloride, calcium chloride, magnesium chloride,
Metal salts such as sodium sulfate, aluminum sulfate, bent lead sulfate, magnesium sulfate, sodium carbonate, sodium bicarbonate, ammonium chloride, potassium alum, sulfuric acid,
Examples include acids such as hydrochloric acid, phosphoric acid, nitric acid, carbonic acid, and acetic acid, and alcohols such as methanol and ethanol, and these may be used alone or in combination. The amount added is not particularly limited, and is usually about 0.05 to 50% by weight based on the solid content of the polymer latex. Preferably about 0
．． It is 1 to 20% by weight.
重合体ラテックスに凝析剤を添加すると、重合体ラテッ
クスの乳化状態か破壊され重合体ラテックスに乳化分散
していた重合体粒子か凝集して凝集体粒子（以下、これ
を「凝析粒子」と略記する）を形成し、この凝析粒子か
重合体ラテ、ンクスの分散媒であった水に分散しスラリ
ー状となる（以下、これを「重合体スラリー」と呼ぶ）
。When a coagulant is added to a polymer latex, the emulsified state of the polymer latex is destroyed, and the polymer particles that have been emulsified and dispersed in the polymer latex are aggregated into aggregate particles (hereinafter referred to as "coagulated particles"). The coagulated particles form a slurry (hereinafter referred to as "polymer slurry") when dispersed in water, which was the dispersion medium for the polymer latte.
.
凝析に必要な時間は非常に短く、通常平均滞在時間とし
て０．０５分〜１時間である。０．０５分未満ては凝析
か不完全になり、未凝析のラテックスが次の工程に流入
して造粒が不安定になりやすいので、好ましくない。１
時間以上にすると、装置か過大となるので好ましくない
。The time required for coagulation is very short, usually with an average residence time of 0.05 minutes to 1 hour. If the time is less than 0.05 minutes, the coagulation will be incomplete and the uncoagulated latex will flow into the next step, making the granulation unstable, which is not preferable. 1
Exceeding the time limit is not preferable because the device will become too large.
重合体ラテックス中の重合体重量は、重合体ラテックス
を凝析剤で凝析し、さらに温度を上げ固化処理して得た
重合体を乾燥し、重合体の重量を測定することにより求
めることかできる。このような方法で得た重合体重量に
は乳化重合時に加えた乳化剤や開始剤等の重合助剤も含
まれる。本発明ではこれら乳化剤や重合助剤を含んだ重
合体を造粒するので、全混合物中の重合体の重量割合を
算出する場合の重合体重量として上述の方法で求めた重
合体重量を用いる。このような重合体重量は、慣用的に
重合体中の固形分と呼ばれている。The weight of the polymer in the polymer latex can be determined by coagulating the polymer latex with a coagulant, then drying the resulting polymer by increasing the temperature and solidifying it, and measuring the weight of the polymer. can. The polymer weight obtained by such a method also includes polymerization aids such as emulsifiers and initiators added during emulsion polymerization. In the present invention, since a polymer containing these emulsifiers and polymerization aids is granulated, the polymer weight determined by the method described above is used as the polymer weight when calculating the weight proportion of the polymer in the entire mixture. Such polymer weight is conventionally referred to as the solids content in the polymer.
本発明の方法においては凝析後の全混合物中の重合体の
割合を１０〜７０重量％の範囲とするのか望ましい。全
混合物中の重合体の割合か１０重量％未満では、同一の
装置で少量の重合体しか処理てきないのて好ましくない
。逆に全混合物中の重合体の割合か７０重量％を超える
と、分散媒である水か少なくスラリーが形成されないの
て好ましくない。In the method of the present invention, it is desirable that the proportion of the polymer in the total mixture after coagulation is in the range of 10 to 70% by weight. If the proportion of the polymer in the total mixture is less than 10% by weight, it is not preferable because only a small amount of the polymer can be treated with the same equipment. On the other hand, if the proportion of the polymer in the total mixture exceeds 70% by weight, water as a dispersion medium is too small to form a slurry, which is not preferable.
