JPS635408B2 - - Google Patents
Info
- Publication number
- JPS635408B2 JPS635408B2 JP58230640A JP23064083A JPS635408B2 JP S635408 B2 JPS635408 B2 JP S635408B2 JP 58230640 A JP58230640 A JP 58230640A JP 23064083 A JP23064083 A JP 23064083A JP S635408 B2 JPS635408 B2 JP S635408B2
- Authority
- JP
- Japan
- Prior art keywords
- acetone
- acid
- water
- butadiene
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 54
- 239000007788 liquid Substances 0.000 claims description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 47
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 46
- 239000002253 acid Substances 0.000 claims description 34
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 150000004715 keto acids Chemical class 0.000 claims description 12
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 10
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000011541 reaction mixture Substances 0.000 claims description 9
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims description 8
- -1 cyanide compound Chemical class 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 238000000034 method Methods 0.000 description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 26
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 20
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 description 19
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000011780 sodium chloride Substances 0.000 description 13
- 239000011734 sodium Substances 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 229940040102 levulinic acid Drugs 0.000 description 8
- 239000010409 thin film Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 150000002429 hydrazines Chemical class 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
この発明は、液状ポリマーであるカルボキシル
末端重合体の製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for producing a carboxyl-terminated polymer, which is a liquid polymer.
カルボキシル末端重合体は、エポキシ樹脂など
の耐衝撃性改質剤として近年注目されており、そ
の使用量も大巾に増加している。特に、１，３―
ブタジエンとアクリロニトリルとを共重合して得
られるカルボキシル末端１，３―ブタジエン―ア
クリロニトリル共重合体はエポキシ樹脂との相溶
性がよいため、高い性能が要求される分野の用途
に多量使用されている。 Carboxyl-terminated polymers have attracted attention in recent years as impact modifiers for epoxy resins and the like, and their usage has also increased significantly. In particular, 1,3-
Carboxyl-terminated 1,3-butadiene-acrylonitrile copolymers obtained by copolymerizing butadiene and acrylonitrile have good compatibility with epoxy resins, so they are used in large quantities in fields that require high performance.
しかし、従来工業的に製造販売されているカル
ボキシル末端液状ポリマーは、その製造法におい
て下記の欠点を有している。すなわち、
ａ○ 重合の開始剤として使用する４，4′―アゾビ
ス（４―シアノ吉草酸）（以下、単にACVAと
略記することもある）は水中でレブリン酸また
はそのナトリウム塩とシアン化水素やシアン化
ナトリウムなどのシアン化合物とヒドラジン類
とを反応させた反応生成物を塩素ガスで酸化し
た後、生成した固形物であるACVAを分離取
得することによつて製造されており、ACVA
の収率が低い。 However, carboxyl-terminated liquid polymers that have been commercially manufactured and sold conventionally have the following drawbacks in their manufacturing methods. That is, a○ 4,4'-azobis(4-cyanovaleric acid) (hereinafter sometimes simply abbreviated as ACVA) used as a polymerization initiator is mixed with levulinic acid or its sodium salt and hydrogen cyanide or cyanide in water. It is produced by oxidizing the reaction product of cyanide compounds such as sodium and hydrazines with chlorine gas, and then separating and obtaining ACVA, which is a solid substance produced.
yield is low.
ｂ○ ACVAを合成するさいに、ACVA1モル当り
２モル以上の塩化ナトリウムが副生するので、
塩化ナトリウムを分離除去するためには
ACVA精製工程を設ける必要があり、熱的に
不安定なACVAの収率がさらに低くなる。b○ When synthesizing ACVA, more than 2 mol of sodium chloride is produced per 1 mol of ACVA, so
To separate and remove sodium chloride
It is necessary to provide an ACVA purification step, which further reduces the yield of thermally unstable ACVA.
ｃ○ ACVA精製工程を設けないと、かなりの量
のナトリウムおよび塩素がカルボキシル末端液
状ポリマー中に含まれるため、高度に防食性の
要求される分野の用途、や高度に電気特性の要
求される分野の用途にはこのようなカルボキシ
ル末端液状ポリマーを使用することができな
い。c○ Without the ACVA purification process, a considerable amount of sodium and chlorine will be contained in the carboxyl-terminated liquid polymer, making it suitable for applications in fields that require a high degree of corrosion resistance or fields that require a high degree of electrical properties. Such carboxyl-terminated liquid polymers cannot be used for applications such as
この発明者らは前述の欠点を有さないカルボキ
シル末端液状ポリマーの製造法について鋭意研究
した結果、この発明を完成した。 The inventors completed this invention as a result of intensive research into a method for producing a carboxyl-terminated liquid polymer that does not have the above-mentioned drawbacks.
