JPH0381327A - Diacetylenic polyamic acid, derivative thereof, and polyimide - Google Patents

Abstract

PURPOSE:To prepare a diacetylenic polyamic acid, a deriv. thereof, and a polyimide having an excellent solid-state reactivity and giving a crosslinked product with excellent thermal and mechanical properties by incorporated repeating units represented by specific formulas into these compds. CONSTITUTION:A diacetylenic polyimide contg. at least one repeating unit of formula I (wherein Ar1 is a 2-36C divalent org. group), or a diacetylenic polyamide acid (deriv.) contg. at least one repeating unit of formula II (wherein Ar2 is a 2-36C divalent org. group; X1 and X2 are each OH, halogen, or OR (wherein R is a 1-18C org. group)) is prepd. Examples of formula I and formula II are formula III and formula IV, respectively. Because of the cohesive strength and orientation effect due to the rigid structure and the reactivity of diacetylene linkage under the electronic effect of an electron-attractive group, these compds. are excellent in the solid-state reactivity, can give a crosslinked product excellent in the thermal and mechanical properties, and can be used in applications where an excellent heat resistance and dimensional stability (e.g. a low water absorption and a low linear thermal expansion coefficient) are required.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to diacetylene polyamic acids having diacetylene bonds with excellent crosslinking reactivity, derivatives thereof, and polyamides. This invention relates to a new type of polyamic acid, its derivatives, and polyimide, which have excellent moldability and high reactivity of diacetylene groups.

(Prior art and its problems) In recent years, bolywood has been used in films, adhesives, varnishes, molding materials, etc. as a material with good heat resistance among polymer materials, and some have also been developed as fibers. It's starting to happen. Since these materials are often used in harsh environments and conditions where it is difficult to use ordinary polymer materials, there is a growing demand for improved performance. It is required to have even lower water absorption, high dimensional stability, and high elastic modulus and hardness of the negative layer.

(Problems to be Solved by the Invention) The object of the present invention is to provide a diacetylenic polyamic acid, a derivative thereof, and a derivative thereof, which can provide a crosslinked material with excellent solid phase reactivity and excellent thermal and mechanical properties. The goal is to provide a solid ξ.

(Means for Solving the Problems) As a solution to the problems described above, the present inventors attempted to impart crosslinking reactivity to polyimides and improve the above characteristics through crosslinking, and developed several diacetylene-based Although polyimides have been developed (for example, Japanese Patent Application No. 13010/1982 and Japanese Patent Application No. 158864/1982), these have problems such as insufficient crosslinking reactivity and difficulty in synthesizing raw material monomers.

The present inventors have been conducting detailed research on the tobochemical reactivity of diacetylene bonds and the technology for using them as crosslinking functional groups. We investigated the reactivity, especially the surface reactivity and the vertical reactivity, and as a result, we developed a low-molecular imide compound represented by the general formula (where x and x' represent a -valent organic group). discovered that diacetylene groups exhibit excellent reactivity, and as a result of further research,
As a result of intensive research, we discovered a material with excellent reactivity, especially solid phase reactivity, even with polymeric ξ-do compounds.
We have arrived at the present invention.

That is, the first aspect of the present invention is a diacetylene polyimide having one or more constituent units represented by the general formula (1) (where Ar1 represents a divalent organic group having 2 to 36 carbon atoms). . and its derivatives (where Ar2 is a divalent organic group having 2 to 36 carbon atoms,
+,X! is O) (, ha0gen, -OR, here, R represents an organic group having 1 to 18 carbon atoms).

In the general formula (1) or - formula (It) of the present invention, Ar+ or Ar is a divalent organic group having 2 to 36 carbon atoms, and is an aliphatic, alicyclic or aromatic hydrocarbon group. group, or a hydrocarbon group in which these are connected by some kind of linking group, and aromatic hydrocarbon groups are particularly preferred from the viewpoint of heat resistance. These divalent organic groups are exemplified, and these hydrocarbon groups are substituted with inert groups such as halogen, lower alkyl group, alkoxy group, phenoxy group, phenyl group, nitro group, and cyano group. Also good.