本発明の凝析方法によって得られた凝析粒子は、このグ
ラフト重合体のカラス転位温度（Ｔｇ）℃より１０℃低
い温度（Ｔｇ−１０） ℃以上の温度で加熱処理するこ
とが望ましい。この加熱処理操作を「固化」と呼ぶ。こ
の固化により凝析粒子はより緻密になり、その後の脱水
、乾燥なとの後処理工程ての取扱い性か良くなり、また
製品重合体も取扱いやすい粉粒状になる。−固化処理に
必要な時間は、通常平均滞在時間として１〜６０分程度
である。ここで、本発明でいうＴｇは、例えばポリマー
ハンドブック等に記載されているホモポリマーのＴｇの
値から、Ｆａｘの式により求められる値をいう。The coagulated particles obtained by the coagulation method of the present invention are preferably heat-treated at a temperature higher than or equal to a temperature (Tg-10) 10°C lower than the crow transition temperature (Tg) of the graft polymer. This heat treatment operation is called "solidification." This solidification makes the coagulated particles more dense, making them easier to handle in subsequent post-processing steps such as dehydration and drying, and the product polymer also becomes powdery and granular, which is easier to handle. - The time required for solidification treatment is usually about 1 to 60 minutes as an average residence time. Here, Tg as used in the present invention refers to a value determined by Fax's formula from the Tg value of a homopolymer described in, for example, a polymer handbook.
しかし、重合体によっては、本発明の凝析方法によって
得られた凝析粒子を種型混合機へ導いた後て固化処理を
行うと、凝析粒子か互いに凝集しで、粗大化してしまう
場合かある。このような場合には、同方向回転二軸混練
機内で凝析と固化を同時に行うと粗大化か防止できるた
め、特に好ましい態様である。また、同方向回転二軸混
練機内で固化処理を行うほうが、粒子かより緻密になり
、嵩比重か高い粉粒状重合体が得られる。However, depending on the polymer, if the coagulated particles obtained by the coagulation method of the present invention are solidified after being introduced into the seed mixer, the coagulated particles may aggregate with each other and become coarse. There is. In such a case, coagulation and solidification can be performed simultaneously in a co-rotating twin-screw kneader to prevent coarsening, which is a particularly preferred embodiment. Moreover, when the solidification treatment is performed in a co-rotating twin-screw kneader, the particles become more dense and a powdery polymer with a higher bulk specific gravity can be obtained.
以下、実施例により本発明をさらに詳しく説明する。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
ブチルアクリレートからなるゴム重合体７０重量部に、
メチルメタクリレート３０重量部をグラフト重合し、グ
ラフト重合体ラテックス（固形分含濃度３０重量％、Ｔ
ｇ−−２２℃）を得た。Example 1 70 parts by weight of a rubber polymer consisting of butyl acrylate,
30 parts by weight of methyl methacrylate was graft-polymerized to form a graft polymer latex (solid content 30% by weight, T
g--22°C) was obtained.
この重合体ラテックスを第７図に示した装置を用いて処
理した。図中、２０は、口径２５ｍｍ、 Ｌ ／ Ｄか
２０の同方向回転二軸混練機であり、その概要が第１〜
３図に示されている。また、スクリューの構成を第４表
に示した。また、スクリューの各エレメントは第５図に
示したような形状であり、１は１５ｍｍ、ｔは７．５ｍ
ｍである。２１は容Ｍ ｌの熟成槽であり、中央部に６
枚羽根ファンタービン型の攪拌機２２か配設されている
。２３は、Ｌ／Ｄが１４である以外は２０と同一型式の
同方向回転二軸混練機てあり、スクリューの構成は第５
表に示した通りである。This polymer latex was treated using the apparatus shown in FIG. In the figure, 20 is a co-rotating twin-screw kneading machine with a diameter of 25 mm and L/D of 20, the outline of which is shown in 1 to 2.
This is shown in Figure 3. Further, the configuration of the screw is shown in Table 4. In addition, each element of the screw has a shape as shown in Figure 5, where 1 is 15 mm and t is 7.5 m.
It is m. 21 is a maturing tank with a capacity of ml, and 6 in the center.
A blade fan turbine type stirrer 22 is also provided. No. 23 is a co-rotating twin-screw kneader of the same type as No. 20 except that the L/D is 14, and the screw configuration is the same as No. 5.
As shown in the table.