すなわち、この発明は、ケト酸またはそのナト
リウム塩とシアン化水素やシアン化ナトリウムな
どのシアン化合物とヒドラジン類とを反応させた
後塩素ガスで酸化して得られるジアゾシアノ酸を
開始剤として用い、不活性溶媒中で１，３―ブタ
ジエンを、好ましくは１，３―ブタジエンとアク
リロニトリルとを（共）重合してカルボキシル末
端重合体を製造する方法において、
(イ) 水中でケト酸またはそのナトリウム塩とシア
ン化合物とヒドラジン類とを反応させて反応生
成物の濃厚水溶液を得る工程；
(ロ) 前記濃厚水溶液100容量部に対して100容量部
以上の量のアセトンを加えて、反応生成物のア
セトン―水溶液を得る工程；
(ハ) 得られた溶液に塩素ガスを加えて前記反応生
成物を酸化してジアゾシアノ酸を生成させる工
程；
(ニ) 得られた反応混合物に必要であればアセトン
を加えて混合物中のアセトンと水との割合を容
量比で85：15〜98：２に調節して、混合物から
上澄液であるジアゾシアノ酸を含むアセトン―
水溶液を分離取得する工程；
(ホ) 前記のジアゾシアノ酸を含むアセトン―水溶
液および１，３―ブタジエン、好ましくはさら
にアクリロニトリルを重合槽に供給して、１，
３―ブタジエンを、好ましくは１，３―ブタジ
エンとアクリロニトリルとを（共）重合する工
程；
(ヘ) 得られた重合反応混合物から場合により未反
応の１，３―ブタジエンを除去し、水を加えて
液状ポリマーを分散せしめた後、液状ポリマー
を分離取得する工程；
を含むことを特徴とするカルボキシル末端重合体
の製造法に関する。 That is, this invention uses as an initiator a diazocyano acid obtained by reacting a keto acid or its sodium salt with a cyanide compound such as hydrogen cyanide or sodium cyanide and hydrazine, and then oxidizing the reaction with chlorine gas. In a method for producing a carboxyl-terminated polymer by (co)polymerizing 1,3-butadiene, preferably 1,3-butadiene and acrylonitrile, (a) a keto acid or its sodium salt and a cyanide compound in water; and hydrazines to obtain a concentrated aqueous solution of the reaction product; (b) 100 parts by volume or more of acetone is added to 100 parts by volume of the concentrated aqueous solution to form an acetone-aqueous solution of the reaction product; (c) adding chlorine gas to the obtained solution to oxidize the reaction product to produce diazocyano acid; (d) adding acetone to the obtained reaction mixture, if necessary, to infuse the mixture with The ratio of acetone to water was adjusted to 85:15 to 98:2 by volume, and the supernatant liquid, acetone containing diazocyano acid, was extracted from the mixture.
Step of separating and obtaining the aqueous solution; (e) supplying the acetone-aqueous solution containing the diazocyano acid and 1,3-butadiene, preferably further acrylonitrile, to the polymerization tank;
A step of (co)polymerizing 3-butadiene, preferably 1,3-butadiene and acrylonitrile; (f) optionally removing unreacted 1,3-butadiene from the resulting polymerization reaction mixture, and adding water. The present invention relates to a method for producing a carboxyl-terminated polymer, comprising the steps of: dispersing the liquid polymer in a liquid polymer, and then separating and obtaining the liquid polymer.
この発明の方法によれば、嵩高で微細な結晶で
あるACVAのようなジアゾシアノ酸を集する
精製工程を省略することができ、ジアゾシアノ酸
の収率が高く、しかも塩化ナトリウム含量の少な
いカルボキシル末端液状ポリマーを得ることがで
きる。 According to the method of this invention, it is possible to omit the purification step of collecting diazocyano acids such as ACVA, which are bulky and fine crystals, and the yield of diazocyano acids is high. Polymers can be obtained.
さらに、この発明の方法によれば、前記の(ニ)工
程におけるジアゾシアノ酸および塩化ナトリウム
を含む混合物中の塩化ナトリウムの結晶粒子が大
きいので、前記混合物から簡単な分離操作によつ
て塩化ナトリウムを分離除去することができ、工
程上非常に有利である。 Furthermore, according to the method of the present invention, since the crystal particles of sodium chloride in the mixture containing diazocyano acid and sodium chloride in step (2) are large, sodium chloride can be separated from the mixture by a simple separation operation. It can be removed, which is very advantageous in terms of process.
この発明の方法においては、先ず(イ)工程におい
て水中でケト酸またはそのナトリウム塩とシアン
化水素やシアン化ナトリウムなどのシアン化合物
とヒドラジン類とを反応させて反応生成物の濃厚
水溶液を得る。 In the method of the present invention, first, in step (a), a keto acid or its sodium salt, a cyanide compound such as hydrogen cyanide or sodium cyanide, and a hydrazine are reacted in water to obtain a concentrated aqueous solution of the reaction product.
前記のケト酸またはそのナトリウム塩として
は、レブリン酸、レブリン酸ナトリウムが好適に
挙げられる。 Preferred examples of the keto acid or its sodium salt include levulinic acid and sodium levulinic acid.
また、前記のヒドラジン類としては、ヒドラジ
ン水化物、ヒドラジン硫酸塩などが挙げられる。 Further, examples of the hydrazines include hydrazine hydrate, hydrazine sulfate, and the like.
この発明の方法においては、少量の水中で塩酸
等の鉱酸または水酸化ナトリウム等のアルカリの
存在下または不存在下に、ケト酸またはケト酸の
ナトリウム塩（１モル当り）とシアン化合物（１
モル）とヒドラジン類（0.5モル）とを反応させ
るのが好ましい。この方法において、水の全量と
ケト酸またはケト酸のナトリウムとの割合は、水
の全量100重量部に対してケト酸またはケト酸の
ナトリウム塩が10〜120重量部、特に30〜80重量
部であることが好ましい。 In the method of this invention, a keto acid or a sodium salt of a keto acid (per mole) and a cyanide compound (per mole) are mixed in a small amount of water in the presence or absence of a mineral acid such as hydrochloric acid or an alkali such as sodium hydroxide.
It is preferable to react hydrazines (0.5 mol) with hydrazines (0.5 mol). In this method, the ratio between the total amount of water and the keto acid or the sodium salt of the keto acid is 10 to 120 parts by weight, particularly 30 to 80 parts by weight, per 100 parts by weight of the total amount of water. It is preferable that
また、この発明の方法において、比較的多量の
水中で前記各成分を反応させた後、この水溶液か
ら水を蒸発除去して反応生成物の濃厚水溶液を得
てもよい。 Furthermore, in the method of the present invention, after reacting each of the components in a relatively large amount of water, water may be removed by evaporation from this aqueous solution to obtain a concentrated aqueous solution of the reaction product.