Particularly preferable Ar or Ar z is straight in order to impart excellent rigidity to the molecular structure of formula [1], high elastic modulus, and high degree of orientation, and Other preferable Arc and Ar2 are non-linearly oriented organic groups for imparting flexibility and bendability to the molecular structure of formula (1) and imparting excellent moldability and processability, for example, The cross-linked product obtained after the reaction of diacetylene groups has a high degree of heat resistance and a small coefficient of linear expansion.
13 etc. are preferred.

These A r 1 or Ar are 1 type or 2 types.
A mixture of two or more types may be used, and various organic groups may be used alone or in a mixture of two or more types depending on the purpose.

In the general formula (n), Xl and X2 are selected from -0H, halogen, or -OR, and the halogen is preferably F, C1t, or Br, and particularly preferably C1. Further, in -OR, R is an organic group having 1 to 18 carbon atoms, such as CI+ and CJs.

-C1H1l C4H9゜C5)+111 CIIHI11 In the present invention, the structural unit represented by formula CI) or (II) must account for a part of the total structural units of the polymer, but there is no particular restriction on its content. .

However, from the viewpoint of the effects of diacetylene bonds and diphenyl diacetylene structural linear molecular chains on the polymer molecular properties, that is, the effects on moldability and orientation, and the adjustment and effects of these properties and balance, Utilization of crosslinking reactivity that takes advantage of the extreme reactivity of acetylene bonds or solid phase reactivity, and the effects on properties such as heat resistance, dimensional stability, and water absorption of the crosslinked products produced by these crosslinking reactions. In order to clearly exhibit various effects and fully achieve the purpose of the present invention, 0.5 mol% or more of the total constituent units of the polymer should be composed of diacetylene group-containing units of general formula (I) or CI. is desirable, especially 0.8% to 100
%. -Ar in formula (1) or (It)
, or Ar, or X, or X2, or - formula (
The most preferable amount of general formula CI) or (II) varies depending on the type of structural unit other than 1) or [I[), but is generally 1 mol % or more. In particular, in order to enhance moldability and crosslinking reactivity, and to maximize dimensional stability, the amount of the structural unit represented by formula (1) or [■] is preferably 2 mol% or more, especially 3 mol or more. is more preferable, but on the other hand, as a well-balanced material that takes into consideration heat resistance after crosslinking, control of reaction during crosslinking, suppression of shrinkage of molded products (suppression of crosslinking shrinkage), - Formula CI
) or the structural unit of (II) is 0.5 mol% to 50
mol % is preferred, especially 0.8 mol % to 40 mol %
is the optimal range.

In the present invention, there are no particular restrictions on the structural units other than formula (1) or (It), and examples include polyimide structural units, polyamic acid structural units, polyamide structural units, polyester structural units, polyether and Constituent units such as polyketone, polysulfone, and polysulfide may be used singly or in combination of two or more. However, in order to best achieve the object of the present invention, it is necessary to use polyhydride, polyamic acid, polyamide, polyester, polyether, polyketone, polysulfone, polysulfide, etc., which have an aromatic hydrocarbon group as the molecular skeleton. unit, and particularly preferably a structural unit of polyigod, polyamic acid, or polyamide.

The typical structural units of polyimide and polyamic acid will be explained in more detail in 1. -Formula (III)
(IV) (V) (Vl) or [■].

(Here, z, z' are tetravalent organic groups, Zl, Zl are trivalent organic groups, Z3 is divalent organic group, Y, Y'Y+,
Yt and Ys are divalent organic groups, L and X4.

X represents -OH, halogen, -OR. ) L and Z' are tetravalent hydrocarbon groups having 5 or more carbon atoms, preferably: ◎.