重合体ラテックスを図には示していない定量ポンプによ
り供給口８がら同方向回転二軸混練機２゜に供給し、所
定量の凝析剤の０．３％水溶液を図にはボしていない定
量ポンプにより供給口１０から同方向回転二軸混練機２
０に供給し、重合体ラテックスを凝析し、重合体スラリ
ーを得た。このスラリーを容器２１へ供給し、同化温度
（第１表記載）まて昇温処理した後、脱水乾燥して粉粒
状の重合体を得た。The polymer latex was supplied to the co-rotating twin-screw kneader 2° through the supply port 8 using a metering pump (not shown in the figure), and a predetermined amount of a 0.3% aqueous solution of a coagulant was added (not shown in the figure). Co-rotating twin-screw kneader 2 from supply port 10 by metering pump
The polymer latex was coagulated to obtain a polymer slurry. This slurry was supplied to a container 21, heated to the assimilation temperature (listed in Table 1), and then dehydrated and dried to obtain a powdery polymer.
得られた粉粒状重合体の嵩比重、平均粒子径、粒度分布
、粒子の均整度について測定し、結果を第３表に示した
。The bulk specific gravity, average particle diameter, particle size distribution, and uniformity of the particles of the resulting powdery polymer were measured, and the results are shown in Table 3.
嵩比重はＪＩＳ Ｋ−６７２１により測定し、また流動
性はＪＩＳ Ｋ−６７２１で用いられる嵩比重測定機に
粉粒体を入れ、タンバーを取り外した際の流出状態を観
察し、その流動性を下記の基準で判定した。The bulk specific gravity was measured according to JIS K-6721, and the fluidity was measured by putting the powder into a bulk specific gravity measuring machine used in JIS K-6721, observing the flow out state when the tambour was removed, and measuring the fluidity as shown below. Judgment was made using the following criteria.
流出状態
Ｏ：ダンバーを取り外すと試料が自然流出する△ニー度
衝撃を加えると流出する
×：衝撃を連続的に加えると流出する
××＝衝撃を連続的に加えても流出しない平均粒子径Ｄ
５ｏは、重量基準のメジアン径を意味し、粒子の均整度
Ｎは、下記式
％式％
（式中Ｄ７Ｓは積算重量分布曲線の７５％にある粒子径
（鱗）、またＤ２５は粒子群の積算重量分布曲線の２５
％にある粒子径（−）を表わす。）で表わした。これら
の測定法は以下の実施例でも＃通して使用した
実施例２
ブタジェン７５重量％とスチレン２５重量％とを重合さ
せてなるゴム重合体８０重量部に、メチルメタクリレー
ト１０重量部とスチレン１０重量部の単量体混合物をグ
ラフト重合し、グラフト重合体ラテックス（固形分含濃
度４０重量％、Ｔｇ−−２０℃）を得た。Outflow condition O: The sample naturally flows out when the damper is removed △ It flows out when a shock is applied ×: It flows out when a shock is applied continuously × × = Average particle diameter D that does not flow out even when a shock is applied continuously
5o means the weight-based median diameter, and the symmetry degree N of the particles is determined by the following formula % formula % (where D7S is the particle diameter (scale) at 75% of the integrated weight distribution curve, and D25 is the particle diameter (scale) at 75% of the integrated weight distribution curve). 25 of the integrated weight distribution curve
Represents the particle size (-) in %. ). These measuring methods were also used in the following examples.Example 2 80 parts by weight of a rubber polymer obtained by polymerizing 75% by weight of butadiene and 25% by weight of styrene, 10 parts by weight of methyl methacrylate and 10 parts by weight of styrene were added. A portion of the monomer mixture was graft-polymerized to obtain a graft polymer latex (solid content 40% by weight, Tg--20°C).
この重合体ラテックスを第８図に示した装置を用いて処
理した。図中、２３は実施例１て使用した同方向回転二
軸混練機２ｏと同一の装置であり、スクリューの構成は
第４表に示した。This polymer latex was treated using the apparatus shown in FIG. In the figure, 23 is the same device as the co-rotating twin-screw kneader 2o used in Example 1, and the screw configuration is shown in Table 4.
重合体ラテックスを図には示していない定量ポンプによ
り供給口８から同方向回転二軸混練機２４に供給し、所
定量の凝析剤の１％水溶液を図にはボしていない定量ポ
ンプにより供給口１０がら二軸混練機２３に供給し、混
練して第１表に示した固化温度まて昇温した後排出口１
１から排出し、脱水乾燥し顆粒状の重合体を得た。The polymer latex was supplied from the supply port 8 to the co-rotating twin-screw kneader 24 by a metering pump (not shown), and a predetermined amount of a 1% aqueous solution of coagulant was added by a metering pump (not shown). After the supply port 10 is fed to the twin-screw kneader 23 and the temperature is raised to the solidification temperature shown in Table 1 after kneading, the discharge port 1
1 was discharged and dehydrated and dried to obtain a granular polymer.