前記の水中における各成分の反応は、アルカリ
の存在下にケト酸とシアン化ナトリウムとヒドラ
ジン硫酸塩等のヒドラジン類とを接触させてもよ
く、あるいは鉱酸の存在下にケト酸とシアン化ナ
トリウムとを好ましくは20℃以下の温度で接触さ
せた後ヒドラジン水和物を系に加えて接触させて
もよい。前記の各成分の反応は35℃以下の温度で
行なうのが好ましい。 The reaction of each component in water may be carried out by contacting a keto acid, sodium cyanide, and a hydrazine such as hydrazine sulfate in the presence of an alkali, or by contacting a keto acid with sodium cyanide in the presence of a mineral acid. The hydrazine hydrate may be added to the system and contacted after contacting them at a temperature preferably below 20°C. The reaction of each of the above components is preferably carried out at a temperature of 35°C or lower.
この発明の方法においては、前記の方法によつ
て反応生成物である下記の式で示される化合物の
濃厚水溶液を得ることができる。 In the method of the present invention, a concentrated aqueous solution of the reaction product, a compound represented by the following formula, can be obtained by the method described above.
（式中、Ｒは炭素数１〜６のアルキル基であ
り、ｎは１〜６の整数である）
この発明の方法においては、(ロ)工程において(イ)
工程で得られた濃厚水溶液100容量部に対して100
容量部以上の量、好ましくはアセトンと水との割
合が容量比で85：15〜98：２となる量のアセトン
を加えて、反応生成物のアセトン―水溶液を得
る。 (In the formula, R is an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.) In the method of this invention, in step (b), (a)
100 parts by volume of the concentrated aqueous solution obtained in the process
Acetone is added in an amount of at least parts by volume, preferably in an amount such that the ratio of acetone to water is 85:15 to 98:2 by volume to obtain an acetone-aqueous solution of the reaction product.
アセトンと水との割合が前記範囲外であると、
ジアゾシアノ酸の収率が低下するので好ましくな
い。 When the ratio of acetone and water is outside the above range,
This is not preferred because the yield of diazocyano acid decreases.
この発明の方法においては、(ハ)工程において前
記の工程で得られた溶液に、好ましくは使用した
レブリン酸またはそのナトリウム塩１モルに対し
て0.5モル以上、特に0.5〜１モル、さらに0.5〜
0.6モルの塩素ガスを加えて前記式で示される反
応生成物を酸化してジアゾシアノ酸を生成させ
る。前記の酸化反応は30℃以下の温度、特に10℃
以下の温度で行なうのが好ましい。 In the method of the present invention, in step (c), the solution obtained in the above step is preferably added to the solution obtained in the above step at 0.5 mol or more, particularly 0.5 to 1 mol, more preferably 0.5 to 1 mol, per 1 mol of levulinic acid or its sodium salt used.
The reaction product represented by the above formula is oxidized by adding 0.6 moles of chlorine gas to produce diazocyano acid. The above oxidation reaction is carried out at a temperature below 30℃, especially at 10℃
Preferably, the temperature is as follows.
前記のジアゾシアノ酸としては、４，4′―アゾ
ビス（４―シアノ吉草酸）が好適に挙げられる。 Preferred examples of the diazocyano acids include 4,4'-azobis(4-cyanovaleric acid).
前記の方法において塩素ガスを加える方法はそ
れ自体公知の方法が採用される。 In the above method, a method known per se is employed for adding chlorine gas.
この発明の方法においては、(ニ)工程において前
記の工程で得られた反応混合物に必要であればア
セトンを加えて混合物中のアセトンと水との割合
を容量比で85：15〜98：２、好ましくは90：10〜
95：５に調節して、好ましくは混合物の温度を０
〜60℃、特に15〜60℃にして、混合物から上澄液
であるジアゾシアノ酸を含むアセトン―水溶液を
分離取得する。 In the method of this invention, in step (d), acetone is added to the reaction mixture obtained in the above step, if necessary, to adjust the ratio of acetone and water in the mixture to 85:15 to 98:2 by volume. , preferably 90:10~
Preferably the temperature of the mixture is 0 by adjusting the ratio 95:5.
The mixture is heated to ~60°C, particularly 15~60°C, and an acetone-aqueous solution containing diazocyanoic acid, which is a supernatant liquid, is separated and obtained from the mixture.
この発明の方法においては、前記の(ハ)工程にお
いてジアゾシアノ酸を生成させると、ジアゾシア
ノ酸に対して２倍モル以上の量の塩化ナトリウム
が副生する。この発明の方法においては(ニ)工程に
おいてアセトンと水との割合を前記特定の範囲に
調節することによつて、(ハ)工程で副生成物として
生成した塩化ナトリウムは混合物中で大きな結晶
となつて析出し、ジアゾシアノ酸が溶解している
アセトン―水溶液中には塩化ナトリウムが極く少
量溶解しているにすぎない。この発明の方法にお
いて、(ハ)工程で得られた反応混合物中のアセトン
と水との割合がすでに容量比で85：15〜98：２で
あるときは、さらにアセトンを加えてもよく加え
なくともよい。 In the method of the present invention, when diazocyano acid is produced in step (c) above, sodium chloride is by-produced in an amount of twice or more moles relative to the diazocyano acid. In the method of this invention, by adjusting the ratio of acetone and water to the above-mentioned specific range in step (d), the sodium chloride produced as a by-product in step (c) is formed into large crystals in the mixture. Only a small amount of sodium chloride is dissolved in the acetone-water solution in which diazocyanoic acid is dissolved. In the method of this invention, when the ratio of acetone to water in the reaction mixture obtained in step (c) is already 85:15 to 98:2 by volume, it is not possible to add more acetone. Tomoyoshi.
