JPH0546366B2 - - Google Patents
Info
- Publication number
- JPH0546366B2 JPH0546366B2 JP59030931A JP3093184A JPH0546366B2 JP H0546366 B2 JPH0546366 B2 JP H0546366B2 JP 59030931 A JP59030931 A JP 59030931A JP 3093184 A JP3093184 A JP 3093184A JP H0546366 B2 JPH0546366 B2 JP H0546366B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- copper salt
- sodium sulfite
- ppm
- acrylamide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W72/00—Interconnections or connectors in packages
- H10W72/30—Die-attach connectors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W72/00—Interconnections or connectors in packages
- H10W72/30—Die-attach connectors
- H10W72/321—Structures or relative sizes of die-attach connectors
- H10W72/325—Die-attach connectors having a filler embedded in a matrix
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- H10W72/00—Interconnections or connectors in packages
- H10W72/30—Die-attach connectors
- H10W72/351—Materials of die-attach connectors
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
Description
本発明はポリアクリルアミドの製造法に関する
ものである。
ポリアクリルアミドの製造法として、例えば、
アクリルアミド水溶液をアゾ系重合触媒の存在下
で重合させる方法が知られている。アクリルアミ
ドの重合は発熱反応であり重合温度があまり高く
なると得られるポリマーの性能が低下する。その
ため、重合に当たつてモノマー濃度を低くする方
法が考えられるが、モノマー濃度が低い場合に
は、重合後のポリマーの乾燥に手間がかかる欠点
がある。また、重合開始の温度を低くする方法も
考えられるが、アゾ系重合触媒を使用した場合、
あまり低温では重合がスムーズに進行しないた
め、特に、重合初期における重合速度が遅く、そ
のため、重合時間が長くなり生産性に劣る欠点が
あり、更に、得られるポリマーの性能も低いと言
う欠点がある。
本発明者等は上記実情に鑑み、アクリルアミド
水溶液の重合に際し、モノマー濃度を比較的高く
し、また、重合開始の温度を低くしても、重合時
間が短い良好な重合反応が行なわれ、しかも、得
られるポリマーの性能も優れた重合方法を得るこ
とを目的として種々検討した結果、アゾ系重合触
媒とある特定の化合物の共存下で重合することに
よりこの目的が達成されることを見い出し本発明
を完成した。
すなわち、本発明の要旨は、10〜35重量％のア
クリルアミド水溶液を重合させるに当たり、アク
リルアミドモノマーに対して、100〜2000ppm
のアゾ系重合触媒、３〜200ppmの酸性亜硫酸
ソーダ又は亜硫酸ソーダ及び金属として0.1〜
10ppmの銅塩を存在させることを特徴とするポリ
アクリルアミドの製造法に存する。
以下、本発明を詳細に説明する。
本発明で対象となるポリアクリルアミドの製造
法は、アクリルアミドモノマーの水溶液を重合さ
せる方法であり、モノマー濃度は10〜35重量％、
好ましくは20〜30重量％である。モノマー濃度が
あまり高いと重合中に高温となり得られるポリマ
ーの品質が低下し、また、あまり低いとポリマー
の乾燥が大変なので好ましくない。
本発明では触媒として公知のアゾ系重合触媒と
ともに、酸性亜硫酸ソーダあるいは亜硫酸ソーダ
と銅塩とを併用することを必須要件とするもので
ある。アゾ系重合触媒を単独で使用した場合に
は、モノマー濃度を高くして重合開始の温度を低
くしても重合速度が遅く良好な重合が行なわれな
い。銅塩は一般的に、アクリルアミドの重合防止
剤としてよく知られており、重合に際しては、完
全に除去することが必要と考えられているが、本
発明で前提とする特定の重合系の場合には、特定
量の銅塩が逆に、重合速度を向上させるのであ
る。
アゾ系重合触媒としては、例えば、２，2′−ア
ゾビス（２−アミジノプロパン）塩酸塩、アゾビ
スイソブチロニトリル、２，2′−アゾビス（４−
メトキシ−２，４−ジメチルバレロニトリル）、
１，1′−アゾビス（シクロヘキサンカルボニトリ
ル）などが挙げられ、特に、２，2′−アゾビス
（２−アミジノプロパン）塩酸塩が好ましい。こ
のアゾ化合物の添加量はモノマーに対して100〜
2000ppm、好ましくは400〜1400ppmであり、添
加量があまり少ないと重合が良好に行なわれず、
また、あまり多すぎると得られるポリマーの分子
量が低下するので好ましくない。
一方、酸性亜硫酸ソーダ又は亜硫酸ソーダの添
加量はモノマーに対して３〜200ppm、好ましく
は５〜100ppmである。この添加量もあまり少な
すぎると重合が良好に行なわれず、また、あまり
多すぎても得られるポリマーの性能が低下するの
で好ましくない。
また、銅塩としては通常、硫酸第二銅、塩化第
二銅、臭化第二銅、酢酸第二銅、蓚酸第二銅、硝
酸第二銅などの水溶性の２価の銅塩が挙げられ、
なかでも、硫酸第二銅が一般的に利用される。銅
塩の使用量はモノマーに対して、金属として0.1
〜20ppm、好ましくは0.2〜2ppmであり、この量
があまり少ない場合には、重合速度が遅いため短
時間で重合を行なうことができず、逆に、あまり
多い場合には、重合自体が阻害され、重合が進行
しなくなるので好ましくない。
本発明における上述の添加剤の重合系内への添
加順序は通常、酸性亜硫酸ソーダ又は亜硫酸ソー
ダを最後に添加するのが好ましく、例えば、銅
塩、アゾ系重合触媒、次いで、酸性亜硫酸ソーダ