Y, Y', Y+, Yz, Y3 can be selected from the above-mentioned A□ or Ar2 in a similar manner, and Xs, X4. For Xs, a preferable group can be similarly selected from the above-mentioned xl or X2.

Z,,Zt are trivalent organic groups having 5 or more carbon atoms, @@
-CO-◎; ＼＠CmiCCmiC-◎te, etc., and preferably it is mouth frida.

Z3 is a divalent organic group having 2 or more carbon atoms, and
A preferable organic group can be similarly selected from r or Ar, and generally preferable @-0-CHzCHz
-o7e)-natotheal.

Some examples of the diacetylenic polyimide and diacetylenic polyamic acid of the present invention are as follows: -Formula C
Corresponding to I) or (II), these are used alone or in combination of two or more.

In addition, some examples of structural units other than general 2 (1) or (II) are - formula (I[I), (IV),
Those corresponding to (V), (Vl) or [■] are 0 1 0, etc., and these alone or in combination of two or more are combined with the structural unit of the general formula (1) or (II) above. It is used as

Various methods are used to produce the polyimide and polyamic acid of the present invention, but a typical example is that the starting material (where Ar is Ar 1 ) is used as a starting material.

A polyamic acid is obtained by a method of oxidative coupling using a metal catalyst, or a method of reacting with H2N Ar NHZ using as a starting material, and then this polyamide acid is Preferably used is a method of thermally or chemically dehydrating and ring-closing an acid to idate the polyimide.

The above-mentioned method can also be appropriately applied and used in a method for manufacturing the polyimide or polyamic acid of the present invention by incorporating a structural unit other than general formula (1) or (II). For example, when using a method in which an oligoamic acid having a terminal ethynyl group obtained by reacting HEN-Ar NHg in a desired ratio is synthesized and then polymerized by an oxidative coupling reaction to obtain a polyamic acid, A method of obtaining polyamic acid by reacting with this 7-mer in a desired ratio to obtain polyamic acid, and then thermally or chemically dehydrating and ring-closing these to imidize to form polyimide. is preferably used.

Although there are no particular restrictions on the conditions for the oxidative coupling reaction, in order to increase the solubility and reactivity of the amic acid,
Examples of solvents include sulfoxides such as dimethyl sulfoxide and diethyl sulfoxide, formamides such as N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacedeamide, N,N-
Acedoyl acids such as diethylacedeamide, pyrrolidones such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, tertiary amines such as hexamethylphosphoramide, pyridine, picoline, and triethylacetate. Hydrocarbons such as toluene, xylene, chlorobenzene, chloroform, and halogenated hydrocarbons may be used in part.

As the metal catalyst, a metal compound usually used in an oxidative coupling reaction is used, such as a salt or complex of a transition metal such as copper, cobalt, or manganese.
Copper chloride (1), copper acetate (1), etc. are used. The reaction temperature is in the range of O''C to 120''C, preferably 5 to 80C, and the reaction is carried out by introducing oxygen or oxygen diluted with an inert gas.

In the reaction of an acid anhydride and a diamine, reaction conditions commonly used are used, and for example, as a solvent, a solvent used in an oxidative coupling reaction is appropriately selected and used.

Conventional methods and conditions can be applied to the method of forming polyigode from boria-based acid, but the reaction temperature is preferably 330°C or lower, particularly preferably 300°C or lower.
'C or lower, and if this temperature is exceeded, reactions of diacetylene bonds will also be involved, so care must be taken when isolating it as a polyimide.

The method for dehydrating and ring-closing imidization from polyamic acid is as follows:
For example, in the case of thermal processing, boria can also be formed into a film by casting or applying an acid solution, or precipitated in a poor solvent such as water.
After powdering or making into fibers, it is dried at a temperature of 150"C or less, and then heated by gradually increasing the temperature from around 100"C to 330"C or less, especially 30"C.
This can be achieved by maintaining the temperature below 0°C.

In addition, as a method for chemically dehydrating and ring-closing hydride, the above-mentioned boria hydroxide solution is added with a dehydrating agent in a stoichiometric or higher amount and a catalyst if necessary, and then this is applied to form a bottom film, coated, powdered, and fiberized. After drying at a temperature of 150'C or less,
The reaction is achieved by gradually raising the temperature from around °C and maintaining it at 330"C or below, preferably 300"C or below, most preferably 280"C or below. At this time, as a catalyst, triethylamine, dimethylaniline, pyridine, Tertiary opiates such as picoline are preferred.

When synthesizing a polyimide by dehydrating and ring-closing the polyamic acid of the present invention, the above-mentioned upper limit of the reaction temperature is particularly eliminated in applications where it is acceptable for the crosslinking reaction of diacetylene groups to proceed as well. However, in order to develop the properties of the crosslinked product to a high degree, it is desirable that the reaction from polyamic acid to iodization proceed as completely as possible, and for this reason, control of the reaction temperature is extremely important. .

In the present invention, it is also possible to mix the polyamic acids of the present invention together, or to add and mix other polyamic acids or various polymers, stabilizers, additives, etc., before carrying out the dehydration ring-closing reaction of the polyamic acids. be.

〔Effect of the invention〕

The diacetylene bond-containing polyamic acid, derivatives thereof, and polyimide of the present invention have aggregation properties and orientation properties derived from their rigid linear structure, and reactivity of diacetylene bonds due to electronic effects due to electron-withdrawing functional groups. For this reason, it is possible to provide a crosslinked material with excellent solid phase crosslinking reactivity and excellent thermal and mechanical properties.

Therefore, it can be used in applications that require a high degree of heat resistance and dimensional stability (low water absorption, low coefficient of linear expansion). It can be used in various forms such as solution, suspension, etc., and is extremely useful for films, tapes, face coating agents, adhesives, fibers, molding resins, printed circuit board resins, etc.

(Example) Example 1 (1) Ethynyl acid anhydride 1 which bottomed out according to the method described in Journal of Organism Chemistry Vol. 48, page 5135 (1983) After reaction and esterification , this esterified product 22
0 g, 12 g of cuprous chloride to 1.2 f of pyridine! .

After the reaction, the product was dissolved in a dilute NaOH aqueous solution (approx. After the reaction, the mother liquor was acidified with hydrochloric acid.The obtained product was washed with water, dried, and dehydrated by refluxing in xylene for 5 hours. This product was extracted with chloroform, further washed, dried, treated with activated carbon, and crystallized to obtain white O 1 .This diacetylenic acid anhydride was analyzed by elemental analysis and IR.
, confirmed by NMR.

Typical absorption position i! in IR (KBrBr method) (cm-'
)3075.1860.1836.1769'H-NM
R (weight oo ppm in form) 8.09.7.99 (2) 4.4'-diaminodiphenyl ether 40.
0 g (0.2 mol) was placed in a four-piece flask purged with nitrogen and dissolved in 300 d of N-methylpyrrolidone. To this was added 68.4 g (0.2 mol) of the pulverized diacetylene acid anhydride synthesized in (1) above, and the reaction was carried out at 5 to 10° C. for 2 hours while stirring.

After the obtained polyamic acid solution was cast onto a glass plate,
After drying at 100°C for 1 hour, it was further dried under reduced pressure. The obtained polyamic acid film was fixed on a support frame, then heated at 100°C for 30 minutes, then gradually raised to 200°C.
The mixture was heated at 280° C. for 1 hour and then at 280° C. for 1 hour to perform ring-closing dehydration imidization, thereby obtaining a polyimide film with a thickness of 20 μm. The IR of this polyimide film is 1766.
Typical absorption of i4d was observed at 1724 cm-'.

Next, when this polyimide film was heated to 350°C for 30 minutes, the exothermic peak ranging from 320'C to 340'C due to the diacetylene bond in DTA was no longer observed, confirming the progress of the reaction.

The coefficient of linear expansion of the obtained film was 0.18 x 10-0
-5 (/cm/”C), water absorption rate (24 hours underwater) is 0
．． It was less than 0.05%.

Example 2 In (2) of Example 1, diacetylene acid anhydride 1
A similar operation was performed using 3.7 g (0.04 mol) of pyromellitic dianhydride. The resulting polyimide film was approximately 18 μm thick. When this polyimide film was heated at 350"C for 30 minutes to react the diacetylene groups, no absorption of the diacetylene groups was observed.The coefficient of linear expansion of the obtained film was 0.35
1'O-'cm/cm/''Cs water absorption rate was 0.14%.

Comparative Example 1 A polyimide film was created in the same manner as in Example 1 using 43.6 g (0.2 mol) of pyromellitic dianhydride instead of diacetylene acid anhydride in (1) of Example 1. did. The coefficient of linear expansion of this film is 36 x 10
-'(cm/cm/''C) water absorption rate was 0.23%.

Example 3 In Example 1-(2), instead of 4,4'-diaminodiphenyl ether, paraphenylenecyamine 21.
An experiment similar to Example 1 was conducted using 6 g (0.2 mol). The crosslinked film obtained by thermally reacting the diacetylene groups of polyimide film has a coefficient of linear expansion of 0.17 x 1
0-'cm/cm/''C, water absorption rate was 0.05% or less.

Example 4 In Example 3, 23.94 g (0,07
mol) and 28.34 g of pyromellitic dianhydride (
A similar experiment was conducted using 0.13 mol). Although the obtained polyimide film was slightly brittle, its properties as a film could be measured, and the coefficient of linear expansion of the film, which was made by reacting diacetylene bonds at 350"C, was 0.8 x 10-'C.
m/c gong/'C1 water absorption rate was 0.12%.

Comparative Example 2 In Example 3, instead of the diacetylene acid anhydride,
When using pyromellitic dianhydride, the film was extremely brittle and could not be characterized.

Example 5 3,3'-diaminodiphenylsulfone (0.2 mol)
Four of them were placed in a flask, dissolved in 300mf of N,N-dimethylacetic acid, and 68.4 g (0.2 mol) of diacetylene acid anhydride was added thereto.
The reaction was carried out at 0'C for 2 hours to obtain a polyamic acid solution.

To this polyamic acid solution, 51 g (0.5 mol) of acetic anhydride and 7 g of pyridine were added and cast onto a glass plate to form a solution of about 8 mol.
After heating to 0 °C for 10 min, the resulting film was fixed on a support frame, followed by heating at 100 °C for 30 min and 200 °C.
When the obtained polyimide film was further heated at 350°C for 30 minutes, the exothermic reaction peak of the diacetylene bond in DTA disappeared, indicating that the reaction progressed. was confirmed.

The coefficient of linear expansion of this crosslinked film is 0.13X10-'
cm/cm/”C1 water absorption rate was 0.05% or less.

Example 6 In Example 5, the diacetylene acid anhydride was 1.71
A similar experiment was carried out using a biphenyl-type acid anhydride. The obtained polyimide film was
A thermal crosslinking reaction was carried out at 50''C, and the resulting film had a coefficient of linear expansion of 1.8×10”cm/Cπ/°C5 and a water absorption rate of 0.18%.

Example 7 The ethynyl acid anhydride synthesized in Example 1 (1) was
-In 600mf of methylpyrrolidone? Understood 4, 47
-Diamitsudiphenylmethane and reacted at 5-10°C for 1 hour. Thereafter, the reaction solution was poured into water to precipitate the product, which was washed and dried.

The obtained ethynyl-terminated amic acid was confirmed by IR, NMR, and elemental analysis.

54.2 g (0.14 mol) of this ethynyl-terminated amic acid was mixed with 300 ml of pyridine! , N-N methylpyrrolidone 2
00++f mixed system and add 1.2 cuprous chloride to this.
g was added thereto, oxygen was blown into the solution, and the reaction was carried out for 5 hours at a temperature ranging from 30''C to a maximum temperature of 60°C to obtain a polyamic acid solution.

This was poured into a large amount of water, the precipitate was filtered, washed repeatedly with cold dilute hydrochloric acid and water, and then dried.

After crushing this boriamic acid under cooling and making it into powder,
1 hour at 100″C, 1 hour at 200°C, then 260°C
The mixture was heated at °C for 1 hour to perform dehydration and ring closure.

Next, this powder was put into a mold with a diameter of 20 mm and degassed using a vacuum high-pressure press, and then heated under high vacuum (0.2T).
below), 260'C, 2500kg/30 minutes
Pressurize with crA, then increase temperature to finally 340°C
High-pressure powder compression molding was performed at 3000 kg/cJ for 1 hour. In the obtained molded rod, the exothermic peak of the diacetylene bond disappeared in the DTA measurement, and the crosslinking had progressed sufficiently, and the linear expansion coefficient was 0.11 cm/cm/'C1 water absorption rate was 0.
It was less than 0.05%.

Example 8 In Example 7, the diamine component was divided into 21.6 g (0.2 mol) of metaphenylene chloride and reacted with ethynyl acid anhydride separately. Ethynyl-terminated adando acids were mixed in equimolar amounts and subjected to oxidative coupling polymerization.

The obtained boria-metallic acid was further processed in the same manner as in Example 7 to obtain a polyamide powder, and this powder was further subjected to high-pressure compression molding to obtain a molded rod having crosslinked diacetylene bonds. The coefficient of linear expansion of this molded rod is 0.12cm/cm/”C1
The water absorption rate was 0.05% or less.

Example 9 4,4-diaminodiphenyl ether 60 g63.6 in which a mixture of ethynyl acid anhydride and benzophenone type acid anhydride was dissolved in 1.22 N-methylpyrrolidone
g (0.3 mol) was added to the mixed solution, and the reaction was carried out for 1 hour. According to GPC, the obtained ethynyl-terminated oligoamic acid was a mixture of oligomers having different degrees of polymerization. Add 80g of this to 500d of pyridine and 30d of N-methylpyrrolidone.
0d mixed system, 1.7 g of cuprous chloride was added thereto, and the reaction was carried out at a temperature ranging from 30"C to a maximum of 60°C while blowing oxygen to obtain a polyamic acid solution. This was poured into a large amount of water. The precipitate was filtered, washed repeatedly with cold dilute hydrochloric acid and water, and then dried.

This boria is also made by crushing tutaic acid into powder while cooling.
1 hour at 100″C, 1 hour at 200°C, then 260°C
Heated at °C for 1 hour to complete dehydration ring closure. The DTA of this powder had an exothermic peak due to the diacetylene bond. When crosslinking was carried out in the acid form by vacuum high-pressure pressing in the same manner as in Example 7 using this bolioid powder, no exothermic peak due to diacetylene bonds was observed in this molded product, and crosslinking had progressed sufficiently. The expansion rate is 0.250111/C! l/”C, water absorption rate is 0.17
% or less.

Claims (2)

[Claims] (1) Diacetylene polyimide [I] having one or more constituent units represented by the general formula [I] ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (However, Ar_1 has 2 to 36 carbon atoms. (Indicates a divalent organic group.) (2) One or two structural units represented by general formula [II]
Diacetylenic polyamic acid and its derivatives having more than one species [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, Ar_2 is a divalent organic group having 2 to 36 carbon atoms,
X_1 and X_2 are -OH, halogen, -OR, where,
R represents an organic group having 1 to 18 carbon atoms. )