また、この発明の方法において反応混合物中に
塩酸が含まれている場合には、水酸化ナトリウム
のようなアルカリや、炭酸ナトリウム、炭酸水素
ナトリウムなどの弱アルカリ性の化合物を加えて
塩酸を中和し、溶液のPHを３〜５、特に４〜５に
調節するのが好ましい。 In addition, when hydrochloric acid is contained in the reaction mixture in the method of this invention, an alkali such as sodium hydroxide or a weakly alkaline compound such as sodium carbonate or sodium hydrogen carbonate is added to neutralize the hydrochloric acid. It is preferable to adjust the pH of the solution to 3-5, particularly 4-5.
前記のジアゾシアノ酸を含むアセトン―水溶液
を分離取得するときの混合物中のアセトンと水と
の割合が前記範囲外であると、(ホ)工程で重合槽に
供給するジアゾシアノ酸を含む溶液中の塩化ナト
リウムの量が著るしく多くなり、最終的に得られ
るカルボキシル末端液状ポリマー中に多量の塩素
およびナトリウムが含まれるので好ましくない。 If the ratio of acetone and water in the mixture when separating and obtaining the acetone-aqueous solution containing diazocyano acid is outside the above range, chlorination in the solution containing diazocyano acid supplied to the polymerization tank in step (e) will occur. This is undesirable because the amount of sodium increases significantly and the finally obtained carboxyl-terminated liquid polymer contains large amounts of chlorine and sodium.
前記の混合物から上澄液であるジアゾシアノ酸
を含むアセトン―水溶液を分離取得するには、混
合物を過してジアゾシアノ酸のアセトン―水溶
液を液として取得してもよく、混合物の上澄液
としてデカンテーシヨンによつて取得してもよ
い。前記の方法において、塩化ナトリウムの結晶
は分離除去される。 In order to separate and obtain the supernatant acetone-aqueous solution containing diazocyano acid from the above mixture, the mixture may be filtered to obtain the acetone-aqueous solution of diazocyano acid as a liquid, and the supernatant liquid of the mixture may be obtained by separating and obtaining the acetone-aqueous solution containing diazocyano acid. It may also be obtained by station. In the method described above, the sodium chloride crystals are separated and removed.
この発明の方法においては、(ホ)工程において前
記のジアゾシアノ酸を含むアセトン―水溶液およ
び１，３―ブタジエン、好ましくはさらにアクリ
ロニトリルを重合槽に供給し、１，３―ブタジエ
ン、好ましくは１，３―ブタジエンとアクリロニ
トリルとを（共）重合する。 In the method of the present invention, in step (e), an acetone-aqueous solution containing the diazocyano acid and 1,3-butadiene, preferably further acrylonitrile, are supplied to the polymerization tank, and 1,3-butadiene, preferably 1,3 - (Co)polymerize butadiene and acrylonitrile.
前記の重合において、重合温度は70〜130℃が
好ましく、重合時間は１〜20時間が好ましい。ま
た、ジアゾシアノ酸の量は、モノマー成分（１，
３―ブタジエンまたは１，３―ブタジエンとアク
リロニトリルとの合計）100重量部に対して５〜
20重量部が好ましい。ジアゾシアノ酸を含むアセ
トン―水溶液の添加方法には特に制限はなく、一
度に添加してもよく分割して添加してもよい。前
記の重合条件を適宜選択して、アクリロニトリル
含量が特に５〜35重量％、数平均分子量が1000〜
5000、官能基数（／mol）が1.8〜2.5のカルボキ
シル末端液状ポリマーを生成させるのが好まし
い。 In the above polymerization, the polymerization temperature is preferably 70 to 130°C, and the polymerization time is preferably 1 to 20 hours. In addition, the amount of diazocyano acid is the monomer component (1,
5 to 100 parts by weight (total of 3-butadiene or 1,3-butadiene and acrylonitrile)
20 parts by weight is preferred. There is no particular restriction on the method of adding the acetone-aqueous solution containing diazocyano acid, and it may be added all at once or in portions. By appropriately selecting the above polymerization conditions, the acrylonitrile content is particularly 5 to 35% by weight, and the number average molecular weight is 1000 to 1000.
5000, preferably to produce a carboxyl-terminated liquid polymer with a functionality (/mol) of 1.8 to 2.5.
この発明の方法においては、(ヘ)工程において前
記の方法によつて得られた重合反応混合物から場
合により未反応の１，３―ブタジエンを除去し、
水を加えて液状ポリマーを分散せしめた後、液状
ポリマーを分離取得し、好ましくは前記液状ポリ
マーを蒸発器中において恒量になるまで乾燥し
て、カルボキシル未端重合体を得る。 In the method of this invention, in step (f), unreacted 1,3-butadiene is optionally removed from the polymerization reaction mixture obtained by the above method,
After adding water to disperse the liquid polymer, the liquid polymer is separated and obtained, and preferably the liquid polymer is dried in an evaporator to a constant weight to obtain a carboxyl-terminated polymer.
前記の方法において、加える水の量はカルボキ
シル末端液状ポリマー100重量部に対して100〜
400重量部が好ましい。また、重合反応混合物か
ら未反応の１，３―ブタジエンを除去しない場合
には、カルボキシル末端液状ポリマー100重量部
に対してアセトンが50〜300重量部、特に100〜
300重量部、１，３―ブタジエンが10〜150重量
部、特に30〜150重量部、および水が100〜400重
量部となる割合で水を加えるのが好ましい。水を
加えて好ましくは混合し、液状ポリマーを分散せ
しめた後、好ましくは２分間〜10時間静置すると
液状ポリマーとアセトン―水溶液の２相に分離す
るので、液状ポリマーを分離取得する。必要であ
れば、遠心分離によつて液状ポリマー中に少量含
有される水分を除去してもよい。 In the above method, the amount of water added is 100 to 100 parts by weight per 100 parts by weight of the carboxyl-terminated liquid polymer.
