JPH0233052B2 - SHUKUGOJUGOTAINOSEIZOHOHO - Google Patents
SHUKUGOJUGOTAINOSEIZOHOHOInfo
- Publication number
- JPH0233052B2 JPH0233052B2 JP10999382A JP10999382A JPH0233052B2 JP H0233052 B2 JPH0233052 B2 JP H0233052B2 JP 10999382 A JP10999382 A JP 10999382A JP 10999382 A JP10999382 A JP 10999382A JP H0233052 B2 JPH0233052 B2 JP H0233052B2
- Authority
- JP
- Japan
- Prior art keywords
- diamine
- range
- diamines
- acid
- mol
- 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
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 150000004985 diamines Chemical class 0.000 claims description 16
- 238000012643 polycondensation polymerization Methods 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- -1 cyclic diamine Chemical class 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000005263 alkylenediamine group Chemical group 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 13
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229920006158 high molecular weight polymer Polymers 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyamides (AREA)
Description
【発明の詳細な説明】
本発明は、ポリエチレンオキシジグリコール酸
およびジアミン類を用いて縮合重合体を製造する
方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a condensation polymer using polyethyleneoxydiglycolic acid and diamines.
本発明者らは、ポリエチレンオキシジグリコー
ル酸について種々研究を進めた結果、ジアミン類
と縮合重合させることにより高分子量の重合体が
得られることを見出して、本発明を完成させたも
のである。 As a result of conducting various studies on polyethylene oxydiglycolic acid, the present inventors have completed the present invention by discovering that a high molecular weight polymer can be obtained by condensation polymerization with diamines.
本発明の製造方法は、一般式
HOOCCH2O−（CH2CH2O−）oCH2COOH
（式中、ｎは４〜300の範囲にある整数である。）
で示されるポリエチレンオキシジグリコール酸
（以下、PEO酸と記す。）とジアミン類を、前者
１モルに対して0.5〜２モルの範囲の割合で50〜
300℃の範囲の温度で縮合重合させることを特徴
とするものである。 The production method of the present invention is a polyethylene oxydiglycol represented by the general formula HOOCCH 2 O-(CH 2 CH 2 O-) o CH 2 COOH (wherein n is an integer in the range of 4 to 300). acid (hereinafter referred to as PEO acid) and diamines at a ratio of 0.5 to 2 mol per 1 mol of the former.
It is characterized by condensation polymerization at a temperature in the range of 300°C.
PEO酸は前記一般式で示される化合物で、平
均分子量が300〜10000の広い範囲にあるものが本
発明において有効に使用できる。ジアミン類とし
ては特に制限はなく種々のジアミンを用いること
ができるが、例えば一般式
H2N（CH2）nNH2
（式中ｍは、２〜10の範囲にある整数である。）
で示されるアルキレンジアミン（例えば、エチレ
ンジアミン、プロピレンジアミン、ブチレンジア
ミン、ヘキサメチレンジアミンなど。）；フエニレ
ンジアミン、ジアミノジフエニルメタンなどの如
き芳香族ジアミン；H2NC3H6O（C2H4O）p
C3H6NH2の式で示されるポリエチレングリコー
ルジアミン類；ピペラジンなどの如き環状ジアミ
ンを挙げることができる。 The PEO acid is a compound represented by the above general formula, and those having an average molecular weight within a wide range of 300 to 10,000 can be effectively used in the present invention. The diamines are not particularly limited and various diamines can be used, but for example, those with the general formula H 2 N (CH 2 ) n NH 2 (where m is an integer in the range of 2 to 10). alkylene diamines (e.g., ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, etc.); aromatic diamines such as phenylene diamine, diaminodiphenylmethane, etc.; H 2 NC 3 H 6 O (C 2 H 4 O ) p
Examples include polyethylene glycol diamines represented by the formula C 3 H 6 NH 2 ; cyclic diamines such as piperazine.