又は亜硫酸ソーダの順で添加される。
本発明での重合温度は通常、−10〜100℃であ
り、重合開始の温度は例えば、20℃以下、好まし
くは10℃以下とするのがよい。本発明では重合開
始の温度を低くしても、重合が良好に進行する。
重合時間は通常、0.5〜10時間程度である。
本発明を実施するには、例えば、密閉型の重合
槽にモノマー水溶液を仕込み、窒素ガスを吹き込
み水溶液中の溶存酸素を除去したのち、本発明の
触媒を水溶液として添加して重合を行なう。重合
が終了したのちのポリマーはゲル状物であり、次
いで、常法に従つて平均粒径１〜10ｍ／ｍ、好ま
しくは２〜５ｍ／ｍに造粒し、更に、この粒状物
を含水量10重量％以下まで乾燥処理する。
本発明によれば、アクリルアミドの重合に際
し、例えば、重合開始温度を低くしても、短かい
時間で重合がスムーズに行なわれるので、生産性
が極めて高いものである。その上得られるポリマ
ーの粘度及び凝集性能も優れており、工業的に極
めて有利である。
次に、実施例及び比較例を挙げて本発明を更に
具体的に説明するが、本発明はその要旨を超えな
い限り以下の例に限定されるものではない。
実施例１〜４及び比較例１〜３
アクリルアミド25wt％水溶液13を15の密
閉型重合槽に仕込んだ。窒素ガス0.2m3を該水溶
液中に吹き込み完全に脱気したのち、液温10℃に
て先ず、第１表に示した銅塩を添加し、次いで、
２，2′−アゾビス（２−アミジノプロパン）塩酸
塩500ppm及び第１表に示した酸性亜硫酸ソーダ
を順次、添加混合し放置して重合を行なつた。
重合後、ゲル状のポリマーを押出造粒機にて平
均粒径2.5〓に造粒し、次いで、粒状物を80℃の
熱風により３時間乾燥処理した。
このようにして得た粒状ポリマーにつき、粘度
及び凝集性能を測定するとともに、重合系内の温
度変化を測定することにより重合速度を求めたと
ころ、第１表に示す結果を得た。
実施例５及び比較例４
実施例１において、酸性亜硫酸ソーダの代りに
亜硫酸ソーダを使用して実施例１と同様な方法で
重合を行なつた場合の結果を第２表に示す。
The present invention relates to a method for producing polyacrylamide. As a method for producing polyacrylamide, for example,
A method is known in which an aqueous acrylamide solution is polymerized in the presence of an azo polymerization catalyst. Polymerization of acrylamide is an exothermic reaction, and if the polymerization temperature is too high, the performance of the resulting polymer will deteriorate. Therefore, a method of lowering the monomer concentration during polymerization can be considered, but when the monomer concentration is low, there is a drawback that drying the polymer after polymerization is time-consuming. Another option is to lower the polymerization initiation temperature, but when using an azo polymerization catalyst,
Since polymerization does not proceed smoothly at too low a temperature, the polymerization speed is particularly slow at the initial stage of polymerization, which has the disadvantage of prolonging the polymerization time and lowering productivity.Furthermore, the performance of the obtained polymer is also low. . In view of the above-mentioned circumstances, the present inventors have discovered that when polymerizing an aqueous acrylamide solution, even if the monomer concentration is relatively high and the polymerization initiation temperature is low, a good polymerization reaction can be carried out in a short polymerization time, and, As a result of various studies aimed at obtaining a polymerization method with excellent performance of the resulting polymer, it was discovered that this objective could be achieved by polymerizing in the coexistence of an azo polymerization catalyst and a certain specific compound. completed. That is, the gist of the present invention is that in polymerizing a 10 to 35% by weight acrylamide aqueous solution, 100 to 2000 ppm of acrylamide monomer is used.
of azo polymerization catalyst, 3 to 200 ppm of acidic sodium sulfite or sodium sulfite and 0.1 to 200 ppm of metals.