400 parts by weight is preferred. In addition, when unreacted 1,3-butadiene is not removed from the polymerization reaction mixture, 50 to 300 parts by weight of acetone, especially 100 to 300 parts by weight, per 100 parts by weight of the carboxyl-terminated liquid polymer.
Preferably, water is added in a proportion of 300 parts by weight, 10 to 150 parts by weight, especially 30 to 150 parts by weight of 1,3-butadiene, and 100 to 400 parts by weight of water. After water is preferably added and mixed to disperse the liquid polymer, if it is left to stand for preferably 2 minutes to 10 hours, it will separate into two phases, the liquid polymer and the acetone-aqueous solution, and the liquid polymer will be separated and obtained. If necessary, a small amount of water contained in the liquid polymer may be removed by centrifugation.
この発明の方法においては、液状ポリマーとア
セトン―水溶液とを分離することによつて、ジア
ゾシアノ酸製造時に副生する水溶性の化合物はア
セトン―水溶液に溶解して除かれる。さらに、重
合開始剤として使用したジアゾシアノ酸のアセト
ン―水溶液中にごく少量含まれる塩化ナトリウム
のほとんどが液状ポリマーから除かれるのであ
る。 In the method of the present invention, by separating the liquid polymer and the acetone-aqueous solution, water-soluble compounds produced as by-products during the production of diazocyano acid are dissolved in the acetone-aqueous solution and removed. Furthermore, most of the sodium chloride contained in a very small amount in the acetone-aqueous solution of diazocyano acid used as a polymerization initiator is removed from the liquid polymer.
前記のようにして分離された液状ポリマーは、
必要であればそれ自体公知の方法によつて酸化防
止剤を含有せしめた後、蒸発器中において恒量に
なるまで乾燥する。 The liquid polymer separated as described above is
After incorporating antioxidants, if necessary, by methods known per se, it is dried in an evaporator to constant weight.
前記の蒸発器としては、横形遠心薄膜蒸発器、
たて形遠心薄膜蒸発器、VL形遠心薄膜蒸発器な
どの遠心薄膜蒸発器を使用することができる。 The evaporator may include a horizontal centrifugal thin film evaporator;
Centrifugal thin film evaporators such as vertical centrifugal thin film evaporators and VL centrifugal thin film evaporators can be used.
この発明の方法によれば、アクリロニトリル含
量が特に５〜35重量％、数平均分子量が1000〜
5000、官能基数（／mol）が1.8〜2.5、Na含量が
25ppm以下であるカルボキシル末端液状ポリマー
を製造することができる。 According to the method of the invention, the acrylonitrile content is in particular 5 to 35% by weight and the number average molecular weight is 1000 to 1000.
5000, number of functional groups (/mol) is 1.8-2.5, Na content is
Carboxyl-terminated liquid polymers can be produced that have less than 25 ppm.
この発明の方法によつて製造されるカルボキシ
ル末端液状ポリマーは、電着塗料や粉体塗料など
の用途に使用することができる。 The carboxyl-terminated liquid polymer produced by the method of the present invention can be used in applications such as electrodeposition coatings and powder coatings.
以下に実施例および比較例を示す。 Examples and comparative examples are shown below.
実施例 １
撹拌機、ガス導入管、ガスベント、滴下管の付
いた反応容器中にレブリン酸0.963Kg（8.3mol）、
水0.42を取り、５℃に冷却した。ここへ濃塩酸
0.058Kg、水0.08を加えた後、NaCN0.420Kg
（8.5mol）を水0.83に溶解した水溶液を反応温
度が10℃を越えない様に滴下し、そのあと10℃以
下で15分反応させた。この時生成したシアンヒド
リンが析出し、反応系はソフトクリーム状を呈し
た。ここへNH2NH2・H2O0.208Kg（4.15mol）
を滴下し加温すると30℃で液体になり、35℃で３
時間反応をつづけた。次に５℃に冷却し、アセト
ン12を加え、次いでCl2ガス0.315Kg（4.5mol）
を加え、10℃を越えない様に反応させた。反応
後、室温（20℃）に戻し、撹拌を止めると微黄色
液部と白色沈殿部にクリヤーに分離した。液部は
塩酸酸性を示すのでNaHCO3を加えてPH４にし、
紙を用いて自然ろ過で沈殿部を除いた。この液
14中にはACVAが0.85Kg含まれていた。又、他
の副生物は水に可溶であり0.28Kg含まれていた。
NaClはACVAあたり14000ppm存在していた。
この液を開始剤溶液として、重合に用いた。１，
３―ブタジエン16Kg（29.6mol）、アクリロニト
リル3.51Kg（6.6mol）、アセトン６を入れて予
熱して80℃とした100のリアクターヘ、開始剤
溶液を最初5.6、４，８，12時間後に2.8ずつ
加え、16時間80℃で重合した。25℃に冷却後、未
反応１，３―ブタジエンを留去し、20の水を加
えて混合後静置するとすみやかに相分離がおこつ
た。下層の水―アセトン層を除き、ポリマー層を
温度25〜30℃、5000Gにて遠心分離して、含水率
２％の液状ポリマーを得た。この液状ポリマーを
遠心薄膜蒸発器中において恒量になるまで乾燥し
て、カルボキシル末端液状ポリマー9.65Kgを得
た。この液状コポリマーは、アクリロニトリル含
量24.8モル％、数平均分子量4300、酸価は2180
ｇ／eq、ブルツクフイールド粘度580000cps（27
℃）、原子吸光分析によるNa含量は17ppmであつ
た。Example 1 0.963 Kg (8.3 mol) of levulinic acid was placed in a reaction vessel equipped with a stirrer, gas inlet tube, gas vent, and dropping tube.