比較例Ｉ
Ｍ、７Ｆ；Ａ／フ′）［１１１肴ｒ１−１１ｉＦｉ夏−
１；＝−ｍｌ−一４．→日≦−−１８１４Ｑｎ／Ｔ１１
４−＆−、−１−六積２立て中央部に６枚羽根ファンタ
ービン型の攪拌機を設置した容器を使用した以外は実施
例１と同様の条件で重合体ラテックスを処理した。凝析
スラリーが安定にオーバーフローされず、排出口か閉本
し、凝析か不安定であった。Comparative Example I M, 7F; A/F') [111 Appetizers r1-11iFi Summer-
1;=-ml--4. →Sun≦--1814Qn/T11
Polymer latex was treated under the same conditions as in Example 1, except that a 4-&-, -1-6 stacked 2-storey container equipped with a 6-blade fan turbine type stirrer was used in the center. The coagulated slurry did not overflow stably, the outlet was closed, and the coagulation was unstable.
（以下余白）
弔
表
第
表
第
表
刀
表
〔発明の効果〕
本発明の凝固方法によれば、数十−〜数ｍｍの範囲の所
望の平均粒径を有する微粉の少ない粉粒体か得られる。(The following is a blank space) Table 1 Table 1 [Effects of the invention] According to the coagulation method of the present invention, powder and granules with a desired average particle diameter in the range of several tens of millimeters to several millimeters and a small amount of fine powder can be obtained. It will be done.
特にゴム成分を多量に含むグラフト重合体ラテックスの
凝析にオーバーフロー形式の混合槽を使用した場合は、
オーバーフローしにくくなり、閉塞しやすかったか、本
発明方法によれば、閉塞することかない。また、同方向
回転二軸混練機のスクリューフォーメイションあるいは
回転数を変えることにより、粉粒状重合体の粒径を制御
することか可能となった。Especially when using an overflow type mixing tank to coagulate graft polymer latex containing a large amount of rubber components,
Overflow is less likely to occur and occlusion is more likely to occur, but according to the method of the present invention, occlusion does not occur. Furthermore, by changing the screw formation or rotation speed of the co-rotating twin-screw kneader, it has become possible to control the particle size of the powdery polymer.
第１図は、本発明で用いる同方向回転二軸混練機の一例
の平面図、第２図は、第１図の混練機の正面図、第３図
は、第１図の混練機の原料供給口におけるＸ−Ｘ線断面
図である。第４図は、同方向回転二軸混練機で用いられ
るスクリューエレメントの代表例を示す図であり、第４
図（ａ）は二条ねしれタイプ、第４図（ｂ）は三条ねし
れタイプを示す。第５図（第５図（ａ）〜（ｅ））は、
二条ねじれタイブネのスクリューエレメントを機能的に
５つに分類した場合の代表的な形状を示す図であり、第
６図は、スクリューエレメントの組み合せを示す斜視図
である。第７図および第８図は、本発明の実施例で用い
た装置の概要図である。
１：バレル ２ニスクリユー軸３、後シール
プレート ４：後軸受
５：シールプレート兼フランジ
６：フラノン ７：ギヤボックス８：原料供給
口 ９：バレル内孔１吐凝析供給口 １１
：排出口
１４ニスクリユーのフライト頂部
１５ニスクリユーの満
１６：スクリュー軸の通る孔
２０．２３：同方向回転二軸混練機FIG. 1 is a plan view of an example of a co-rotating twin-screw kneader used in the present invention, FIG. 2 is a front view of the kneader of FIG. 1, and FIG. 3 is a raw material for the kneader of FIG. 1. FIG. 3 is a sectional view taken along line X-X at the supply port. FIG. 4 is a diagram showing a typical example of a screw element used in a co-rotating twin-screw kneader.