A method for producing polyacrylamide characterized by the presence of 10 ppm of copper salt. The present invention will be explained in detail below. The method for producing polyacrylamide that is the object of the present invention is a method of polymerizing an aqueous solution of acrylamide monomer, and the monomer concentration is 10 to 35% by weight.
Preferably it is 20 to 30% by weight. If the monomer concentration is too high, the temperature will be high during polymerization and the quality of the resulting polymer will deteriorate, and if it is too low, it will be difficult to dry the polymer, which is not preferable. In the present invention, it is essential to use acidic sodium sulfite or sodium sulfite and a copper salt together with a known azo polymerization catalyst as a catalyst. When an azo polymerization catalyst is used alone, even if the monomer concentration is increased and the polymerization initiation temperature is lowered, the polymerization rate is slow and good polymerization cannot be carried out. Copper salt is generally well known as a polymerization inhibitor for acrylamide, and it is thought that it is necessary to completely remove it during polymerization, but in the case of the specific polymerization system assumed in this invention, On the contrary, a certain amount of copper salt improves the polymerization rate. Examples of azo polymerization catalysts include 2,2'-azobis(2-amidinopropane) hydrochloride, azobisisobutyronitrile, 2,2'-azobis(4-
methoxy-2,4-dimethylvaleronitrile),
Examples include 1,1'-azobis(cyclohexanecarbonitrile), and 2,2'-azobis(2-amidinopropane) hydrochloride is particularly preferred. The amount of this azo compound added is 100 to 100% of the monomer.
The amount is 2000ppm, preferably 400 to 1400ppm, and if the amount added is too small, polymerization will not be carried out well.
On the other hand, if the amount is too large, the molecular weight of the obtained polymer decreases, which is not preferable. On the other hand, the amount of acidic sodium sulfite or sodium sulfite added is 3 to 200 ppm, preferably 5 to 100 ppm, based on the monomer. If the amount added is too small, polymerization will not be carried out well, and if it is too large, the performance of the resulting polymer will deteriorate, which is not preferable. In addition, examples of copper salts usually include water-soluble divalent copper salts such as cupric sulfate, cupric chloride, cupric bromide, cupric acetate, cupric oxalate, and cupric nitrate. is,
Among them, cupric sulfate is commonly used. The amount of copper salt used is 0.1 as metal per monomer.
~20 ppm, preferably 0.2 to 2 ppm; if this amount is too small, the polymerization rate will be slow and polymerization cannot be carried out in a short time; on the other hand, if it is too large, the polymerization itself will be inhibited. , is not preferable because polymerization will not proceed. In the present invention, the order of addition of the above-mentioned additives into the polymerization system is usually that acidic sodium sulfite or sodium sulfite is preferably added last, for example, copper salt, azo polymerization catalyst, and then acidic sodium sulfite or sulfurous acid. Added in order of soda. The polymerization temperature in the present invention is usually -10 to 100°C, and the polymerization initiation temperature is, for example, 20°C or lower, preferably 10°C or lower. In the present invention, even if the polymerization initiation temperature is lowered, the polymerization proceeds favorably.