0.42 of water was taken and cooled to 5°C. Concentrated hydrochloric acid here
0.058Kg, after adding water 0.08, NaCN0.420Kg
(8.5 mol) dissolved in 0.83 mol of water was added dropwise so that the reaction temperature did not exceed 10°C, and then the reaction was carried out at 10°C or lower for 15 minutes. The cyanohydrin produced at this time precipitated, and the reaction system took on a soft cream-like appearance. Here NH 2 NH 2・H 2 O0.208Kg (4.15mol)
When added dropwise and heated, it becomes liquid at 30℃, and becomes liquid at 35℃.
The reaction continued for hours. Then cool to 5℃, add acetone 12, then 0.315Kg (4.5mol) of Cl2 gas
was added and allowed to react at a temperature not exceeding 10°C. After the reaction, the temperature was returned to room temperature (20°C), and when stirring was stopped, the mixture was clearly separated into a slightly yellow liquid part and a white precipitate part. The liquid part shows hydrochloric acid acidity, so add NaHCO 3 to make the pH 4.
The precipitate was removed by natural filtration using paper. this liquid
14 contained 0.85Kg of ACVA. In addition, other by-products were soluble in water and contained 0.28 kg.
NaCl was present at 14000 ppm per ACVA.
This liquid was used as an initiator solution for polymerization. 1,
16 Kg (29.6 mol) of 3-butadiene, 3.51 Kg (6.6 mol) of acrylonitrile, and 6 acetone were added to 100 reactors preheated to 80°C. In addition, polymerization was carried out at 80°C for 16 hours. After cooling to 25°C, unreacted 1,3-butadiene was distilled off, 20ml of water was added, and after mixing, the mixture was allowed to stand, and phase separation occurred immediately. The lower water-acetone layer was removed, and the polymer layer was centrifuged at 5000G at a temperature of 25 to 30°C to obtain a liquid polymer with a water content of 2%. This liquid polymer was dried to constant weight in a centrifugal thin film evaporator to obtain 9.65 Kg of carboxyl-terminated liquid polymer. This liquid copolymer has an acrylonitrile content of 24.8 mol%, a number average molecular weight of 4300, and an acid value of 2180.
g/eq, Burtskfield viscosity 580000cps (27
℃), and the Na content was 17 ppm by atomic absorption spectrometry.
実施例 ２
ACVAの合成および１，３―ブタジエン―ア
クリロニトリルの共重合は実施例１と全く同様に
行つた。重合液を25℃に冷却後、１，３―ブタジ
エンを留去しないで、ここへ20の水を加え、水
洗浄した。洗浄後25℃で7.5時間、静置分離した。
ポリマー層の含水率は２％であつた。この液状ポ
リマーを遠心薄膜蒸発器中において恒量になるま
で乾燥して、カルボキシル末端液状ポリマー9.55
Kgを得た。この液状ポリマーは、アクリロニトリ
ル含量24.7モル％、酸価は2180ｇ／eq、ブルツク
フイールド粘度580000cps（27℃）、原子吸光によ
るNa含量は19ppmであつた。Example 2 The synthesis of ACVA and the copolymerization of 1,3-butadiene-acrylonitrile were carried out in exactly the same manner as in Example 1. After the polymerization solution was cooled to 25° C., 1,3-butadiene was not distilled off, but 20 g of water was added thereto, and the solution was washed with water. After washing, the mixture was allowed to stand at 25°C for 7.5 hours for separation.
The water content of the polymer layer was 2%. This liquid polymer was dried to a constant weight in a centrifugal thin film evaporator to obtain a carboxyl-terminated liquid polymer of 9.55%.
Got Kg. This liquid polymer had an acrylonitrile content of 24.7 mol%, an acid value of 2180 g/eq, a Bruckfield viscosity of 580,000 cps (27°C), and an Na content of 19 ppm by atomic absorption.
実施例 ３
撹拌機、ガス導入管、ガスベント、滴下管の付
いた反応容器中にレブリン酸0.963Kg（8.3mol）、
水0.42を取り、５℃に冷却した。ここへ濃塩酸
0.058Kg、水0.08を加えた後、NaCN0.420Kg
（8.5mol）を水0.83に溶解した水溶液を反応温
度が10℃を越えない様に滴下し、そのあと10℃以
下で15分反応させた。この時生成したシアンヒド
リンが析出し、反応系はソフトクリーム状を呈し
た。ここへNH2NH2・H2O0.208Kg（4.15mol）
を滴下し、加温すると、30℃で液体となり、35℃
で３時間反応後、この温度で系中の水が0.63に
なるまで水を減圧留去した。次に５℃に冷却し、
アセトン12を加え、次いでCl2ガス0.315Kg
（4.5mol）を加え、10℃を越えない様反応させ
た。反応後室温に戻し、撹拌を止めると、微黄色
液部と白色沈殿部にクリヤーに分離した。液部は
塩酸酸性を示すのでNaHCO3を加えてPH４にし
て沈殿部を除いた。この液13.3中にはACVAが
0.85Kg含まれていた。又、副生物は水に可溶であ
り、0.28Kg含まれていた。NaClはACVAあたり
6500ppm含まれていた。この液を開始剤溶液とし
て重合に用いた。重合条件は、この開始剤溶液を
最初5.5、４，８，12時間後に2.6ずつ加えた
以外は全く実施例１と同様に行つた。又、後処理
も実施例１と同様にして、カルボキシル末端液状
ポリマー9.73Kgを得た。この液状コポリマーはア
クリロニトリル含量25.0モル％、酸価は2150ｇ／
eq、ブルツクフイールド粘度570000cps（27℃）、
原子吸光によるNa含量は8ppmであつた。Example 3 0.963 kg (8.3 mol) of levulinic acid was placed in a reaction vessel equipped with a stirrer, gas inlet tube, gas vent, and dropping tube.
