JP2014201740A5

JP2014201740A5 -

Info

Publication number: JP2014201740A5
Application number: JP2013090734A
Authority: JP
Filing date: 2013-04-05
Publication date: 2016-08-18

Description

すなわち、本発明にかかるイミドオリゴマーは、非軸対称性ａ−ＢＰＤＡに由来する非軸対称部位をオリゴマー鎖に酸二無水化物主分子として４量体あたり３分子以上有し、１，４，４−ＡＰＢをジアミン主分子として４量体あたり３分子以上、３，４’−ＯＤＡ、１，３，３−ＡＰＢ、１，３，４−ＡＰＢ１分子以下のみ有し、且つ架橋性末端が４−ＰＥＰＡからなり、下記一般式（１）により表されることを特徴とするものである。
That is, the imide oligomer according to the present invention has 3 or more molecules per tetramer as non-axisymmetric sites derived from non-axisymmetric a-BPDA as an acid dianhydride main molecule in the oligomer chain. -APB as a diamine main molecule having 3 or more molecules per tetramer, 3,4'-ODA, 1,3,3-APB, 1,3,4-APB only 1 molecule or less, and a crosslinkable terminal is 4- It consists of PEPA and is represented by the following general formula (1).

また、本発明にかかるアミック酸オリゴマーは、４量体あたり非軸対称性酸二無水化物ａ−ＢＰＤＡ３分子以上、１，４，４−ＡＰＢを３分子以上と主分子とし、３，４’−ＯＤＡ、１，３，３−ＡＰＢ、１，３，４−ＡＰＢから選ばれたジアミン単独または組み合わせて１分子以下のみ有するオリゴマー鎖を特徴とし、且つ架橋性末端基が４−ＰＥＰＡからなり、下記一般式（２）により表されることを特徴とするものである。
（ｍ、ｎは各イミド繰り返し構造の平均重合度でｍは１〜１２、ｎは０〜３である。） In addition, the amic acid oligomer according to the present invention comprises 3 or more non-axisymmetric acid dianhydrides a-BPDA per tetramer, 3 or more 1,4,4-APB as main molecules, and 3,4′- Characterized by an oligomer chain having only one molecule or less in combination of diamines selected from ODA, 1,3,3-APB, 1,3,4-APB, alone or in combination, and the crosslinkable end group is composed of 4-PEPA, It is represented by the general formula (2).
(M and n are average polymerization degrees of each imide repeating structure, m is 1 to 12, and n is 0 to 3.)

本発明にかかるイミドオリゴマーは、下記一般式（１）により表される。
The imide oligomer according to the present invention is represented by the following general formula (1).

実施例１
下記７−３としたイミドオリゴマーを例示すると（他も７−３と同じ操作手順）、四つ口フラスコ（５００ｍｌ）を室温下、窒素置換し、窒素気流下、ＮＭＰ２３０ｇをＮ／Ｎ〜３０％となるように攪拌し、１，４，４−ＡＰＢ４１．１５０ｇ、３，４’−ＯＤＡ８．０５３ｇとａ−ＢＰＤＡ４７．３３２ｇを加え、室温下攪拌する。２時間後温度センサーが発熱の終了を確認後、４−ＰＥＰＡを９．９８４ｇ加え、二時間後温度センサーで発熱の終了を確認した。その後、窒素気流下、無水酢酸４００ｇ、トリエチルアミン３６．７ｇ、を加え１２〜２４時間続け、淡い黄色を呈したポリイミドオリゴマーワニスを得た。
その後、生成した酢酸とトリエチルアミン等を真空下留去して得たワニスを洗浄乾燥させたガラス板にカプトンテープを用い、成形型とし、ガラス棒を用い、均一にガラス板に塗布し、１９０℃で１時間乾燥させ、３８０℃で２時間加熱処理をした。冷却後、ナイフで切れ目を入れ、水の入ったビーカーにガラス板ごと付けた。剥離したフィルムを室温で一昼夜乾燥させ、幅３ｍｍ、長さ５０ｍｍに切り取り、膜厚測定後、力学試験を行った。 Example 1
Below 7 -3 and the To illustrate imide oligomer (other same operating procedure as 7-3), at room temperature under a four-necked flask (500 ml), purged with nitrogen, a nitrogen stream, NMP230g the N / N~30% Then, 41,150 g of 1,4,4-APB, 8.053 g of 3,4'-ODA and 47.332 g of a-BPDA are added, and the mixture is stirred at room temperature. Two hours later, after the temperature sensor confirmed the end of heat generation, 9.984 g of 4-PEPA was added, and after two hours, the temperature sensor confirmed the end of heat generation. Thereafter, 400 g of acetic anhydride and 36.7 g of triethylamine were added under a nitrogen stream and continued for 12 to 24 hours to obtain a polyimide oligomer varnish exhibiting a pale yellow color.
Thereafter, the produced acetic acid and triethylamine and the like were distilled off under vacuum, and the varnish obtained by washing and drying was used with a Kapton tape to form a mold, using a glass rod, uniformly applied to the glass plate, 190 ° C. And dried at 380 ° C. for 2 hours. After cooling, a cut was made with a knife, and the glass plate was attached to a beaker containing water. The peeled film was dried at room temperature for a whole day and night, cut into a width of 3 mm and a length of 50 mm, measured for film thickness, and then subjected to a mechanical test.

Claims

Three or more molecules of non-axisymmetric aromatic acid anhydride 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (a-BPDA) per tetramer, 1,4-bis (4-aminophenoxy) ) 3 or more molecules of benzene (1,4,4-APB) alone or in combination, 1 or less molecule of 3,4'-oxydianiline (3,4'-ODA) and 4 crosslinkable ends An imide oligomer comprising a phenylethynylphthalic anhydride (4-PEPA) residue and represented by the following general formula (1).
(In the above formula (1), m and n are the average degree of polymerization of each imide repeating structure, m is 1 to 8, n is 0 to 3, and m + n ≦ 8)

The imide oligomer according to claim 1, wherein the average molecular weight of the whole imide oligomer is 8,000 or less.

Amic acid oligomer under following general formula (2), wherein.

Amic acid oligomer according to claim 3 - N- methyl-2-pyrrolidone (NMP), N, N- dimethylacetamide (DMAc), γ- Buchirotakuton and any polar solvent presence of Aquamid (TM) Imide oligomer obtained by imidization by heat dehydration reaction.

Claims amic acid according to claim 3 oligomers - the use of a triethylamine / acetic anhydride such as chemical imidization agent at a low temperature of 60 ° C. or less, after the imidization, the remaining chemical imidization agent and its by-product was distilled off under reduced pressure The resulting imide oligomer .

A powdered imide oligomer obtained by precipitating the imide oligomer obtained in claim 1, 2, 4 or 5 using an alcohol such as methanol.

A polyimide resin obtained by heat-curing the oligomer according to any one of claims 1 to 6.