縮合重合反応は、PEO酸とアミン類を、前者
１モルに対して後者0.5〜２モルの範囲、好まし
くは0.8〜1.7の範囲の割合で、50〜300℃、好ま
しくは90〜250℃の範囲の温度で、１〜30時間、
好ましくは５〜25時間の範囲の反応時間で行なう
ものである。この際、PEO酸１モルに対してジ
アミン類１モルの割合では縮合度の極めて高い、
即ち高分子量の重合体を得ることができ、PEO
酸１モルに対してジアミン類１モル未満の割合で
は両末端カルボキシル基の重合体が得られ、逆に
１モルを越える割合では両末端アミンの重合体が
得られる。反応温度を50℃未満の低温としたので
はPEO酸−ジアミン類の塩が形成されるにとど
まり、逆に300℃を越える高温としたのでは生成
物に着色があつたり、あるいは分解が起つてくる
ので好ましくない。反応圧力に関しては特に制限
はないが、生成水を系外に除去する観点から、減
圧〜数Kg／cm2の範囲とするのが好ましい。また、
必要に応じて、トルエン、キシレン、ベンゼン、
クメン、ジオキサンなどの如き化合物の反応溶媒
として使用できる。生成水を共沸蒸溜により除去
することを考慮するなら、反応溶媒としてトルエ
ンを用いるのが好ましい。 The condensation polymerization reaction is carried out at a temperature of 50 to 300°C, preferably 90 to 250°C, at a ratio of 0.5 to 2 mol of the latter, preferably 0.8 to 1.7, per 1 mol of the PEO acid and amines. At a temperature of 1 to 30 hours,
Preferably, the reaction time is in the range of 5 to 25 hours. At this time, the ratio of 1 mole of diamines to 1 mole of PEO acid has an extremely high degree of condensation.
In other words, a high molecular weight polymer can be obtained, and PEO
If the ratio is less than 1 mol of diamine per 1 mol of acid, a polymer with carboxyl groups at both ends will be obtained, whereas if the ratio exceeds 1 mol, a polymer with amines at both ends will be obtained. If the reaction temperature is set to a low temperature of less than 50°C, only PEO acid-diamine salts will be formed, whereas if the reaction temperature is set to a high temperature of over 300°C, the product may be colored or decomposed. This is not desirable because it causes There is no particular restriction on the reaction pressure, but from the viewpoint of removing produced water from the system, it is preferably in the range of reduced pressure to several kg/cm 2 . Also,
Toluene, xylene, benzene,
It can be used as a reaction solvent for compounds such as cumene, dioxane, etc. If removing produced water by azeotropic distillation is considered, toluene is preferably used as the reaction solvent.
PEO酸とジアミン類の使用割合は前者の通り
であるが、高分子量の重合体を得る場合、等モル
で縮合重合反応を進行させるのが好ましい。この
場合、例えばPEO酸とジアミン類の塩をインー
シチユー（in−situ）で形成させ、即ち両者の等
モル性を高め、引続いて当該塩を所望の反応温度
に保つて縮合重合反応を進行させる方法を挙げる
ことができる。この製造方法を化学反応式で示す
ならば、IRおよびNMRによる生成重合体の構造
確認から、次の通りであると考えられる。しか
し、本発明の範囲は当該反応式のみで制限されな
いことは言うまでもない。 The ratio of PEO acid and diamine used is the same as the former, but when obtaining a high molecular weight polymer, it is preferable to proceed with the condensation polymerization reaction in equimolar amounts. In this case, for example, a salt of PEO acid and diamines is formed in-situ, that is, the equimolar nature of both is increased, and the condensation polymerization reaction is then carried out by keeping the salt at a desired reaction temperature. Here are some methods. If this production method were to be expressed as a chemical reaction formula, it would be as follows based on the structural confirmation of the produced polymer by IR and NMR. However, it goes without saying that the scope of the present invention is not limited only by the reaction formula.
HOOCCH2O−（CH2CH2O−）oCH2COOH
＋H2N（CH2）6NH2→
以下、実施例により本発明を更に詳しく説明す
る。HOOCCH 2 O− (CH 2 CH 2 O−) o CH 2 COOH +H 2 N (CH 2 ) 6 NH 2 → Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
分子量400のPEO酸４モルとヘキサメチレンジ
アミン４モルを混合し、得られた混合物を200℃
の温度に６時間保ち縮合重合反応を進めた。得ら
れた重合体の0.5ｇ／dlにおけるηsp／Ｃ（H2O）
は0.063であつた。Example 1 4 moles of PEO acid with a molecular weight of 400 and 4 moles of hexamethylene diamine were mixed, and the resulting mixture was heated at 200°C.
The condensation polymerization reaction was carried out by maintaining the temperature at . ηsp/C(H 2 O) at 0.5 g/dl of the obtained polymer
was 0.063.
実施例 ２
実施例１において、混合物の代りにPEO酸と
ヘキサメチレンジアミンを60℃で２時間反応させ
て得られた生成物を用いる他は同様にして縮合重
合反応を進めた。得られた重合体の0.5ｇ／dlに
おけるηsp／Ｃ（H2O）は0.124であつた。Example 2 A condensation polymerization reaction was carried out in the same manner as in Example 1, except that instead of the mixture, a product obtained by reacting PEO acid and hexamethylene diamine at 60° C. for 2 hours was used. The obtained polymer had a ηsp/C(H 2 O) of 0.124 at 0.5 g/dl.
尚、PEO酸の0.5ｇ／dlにおけるηsp／Ｃ（H2O）
は0.030であつた。 In addition, ηsp/C (H 2 O) at 0.5 g/dl of PEO acid
was 0.030.
実施例 ３
実施例２において、分子量400のPEO酸の代り
に分子量1000のPEO酸を用いる他は同様にして
縮合重合反応を進めた。得られた重合体のηsp／
Ｃ（H2O）は0.310であつた。Example 3 The condensation polymerization reaction was carried out in the same manner as in Example 2, except that PEO acid with a molecular weight of 1000 was used instead of PEO acid with a molecular weight of 400. ηsp/ of the obtained polymer
C(H 2 O) was 0.310.
尚、PEO酸のηsp／Ｃ（H2O）は0.053であつた。 Incidentally, ηsp/C(H 2 O) of the PEO acid was 0.053.
実施例 ４
実施例３において、ヘキサメチレンジアミンの
代りにピペラジンを用いる他は同様にして縮合重
合反応を進めた。得られた重合体のηsp／Ｃ
（H2O）は0.259であつた。Example 4 The condensation polymerization reaction was carried out in the same manner as in Example 3, except that piperazine was used instead of hexamethylene diamine. ηsp/C of the obtained polymer
(H 2 O) was 0.259.
Claims (1)
ジアミン類を、前者１モルに対して後者0.5〜２
モルの範囲の割合で、50〜300℃の範囲の温度で
縮合重合させることを特徴とする縮合重合体の製
造方法。 ２ ジアミン類が一般式 H2N（CH2）nNH2 （式中、ｍは２〜10の範囲にある整数である。） で示されるアルキレンジアミンである特許請求の
範囲第１項記載の製造方法。 ３ ジアミン類が環状ジアミンである特許請求の
範囲第１項記載の製造方法。 ４ ジアミン類が一般式 H2NC3H6O（C2H4O）pC3H6NH2 （式中、ｐは３〜300の範囲にある整数である。） で示されるポリエチレングリコールジアミン類で
ある特許請求の範囲第１項記載の製造方法。[Claims] 1. Polyethyleneoxydiglycol represented by the general formula HOOCCH 2 O-(CH 2 CH 2 O-) o CH 2 COOH (wherein n is an integer in the range of 4 to 300) Acid and diamines, 0.5 to 2 mol of the latter per 1 mol of the former.
A method for producing a condensation polymer, characterized in that the condensation polymerization is carried out at a temperature in the range of 50 to 300° C. in a proportion in the molar range. 2. The diamine according to claim 1, wherein the diamine is an alkylene diamine represented by the general formula H 2 N (CH 2 ) n NH 2 (wherein m is an integer in the range of 2 to 10). Production method. 3. The manufacturing method according to claim 1, wherein the diamine is a cyclic diamine. 4 Polyethylene glycol whose diamines are represented by the general formula H 2 NC 3 H 6 O (C 2 H 4 O) p C 3 H 6 NH 2 (wherein p is an integer in the range of 3 to 300) The manufacturing method according to claim 1, which is a diamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10999382A JPH0233052B2 (en) | 1982-06-28 | 1982-06-28 | SHUKUGOJUGOTAINOSEIZOHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10999382A JPH0233052B2 (en) | 1982-06-28 | 1982-06-28 | SHUKUGOJUGOTAINOSEIZOHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS591532A JPS591532A (en) | 1984-01-06 |
| JPH0233052B2 true JPH0233052B2 (en) | 1990-07-25 |
Family
ID=14524361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10999382A Expired - Lifetime JPH0233052B2 (en) | 1982-06-28 | 1982-06-28 | SHUKUGOJUGOTAINOSEIZOHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0233052B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5597579A (en) * | 1995-03-06 | 1997-01-28 | Ethicon, Inc. | Blends of absorbable polyoxaamides |
| US5962023A (en) * | 1995-03-06 | 1999-10-05 | Ethicon, Inc. | Hydrogels containing absorbable polyoxaamides |
| JP5503111B2 (en) * | 2007-04-03 | 2014-05-28 | ローム・アンド・ハース・エレクトロニック・マテリアルズ，エル．エル．シー． | Metal plating composition and method |
-
1982
- 1982-06-28 JP JP10999382A patent/JPH0233052B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS591532A (en) | 1984-01-06 |
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