0.42 of water was taken and cooled to 5°C. Concentrated hydrochloric acid here
0.058Kg, after adding water 0.08, NaCN0.420Kg
(8.5 mol) dissolved in 0.83 mol of water was added dropwise so that the reaction temperature did not exceed 10°C, and then the reaction was carried out at 10°C or lower for 15 minutes. The cyanohydrin produced at this time precipitated, and the reaction system took on a soft cream-like appearance. Here NH 2 NH 2・H 2 O0.208Kg (4.15mol)
When added dropwise and heated, it becomes a liquid at 30℃, and the temperature rises to 35℃.
After reacting for 3 hours at this temperature, water was distilled off under reduced pressure until the water content in the system became 0.63. Next, cool to 5℃,
Add acetone 12, then Cl2 gas 0.315Kg
(4.5 mol) was added, and the reaction was carried out at a temperature not exceeding 10°C. After the reaction, the temperature was returned to room temperature and stirring was stopped, and the mixture was clearly separated into a slightly yellow liquid part and a white precipitate part. Since the liquid part was acidic with hydrochloric acid, NaHCO 3 was added to adjust the pH to 4 and the precipitate part was removed. This liquid 13.3 contains ACVA.
It contained 0.85Kg. In addition, by-products were soluble in water and contained 0.28 kg. NaCl per ACVA
It contained 6500ppm. This liquid was used as an initiator solution for polymerization. The polymerization conditions were exactly the same as in Example 1, except that 2.6 hours of this initiator solution was added at the beginning, 4 hours, 8 hours, and 12 hours later. Further, the post-treatment was carried out in the same manner as in Example 1 to obtain 9.73 kg of a carboxyl-terminated liquid polymer. This liquid copolymer has an acrylonitrile content of 25.0 mol% and an acid value of 2150 g/
eq, Burtskfield viscosity 570000cps (27℃),
The Na content determined by atomic absorption was 8 ppm.
比較例 １
撹拌機、ガス導入管、ガスベント、滴下管の付
いた反応容器中にレブリン酸0.963Kg（8.3mol）、
水1.0を取り５℃に冷却した。ここへ濃塩酸
0.058Kg、水0.3を加えた後、NaCN0.420Kg
（8.6mol）を水1.6に溶解した水溶液を反応温度
が10℃を越えない様に滴下し、そのあと10℃以下
で15分反応させた。この時実施例１と異なり、生
成物の析出はみられなかつた。ここへNH2・
NH2・H2O0.208Kg（4.15mol）滴下後、35℃で３
時間反応した。次に５℃に冷却し、アセトン3.3
加え、次いでCl2ガス0.31Kg（4.4mol）加え、
10℃を越えない様反応させた。生成ACVAが一
部析出した反応液から、アセトンを20℃で減圧留
去するとACVAが大量に析出した。G4ガラスフ
イルターで吸引ろかで３時間要して粗ACVAを
得た。これを更に0.7の水で洗い、ろ別後、減
圧乾燥してACVA0.69Kgを得た。このACVA中
には、2000ppmのNaClが含まれていた。この
ACVA全量をアセトンと水の90／10の混合溶媒
に溶かし全量を11.4とした。これを開始剤溶液
として重合に用いた。ブタジエン13Kg
（24.1mol）、アクリロニトリル2.86Kg（5.4mol）、
アセトン4.9の入つた予熱して80℃にした100
のリアクターへ最初4.5、４，８，12時間後に
2.3ずつ加え、16時間80℃で重合した。25℃に
冷却後、ブタジエンを留去し、16の水を加えて
撹拌洗浄し、静置すると、すみやかに相分離がお
こつた。下層の水―アセトン層を除き、ポリマー
層を遠心薄膜蒸発器中において恒量になるまで乾
燥してカルボキシル末端液状ポリマー7.74Kgを得
た。この液状コポリマーは、アクリロニトリル含
量24.7モル％、酸価は2130ｇ／eq、ブルツクフイ
ールド粘度570000cps（27℃）、原子吸光によるNa
含量は18ppmであつた。実施例１と比較例１よ
り、同等のポリマー１Kg得るのに原料レブリン酸
は実施例１の方法では0.100Kg、それに対して比
較例１の方法では0.125Kg必要であつた。Comparative Example 1 0.963 kg (8.3 mol) of levulinic acid was placed in a reaction vessel equipped with a stirrer, gas inlet tube, gas vent, and dropping tube.
1.0% of water was taken and cooled to 5°C. Concentrated hydrochloric acid here
0.058Kg, after adding water 0.3, NaCN0.420Kg
An aqueous solution of (8.6 mol) dissolved in 1.6 mol of water was added dropwise so that the reaction temperature did not exceed 10°C, and then the reaction was carried out for 15 minutes at 10°C or lower. At this time, unlike in Example 1, no product precipitation was observed. NH2 here
After dropping 0.208Kg (4.15mol) of NH 2 H 2 O,
Time reacted. Then cool to 5℃ and add 3.3% acetone.
Then add 0.31Kg (4.4mol) of Cl2 gas,
The reaction was carried out at a temperature not exceeding 10°C. When acetone was distilled off under reduced pressure at 20°C from the reaction solution in which some of the produced ACVA was precipitated, a large amount of ACVA was precipitated. Crude ACVA was obtained by suction filtering through a G4 glass filter for 3 hours. This was further washed with 0.7 kg of water, filtered, and dried under reduced pressure to obtain ACVA of 0.69 kg. This ACVA contained 2000 ppm NaCl. this
The total amount of ACVA was dissolved in a 90/10 mixed solvent of acetone and water to make the total amount 11.4. This was used as an initiator solution for polymerization. Butadiene 13Kg
(24.1mol), acrylonitrile 2.86Kg (5.4mol),
100 preheated to 80℃ with acetone 4.9
first to the reactor after 4.5, 4, 8, and 12 hours.