Fig. 4(a) shows a two-striped type, and Fig. 4(b) shows a three-striped type. FIG. 5 (FIG. 5(a) to (e)) is
FIG. 6 is a diagram showing typical shapes when the screw elements of the double-threaded tie are functionally classified into five types, and FIG. 6 is a perspective view showing a combination of the screw elements. FIGS. 7 and 8 are schematic diagrams of the apparatus used in the embodiment of the present invention. 1: Barrel 2 Varnish screw shaft 3, rear seal plate 4: Rear bearing 5: Seal plate and flange 6: Flanone 7: Gear box 8: Raw material supply port 9: Barrel inner hole 1 discharge coagulation supply port 11
: Discharge port 14 Top of the flight of the varnish screw 15 Full 16 of the varnish screw: Hole through which the screw shaft passes 20. 23: Same direction rotating twin screw kneader
Claims (1)
フト重合することにより得られたグラフト重合体で、そ
の弾性幹重合体の含有率が６０重量％以上であるグラフ
ト重合体のラテックスを凝析させるに際して、該ラテッ
クスと凝析剤との混合を同方向回転二軸混練機で実施す
ることを特徴とする重合体ラテックスの凝析方法。 ２）弾性幹重合体に硬質重合体を形成する単量体をグラ
フト重合することにより得られたグラフト重合体で、そ
の弾性幹重合体の含有率が６０重量％以上であるグラフ
ト重合体のラテックスと凝析剤とを同方向回転二軸混練
機で混合して凝析し、得られた重合体スラリーを、該グ
ラフト重合体のガラス転移温度（Ｔｇ）より１０℃低い
温度（Ｔｇ−１０）℃以上で加熱処理する工程を有する
ことを特徴とする粉粒状重合体の製造方法。 ３）弾性幹重合体に硬質重合体を形成する単量体をグラ
フト重合することにより得られたグラフト重合体で、そ
の弾性幹重合体の含有率が６０重量％以上であるグラフ
ト重合体のラテックスと凝析剤とを、同方向回転二軸混
練機内で混合して凝析させつつ、該グラフト重合体のガ
ラス転移温度（Ｔｇ）より１０℃低い温度（Ｔｇ−１０
）℃以上で加熱処理する工程を有することを特徴とする
粉粒状重合体の製造方法。[Scope of Claims] 1) A graft polymer obtained by graft polymerizing a monomer forming a hard polymer onto an elastic backbone polymer, the content of the elastic backbone polymer being 60% by weight or more. A method for coagulating a polymer latex, which comprises mixing the latex and a coagulant with a co-rotating twin-screw kneader when coagulating the latex of a certain graft polymer. 2) Graft polymer latex obtained by graft polymerizing a monomer forming a hard polymer onto an elastic backbone polymer, the content of the elastic backbone polymer being 60% by weight or more. and a coagulant are mixed and coagulated in a co-rotating twin-screw kneader, and the resulting polymer slurry is heated to a temperature (Tg-10) 10° C. lower than the glass transition temperature (Tg) of the graft polymer. A method for producing a particulate polymer, comprising a step of heat treatment at a temperature of 0.degree. C. or higher. 3) Latex of a graft polymer obtained by graft polymerizing a monomer forming a hard polymer to an elastic backbone polymer, and the content of the elastic backbone polymer is 60% by weight or more. and a coagulant are mixed and coagulated in a co-rotating twin-screw kneader at a temperature 10°C lower than the glass transition temperature (Tg) of the graft polymer (Tg-10
) A method for producing a particulate polymer, the method comprising the step of heat treatment at a temperature of at least 100°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4266390A JPH03247603A (en) | 1990-02-26 | 1990-02-26 | Coagulation of polymer latex and production of granular polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4266390A JPH03247603A (en) | 1990-02-26 | 1990-02-26 | Coagulation of polymer latex and production of granular polymer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03247603A true JPH03247603A (en) | 1991-11-05 |
Family
ID=12642257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4266390A Pending JPH03247603A (en) | 1990-02-26 | 1990-02-26 | Coagulation of polymer latex and production of granular polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03247603A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100381929B1 (en) * | 1998-06-03 | 2004-03-26 | 주식회사 엘지화학 | Process and apparatus for continuously producing polymer latex into granules |
| WO2023208918A1 (en) | 2022-04-28 | 2023-11-02 | Röhm Gmbh | Poly(meth)acrylat impact modifier with improved optical properties and method for its production |
-
1990
- 1990-02-26 JP JP4266390A patent/JPH03247603A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100381929B1 (en) * | 1998-06-03 | 2004-03-26 | 주식회사 엘지화학 | Process and apparatus for continuously producing polymer latex into granules |
| WO2023208918A1 (en) | 2022-04-28 | 2023-11-02 | Röhm Gmbh | Poly(meth)acrylat impact modifier with improved optical properties and method for its production |
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