Polymerization time is usually about 0.5 to 10 hours. To carry out the present invention, for example, an aqueous monomer solution is charged into a closed polymerization tank, nitrogen gas is blown into the aqueous solution to remove dissolved oxygen in the aqueous solution, and then the catalyst of the present invention is added as an aqueous solution to carry out polymerization. After the polymerization is completed, the polymer is in the form of a gel, which is then granulated to an average particle size of 1 to 10 m/m, preferably 2 to 5 m/m, according to a conventional method. Dry to 10% by weight or less. According to the present invention, when polymerizing acrylamide, for example, even if the polymerization initiation temperature is lowered, the polymerization is smoothly carried out in a short period of time, resulting in extremely high productivity. Furthermore, the resulting polymer has excellent viscosity and aggregation performance, and is extremely advantageous industrially. Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Examples 1 to 4 and Comparative Examples 1 to 3 Thirteen 25 wt% acrylamide aqueous solutions were charged into 15 closed polymerization tanks. After blowing 0.2 m 3 of nitrogen gas into the aqueous solution to completely degas it, first add the copper salts shown in Table 1 at a liquid temperature of 10°C, and then
500 ppm of 2,2'-azobis(2-amidinopropane) hydrochloride and acidic sodium sulfite shown in Table 1 were successively added and mixed and allowed to stand for polymerization. After polymerization, the gel-like polymer was granulated using an extrusion granulator to an average particle size of 2.5㎜, and then the granulated material was dried with hot air at 80° C. for 3 hours. Regarding the granular polymer thus obtained, the viscosity and aggregation performance were measured, and the polymerization rate was determined by measuring the temperature change within the polymerization system, and the results shown in Table 1 were obtained. Example 5 and Comparative Example 4 Table 2 shows the results when polymerization was carried out in the same manner as in Example 1 except that sodium sulfite was used instead of acidic sodium sulfite.
【表】【table】
【表】【table】
Claims (1)
させるに当たり、アクリルアミドモノマーに対し
て、100〜2000ppmのアゾ系重合触媒、３〜
200ppmの酸性亜硫酸ソーダ又は亜硫酸ソーダ及
び金属として0.1〜10ppmの銅塩を存在させる
ことを特徴とするポリアクリルアミドの製造法。 ２ 銅塩が水溶性の２価の銅塩であることを特徴
とする特許請求の範囲第１項記載の方法。 ３ 銅塩が硫酸第二銅であることを特徴とする特
許請求の範囲第１項記載の方法。 ４ 銅塩を酸性亜硫酸ソーダあるいは亜硫酸ソー
ダよりも先に重合系内に添加することを特徴とす
る特許請求の範囲第１項記載の方法。 ５ 銅塩の使用量がアクリルアミドモノマーに対
して、金属として0.2〜2ppmであることを特徴と
する特許請求の範囲第１項記載の方法。 ６ アゾ系重合触媒が２，2′−アゾビス（２−ア
ミジノプロパン）塩酸塩であることを特徴とする
特許請求の範囲第１項記載の方法。 ７ 重合開始の温度が20℃以下であることを特徴
とする特許請求の範囲第１項記載の方法。[Claims] 1. In polymerizing a 10 to 35% by weight aqueous solution of acrylamide, 100 to 2000 ppm of an azo polymerization catalyst to the acrylamide monomer;
A method for producing polyacrylamide, characterized in that 200 ppm of acidic sodium sulfite or sodium sulfite and 0.1 to 10 ppm of copper salt as a metal are present. 2. The method according to claim 1, wherein the copper salt is a water-soluble divalent copper salt. 3. The method according to claim 1, wherein the copper salt is cupric sulfate. 4. The method according to claim 1, characterized in that the copper salt is added to the polymerization system before the acidic sodium sulfite or the sodium sulfite. 5. The method according to claim 1, wherein the amount of copper salt used is 0.2 to 2 ppm as a metal based on the acrylamide monomer. 6. The method according to claim 1, wherein the azo polymerization catalyst is 2,2'-azobis(2-amidinopropane) hydrochloride. 7. The method according to claim 1, wherein the polymerization initiation temperature is 20° C. or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59030931A JPS60177010A (en) | 1984-02-21 | 1984-02-21 | Preparation of polyacrylamide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59030931A JPS60177010A (en) | 1984-02-21 | 1984-02-21 | Preparation of polyacrylamide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60177010A JPS60177010A (en) | 1985-09-11 |
| JPH0546366B2 true JPH0546366B2 (en) | 1993-07-13 |
Family
ID=12317422
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59030931A Granted JPS60177010A (en) | 1984-02-21 | 1984-02-21 | Preparation of polyacrylamide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60177010A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100318327B1 (en) * | 1995-12-16 | 2002-04-22 | 구광시 | Manufacturing method of emulsion type polymer coagulant |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5946247B2 (en) * | 1976-03-18 | 1984-11-12 | 三井東圧化学株式会社 | Production method of acrylamide water-soluble polymer |
| JPS56103210A (en) * | 1980-01-21 | 1981-08-18 | Mitsubishi Gas Chem Co Inc | Preparation of water-soluble cationic polymer |
| JPS57121007U (en) * | 1981-01-20 | 1982-07-27 |
-
1984
- 1984-02-21 JP JP59030931A patent/JPS60177010A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60177010A (en) | 1985-09-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |