JPH03232840A - Fumarate-type diacetylene co-oligomer - Google Patents

Abstract

PURPOSE:To obtain the subject oligomer by using a fumarate-type diacetylene compound as a main raw material and copolymerizing with a compound such as a nadic esfer-type diacetylene compound at a specific molar ratio and polymerization degree. CONSTITUTION:The objective copolymerized diacetylene oligomer is composed of a fumarafe-type recurring unit of formula I and a recurring unit of formula II (X is 2-8C bivalent aliphatic or alicyclic unsaturated hydrocarbon group), wherein the molar ratio of the recurring units (I/Il) is 1-10 and the polymerization degree is 4-25. The objective oligomer also includes a copolymerized diacetylene oligomer containing the recurring units of formula I, formula II and formula III, wherein the sum of the recurring units of formula I and formula II is 60-100% (excluding 100%), the amount of the recurring unit of formula III is <=40mol%, and the molar ratio (I/II) and the polymerization degree are same as those of the first oligomer. The oligomer can suppress the decomposition with heat generated in the production process and has excellent handleability and moldability.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to precision machinery and electronics fields, and has excellent curing reactivity, ease of handling, rigidity, hardness, dimensional stability, heat resistance, etc. This invention relates to fumaric acid ester diacetylene cooligomers with good properties.

[Conventional technology]

In recent years, the synthesis of single-crystalline polymers using topochemical reactions with diacetylene compounds has attracted attention, and attempts have been made to develop various functional polymers with high elastic modulus using this method.

The present inventors have already synthesized a novel diacetylene compound and have used it to develop various polymer molded bodies having a high elastic modulus. In particular, we have discovered that the elastic modulus of scales can be further increased by combining a carbon-carbon single bond with a diacetylene group.

For example, it has been discovered that an ester compound of fumaric acid and 1,6-hexadiyne exhibits excellent performance in terms of elastic modulus and various properties by thermosetting by high-pressure molding (Japanese Patent Laid-Open No. 63-96144). Publication, JP-A-63-295
612, JP-A-63-295639).

[Problems to be Solved by the Invention] However, these fumaric acid ester-based diacetylene compounds have a low degree of polymerization, are crystalline, have poor solubility, and are unsuitable as molding materials. There are many issues that need to be resolved, such as being dangerous as it is prone to decomposition reactions, and requiring special curing conditions such as ultra-high pressure.

[Means to solve the problem]

In order to control the crosslinking reaction and improve moldability, the inventors of the present invention conducted intensive studies on the molecular skeleton, types of double bonds, types of diacetylene bonds, etc., and as a result, the inventors of the present invention mainly used fumaric acid ester-based diacetylene compounds. For example, by copolymerizing this with a nadic acid ester diacetylene compound, the resulting fumaric acid ester diacetylene co-oligomer exhibits a melting point of 100°C or less and also has good solubility in organic solvents. I discovered something. Therefore, after further careful consideration of the appropriate types and molar ratios of copolymerization components, we found that the fumaric acid-based heavy bond and diacetylene group in general formula (1) are the carbon-carbon group shown in general formula (II). The present invention has been made based on the discovery that it exhibits good reactivity with unsaturated groups and diacetylene groups, causes a co-reaction, allows the crosslinking reaction to proceed in good yield, and can suppress rapid decomposition reactions during heat curing. has been reached.

That is, the present invention is as shown below.

1. In a copolymerized diacetylene oligomer consisting of a fumaric acid ester-based repeating unit represented by general formula (I) and a repeating unit represented by general formula (II), the molar ratio of repeating units (1) and (II) (I) / (II
) is in the range of 1 to 10, and the degree of polymerization of the copolymerized diacetylene oligomer is 4 to 25.
CmiCCH2-0+ ------(II) 2゜The sum of the repeating units of the fumarate ester represented by the general formula (1) and the repeating units represented by the general formula (II) is 60 to less than 100% In the copolymerized diacetylene oligomer in which the repeating unit represented by the general formula (II[) is 40 mol% or less, the repeating unit (I)
and (II), the molar ratio (1)/(II) is in the range of 1 to 10, and the degree of polymerization of the copolymerized diacetylene oligomer is 4 to 25. -C00CH2-C= C-C= CCH
g-0+ ---(II)+ GO-R'
-COO-R"-0+ -1-・-
--(IIl) In the general formula (I[), X has 2 carbon atoms
~8 aliphatic or alicyclic divalent unsaturated hydrocarbon group, exemplified by: CH3 Cl1=CII-C)l=CII- CH2 1 -CHz CHz-CH=CH- CHz, etc., and also includes unsaturated hydrocarbon groups in which these hydrogen atoms are substituted with halogen atoms.

When a compound represented by the general formula (II) containing such a preferable group is used, the reactivity of the diacetylene cooligomer of the present invention during heat curing becomes stable, rapid runaway reactions are suppressed, and During molding and curing, it has good solubility and meltability in solvents, and furthermore, the resulting cured molded product has excellent heat resistance, dimensional stability, etc.

Further, R1 in the general formula (I[[) is a divalent aryl group having 6 to 12 carbon atoms, and examples thereof include the following.

In addition, 2 is a divalent hydrocarbon CH3 group having 2 to B carbon atoms, for example, CH2CH2 CH2CH, + GHz +a Hz-C= C-C= C-CH2-, etc., and the physical properties of the cured molded product , especially in order not to impair the elastic modulus and dimensional stability, especially -CH2-CmiC-CmiC-C)
I2- is preferably used.

Regarding the molar ratio of general formulas CI) and (II) of the present invention, (
1)/(II) is in the range of 1 to 10, but considering the heat resistance, reactivity, and control of the reaction of the molded product obtained, the molar ratio of general formulas (I) and (II) (
(I)/(II)) is preferably 1.2-7, more preferably 1.5-5. Molar ratio ((I)/(■
)) is less than 1, the physical properties of the cured molded product, especially the highest physical property value in terms of elastic modulus, cannot be obtained, which is not preferable.
If 1)/(II) is 10 or more, handling during molding is not good, and rapid decomposition reaction during curing is not sufficiently suppressed, which is not preferable.

In the present invention, the sum of the repeating units of the fumarate ester represented by the general formula (I) and the repeating units represented by the general formula (II) is selected within the range of 60 to less than 100 mol%, but ) and (II), particularly preferably from 70 to less than 100 mol% in order not to impair the excellent physical properties such as high elastic modulus, high heat resistance, and dimensional stability.

Represented by the general formula (I[[), the repeating unit is selected within a range of 40 mol% or less, but the fumaric acid-based diacetylene co-oligomer has high elastic modulus, high heat resistance, dimensional stability, and molding processability. The content is preferably 30 mol% or less in order not to impair properties.

The degree of polymerization of the fumaric acid-based diacetylene cooligomer of the present invention is in the range of 4 to 25, but preferably in the range of 4 to 20 in consideration of reactivity and moldability. When the degree of polymerization is less than 4, when molded as a thermosetting resin, handling becomes difficult, decomposition occurs during molding, and foaming occurs, resulting in deterioration of the physical properties of the molded product. If the degree of polymerization is 0.25 or more, the solubility in solvents will be poor and the melting point will be high, causing decomposition before melting and making molding difficult.

The method for producing the fumaric acid-based diacetylene cooligomer includes, for example, JP-A-64-74219 and JP-A-6474.
For example, the method disclosed in 218 can be applied, for example, by mixing 2.4 hexadiine 1,6 diol and a halide such as fumaric acid, nadic acid, maleic acid, acrylic acid, etc. with other compounds as raw materials. or fumaric acid dipropargyl ester, HC=C
-CH2-Coo-X-C00CH2C=CH dibropargyl ester compound, and IC=C-
Examples of the manufacturing method include a method in which a predetermined amount of dipropargyl ester represented by C00CHz-CmiCH is mixed and oxidative coupling polymerization is carried out using a metal catalyst.

One example of the condensation polymerization method is to dissolve 2,4-hexadiyne 1,6 diol in an alkaline aqueous solution and mix the solution with dichloride represented by Cff QC-X-COCn,
If necessary, it can be synthesized by mixing and reacting a solution obtained by mixing a predetermined amount of dichloride represented by C1)C-R'-Cock in an organic solvent. There are no particular restrictions on the type, concentration, and amount of the alkaline aqueous solution and organic solvent used at this time.As the alkali, commonly used NaOH and KOI are preferred, and as the organic solvent, chloroform, toluene, chlorobenzene,
Various solvents such as dichlorobenzene, cyclohexane, and methyl ethyl ketone can be used. There are also no particular restrictions on the reaction temperature and time, and the conditions may be set as necessary, but preferably the reaction temperature is -20°C to 30°C.
The temperature is 0°C, and the reaction time is 1 minute to 10 hours.

Next, to give an example of the oxidative coupling polymerization method, for example, separately synthesized HC=C-CH2-00C-X-Coo-CH2-C-
Dipropargyl esters such as fumaric acid, nadic acid, maleic acid, acrylic acid, muconic acid, etc., represented by CI (represented by CI) are mixed at the required concentration, using cuprous chloride as a metal catalyst, and pyridine as a solvent. The concentration of the metal catalyst used is not particularly limited, but is preferably 0.01.
~1.0 equivalent. Furthermore, there are no particular limitations on the solvent, but pyridine is preferred in order to increase the yield of the compound. Further, there are no particular restrictions on the amount of oxygen, reaction temperature, and reaction time, and the conditions may be set depending on the target product and necessity.

The degree of polymerization of the fumaric oxygen-based diacetylene cooligomer in the present invention can be measured by nuclear magnetic resonance (NMR) and terminal group quantitative measurement. Nuclear magnetic resonance (NMR) can determine the degree of polymerization from the ratio of protons of terminal ethynyl groups to protons of methylene groups. Furthermore, as a method for quantitatively measuring end groups, the amounts of carboxylic acid ends and alcohol ends can be measured by alkaline titration. The alcohol terminals are determined by first reacting the terminal groups of fumaric acid diacetylene co-oligomer with divalent acid chloride, then hydrolyzing it to carboxylic acid, titrating with alkali to determine the amount of both terminal groups, and determining the amount of both terminal groups. degree can be calculated.

3 [Example] In order to explain the present invention in detail, the present invention will be specifically explained using Examples, but the present invention is not limited thereto.

Example 1 0.416 moles of propargyl alcohol and 0.208 to 0.208 moles of fumaric acid dichloride were reacted under dimethylaniline to form IC= CCHzCOOCH=CHCOOCH2
-C=CI was synthesized in an amount of 0.208 mol. Similarly, 0.416 mol of propargyl alcohol and 0.066 mol of nadic acid dichloride were added to 200 ml of pyridine.
The mixture was mixed with a solution containing 0.005 mol of cuprous chloride in 1 liter of water and reacted while bubbling oxygen to obtain the desired product.

Obtained 4 The yield of cooligomer was 95%.

IR (KBr): 3084cm-' 2984c
m-', 2944cm-'2160cm"', 21
27CT11-', 1729cm-', 1293c
m-'1160cm-' etc.

As a result of comparing the protons of the terminal ethynyl group and the protons of the methylene group by NMR, it was confirmed that the polymer was a fumaric acid diacetylene co-oligomer with a nonamer polymerization degree. Next, the meltability and solubility of the obtained fumaric acid-based diacetylene cooligomer were investigated using heat and organic solvents such as chlorobenzene and dimethyl sulfoxide. , was found to be soluble in dimethyl sulfoxide. When a glass fiber cloth was impregnated with this solution and the solvent was evaporated, a uniformly integrated and good prepreg was obtained.

Synthesis of Example 2 CH= CCH2C00CH=CHCOOCII2C=
The desired product was obtained in the same manner as in Example 1, except that 0.1 mol of CH was added.

The yield of the obtained cooligomer was 93%.

IR (KBr): 3084cm-', 2984c
+++-', 2944c+n2160c+n-',
2127cm-', 1723an-', 1304c
m-'1164c+n-' etc.

The degree of polymerization was determined by IJMR in the same manner as in Example 1, and the result was that of a heptamer. Furthermore, the meltability and solubility were investigated in the same manner as in Example 1, and as a result, melting behavior was observed at around 70°C, and dissolution in chlorobenzene and dimethyl sulfoxide was observed. When a glass fiber cloth was impregnated with this solution in the same manner as in Example 1 and the solvent was evaporated, a uniformly integrated and good prepreg was obtained.

Example 3 Synthesis of ClmiCCHzCOOCH=CHCOOCHzCmiCH
0.1 mole of the mixture was mixed with 200% of pyridine in which 0.05 mole of cuprous chloride was dissolved, and the mixture was reacted while bubbling oxygen to obtain the desired product. The yield of cooligomer obtained was 9
It was 8%.

IR (KBr): 3084cm-', 2938c
+n-', 2160cm-'2127cm-',
Published by 1722cm, 1304cm-Sumi etc.

The degree of polymerization was determined by NMR in the same manner as in Example 1, and it was found to be a decamer. Furthermore, as in Example 1, the melting properties and solubility were investigated, and it was found that it melts at around 70°C and dissolves in solvents such as chlorobenzene and dimethyl sulfoxide. Further, when a prepreg was made in the same manner as in the example, a uniform and integrated prepreg was obtained.

Synthesis of Example 4 Synthesis was carried out in the same manner as in Example 1 except that tetrahydrophthalic acid dichloride was used instead of nadic acid dichloride. The yield of the obtained cooligomer was 98%.