2.3 of each were added and polymerized at 80°C for 16 hours. After cooling to 25°C, butadiene was distilled off, water was added from 16 and washed with stirring, and when the mixture was allowed to stand, phase separation occurred immediately. The lower water-acetone layer was removed and the polymer layer was dried in a centrifugal thin film evaporator to constant weight to obtain 7.74 Kg of carboxyl-terminated liquid polymer. This liquid copolymer has an acrylonitrile content of 24.7 mol%, an acid value of 2130 g/eq, a Bruckfield viscosity of 570,000 cps (27°C), and a Na
The content was 18 ppm. From Example 1 and Comparative Example 1, to obtain 1 kg of the same polymer, the method of Example 1 required 0.100 Kg of raw material levulinic acid, whereas the method of Comparative Example 1 required 0.125 Kg.
Claims (1)
素やシアン化ナトリウムなどのシアン化合物とヒ
ドラジン類とを反応させた後塩素ガスで酸化して
得られるジアゾシアノ酸を開始剤として用い、不
活性溶媒中で１，３―ブタジエンを、好ましくは
１，３―ブタジエンとアクリロニトリルとを
（共）重合してカルボキシル末端重合体を製造す
る方法において、 (イ) 水中でケト酸またはそのナトリウム塩とシア
ン化合物とヒドラジン類とを反応させて反応生
成物の濃厚水溶液を得る工程； (ロ) 前記濃厚水溶液100容量部に対して100容量部
以上の量のアセトンを加えて、反応生成物のア
セトン―水溶液を得る工程； (ハ) 得られた溶液に塩素ガスを加えて前記反応生
成物を酸化してジアゾシアノ酸を生成させる工
程； (ニ) 得られた反応混合物に必要であればアセトン
を加えて混合物中のアセトンと水との割合を容
量比で85：15〜98：２に調節して、混合物から
上澄液であるジアゾシアノ酸を含むアセトン―
水溶液を分離取得する工程； (ホ) 前記のジアゾシアノ酸を含むアセトン―水溶
液および１，３―ブタジエン、好ましくはさら
にアクリロニトリルを重合槽に供給し、１，３
―ブタジエンを、好ましくは１，３―ブタジエ
ンとアクリロニトリルとを（共）重合する工
程； (ヘ) 得られた重合反応混合物から場合により未反
応の１，３―ブタジエンを除去し、水を加えて
液状ポリマーを分散せしめた後、液状ポリマー
を分離取得する工程； を含むことを特徴とするカルボキシル末端重合体
の製造法。 ２ (ロ)工程における反応生成物のアセトン―水溶
液中のアセトンと水との割合が容量比で85：15〜
98：２であることを特徴とする特許請求の範囲第
１項記載のカルボキシル末端重合体の製造法。[Claims] 1. Diazocyano acid obtained by reacting a keto acid or its sodium salt with a cyanide compound such as hydrogen cyanide or sodium cyanide and hydrazine and then oxidizing it with chlorine gas is used as an initiator, and an inert In a method for producing a carboxyl-terminated polymer by (co)polymerizing 1,3-butadiene, preferably 1,3-butadiene and acrylonitrile in a solvent, (a) a keto acid or its sodium salt and cyanide are copolymerized in water. A step of reacting a compound with a hydrazine to obtain a concentrated aqueous solution of the reaction product; (b) Adding 100 parts by volume or more of acetone to 100 parts by volume of the concentrated aqueous solution to obtain an acetone-aqueous solution of the reaction product. (c) adding chlorine gas to the obtained solution to oxidize the reaction product to produce diazocyano acid; (d) adding acetone to the obtained reaction mixture, if necessary, to form a mixture. The ratio of acetone and water in the mixture was adjusted to a volume ratio of 85:15 to 98:2, and the supernatant liquid, acetone containing diazocyano acid, was extracted from the mixture.
Step of separating and obtaining the aqueous solution; (e) supplying the acetone-aqueous solution containing the diazocyano acid and 1,3-butadiene, preferably further acrylonitrile, to the polymerization tank;
- a step of (co)polymerizing butadiene, preferably 1,3-butadiene and acrylonitrile; (f) optionally removing unreacted 1,3-butadiene from the resulting polymerization reaction mixture, and adding water; A method for producing a carboxyl-terminated polymer, comprising the steps of: dispersing the liquid polymer and then separating and obtaining the liquid polymer. 2. The reaction product in step (b) is acetone - the ratio of acetone to water in the aqueous solution is 85:15 to 85:15 by volume.
A method for producing a carboxyl-terminated polymer according to claim 1, characterized in that the ratio is 98:2.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23064083A JPS60123513A (en) | 1983-12-08 | 1983-12-08 | Production of carboxyl-terminated polymer |
| US06/676,264 US4684717A (en) | 1983-12-08 | 1984-11-29 | Preparation of azo compounds having carboxyl and cyano groups |
| US06/676,265 US4684718A (en) | 1983-12-08 | 1984-11-29 | Process for the preparation of diazocyano acids by reacting keto-acids with cyanogen compounds |
| DE19843444874 DE3444874A1 (en) | 1983-12-08 | 1984-12-08 | METHOD FOR PRODUCING DIAZOCYANOSAURS |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23064083A JPS60123513A (en) | 1983-12-08 | 1983-12-08 | Production of carboxyl-terminated polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60123513A JPS60123513A (en) | 1985-07-02 |
| JPS635408B2 true JPS635408B2 (en) | 1988-02-03 |
Family
ID=16910952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23064083A Granted JPS60123513A (en) | 1983-12-08 | 1983-12-08 | Production of carboxyl-terminated polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60123513A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133305A (en) * | 1980-02-22 | 1981-10-19 | Goodrich Co B F | Carboxyl-terminated diene polymer composition |
-
1983
- 1983-12-08 JP JP23064083A patent/JPS60123513A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56133305A (en) * | 1980-02-22 | 1981-10-19 | Goodrich Co B F | Carboxyl-terminated diene polymer composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60123513A (en) | 1985-07-02 |
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