IR (KBr): 3084cm', 2160c
m-', 2127cm-'1718cm-', 13
08cm-', 1168cm-', etc.

As a result of determining the degree of polymerization in the same manner as in Example 1, a 12-mer fumaric acid diacetylene cooligomer was obtained. In addition, as a result of examining meltability and solubility in the same way, 70°C
It was observed that the substance melted in the vicinity and dissolved in solvents such as florbenzene and dimethyl sulfoxide. Further, when a prepreg was made in the same manner as in Example 1, a uniform and integrated prepreg was obtained.

Example 5 synthesis of.

■.

CHmiC-Cl1z-Coo-C=C=C00CH2
-CmiCH0. I mole CI = C-CH2-COO-C-C-COOCH2
-C = 0.045 mol of CI was dissolved in 200 mfl of a pyridine solution containing 0.05 mol of cuprous chloride, and oxygen gas was blown into this solution to carry out the reaction while bubbling. Ta. The yield of the obtained cooligomer was 93%.

IR (KBr): 30B4cm-', 29
39CII+-', 2160cm-'2127cm
-', 1723c+n-', 1304cm-'
1257CTIl-'1152CT11-' etc.

The degree of polymerization determined by NMR was 12-mer.

Further, the meltability and solubility were examined in the same manner as in Example 1, and as a result, melting was observed at around 60°C, and the solubility in solvents such as chlorobenzene and dimethyl sulfoxide was good.

When a prepreg was prepared using this cooligomer solution in the same manner as in Example 1, a uniformly integrated and good prepreg was obtained.

Example 6 The fumaric acid-based diacetylene co-oligomers obtained in Examples 1 to 5 were shaped into a 10 mm diameter disc and molded in an autoclave at a temperature of 150°C under a pressure of 5 atm in a nitrogen atmosphere. As a result, a strong molded body was obtained. As a result of measuring the elastic modulus of the obtained molded body, the cooligomer of Example 1 was 13 GPa, Example 2 was 11 GPa, Example 3 was 8 GPa, Example 4 was 106 Pa, and Example 5 was 7 GPa.
a, and it was confirmed that each had a high elastic modulus.

Comparative Example 1 As a result of trying to synthesize a diacetylene homopolymer represented by general formula (1) under the same conditions as in Example 1, the degree of polymerization was 1.
A dimer was obtained as a crystal. This crystal was insoluble in solvents such as chlorobenzene and dimethyl sulfoxide, and prepreg with glass fiber could not be formed. When the crystals were heated to melt them, violent decomposition occurred before the crystals reached their melting point. Therefore, as a result of molding this diacetylene homopolymer under the same conditions as in Example 6 with a slow temperature increase rate, a large number of defects such as voids and cracks were observed in the molded product, and the physical properties were also deteriorated. 2 GP
It had a low elastic modulus of a~3 GPa.

〔Effect of the invention〕

The fumaric acid-based diacetylene cooligomer of the present invention can suppress decomposition accompanied by rapid heat generation during a molding reaction through copolymerization, and has a relatively low melting point, so it has excellent handleability and moldability.

The resulting molded product has excellent elastic modulus, dimensional stability, heat resistance 21 and thermal conductivity, and is therefore useful as a raw material for general structural materials, including precision mechanical parts and electronics fields.

Claims (1)

[Scope of Claims] 1. In a copolymerized diacetylene oligomer consisting of a fumaric acid ester-based repeating unit represented by the general formula (I) and a repeating unit represented by the general formula (II), the repeating unit (I) and A fumaric acid-based diacetylene cooligomer in which the molar ratio (I)/(II) of (II) is in the range of 1 to 10, and the degree of polymerization of the copolymerized diacetylene oligomer is in the range of 4 to 25. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼......(II) (Here, X is an aliphatic or alicyclic group with 2 to 8 carbon atoms. (Represents a divalent unsaturated hydrocarbon group.) 2. The sum of the repeating units of the fumarate ester represented by the general formula (I) and the repeating units represented by the general formula (II) is 60 to 100.
% and in which the repeating units represented by the general formula (III) are 40 mol% or less, the molar ratio (I)/(II) of the repeating units (I) and (II) is 1 to 10, and the degree of polymerization of the copolymerized diacetylene oligomer is 4 to 25. ▲There are mathematical formulas, chemical formulas, tables, etc.▼......(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼......(II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼......(III) (Here X represents an aliphatic or alicyclic divalent unsaturated hydrocarbon group having 2 to 8 carbon atoms. R^1 represents a divalent aryl group having 6 to 12 carbon atoms,
R^2 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. )