JPH0468002A - Diacetylene polymer and its crosslinked product - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to diacetylene-containing polymers, and more specifically to diacetylene-containing polymers that have excellent crosslinking reactivity and provide highly tough crosslinked products, and crosslinked products thereof. It is related to.

[Conventional technology]

The high modulus of elasticity in the uniaxial direction due to the orientation of linear polymers has reached a level that surpasses that of aluminum and steel. On the other hand, no attempt has been made to increase the elastic modulus of isotropic materials such as thermosetting resins. Against this background, the present inventors have been developing high elastic modulus materials using compounds having diacetylene groups and carbon-carbon unsaturated bonds (for example, JP-A-63-145337). Public notice,
(Japanese Patent Application Laid-Open No. 63295612).

The high modulus diacetylene crosslinked material developed by the present inventors exhibits an elastic modulus of 10 GPa or more in isodirection, and 20 GPa or more by optimizing the crosslinking conditions and molecular structure. Such a high modulus of elasticity may be achieved by increasing the crosslink density, or the crosslinked product obtained by increasing the crosslink density becomes brittle, which poses a problem in use depending on the application requiring a certain degree of strength. In order to increase toughness, the crosslinking density must be lowered, or attempts to simply reduce the number of crosslinking groups in the polyfunctional diacetylene monomer will also reduce the bullet velocity of the crosslinked product. There has been no attempt to produce a crosslinked body with high toughness without lowering the elastic modulus, or any concept that could realize this.

[Problem to be Solved by the Invention: The object of the present invention is to provide a diacetylene-containing polymer and a crosslinked product thereof that provide a crosslinked product having high toughness without reducing the elastic modulus.

[Means to solve the problem]

In order to improve toughness, it is necessary to make the distance between crosslinking points as long as possible. Therefore, as a result of synthesizing various crosslinked materials, it was discovered that by introducing diacetylene groups into the side chains of certain linear polymers and crosslinking them, a crosslinked product with high toughness and high modulus of elasticity could be obtained.

Furthermore, as a result of intensive studies on the type of linking group, the design of the molecular structure, the optimization of the crosslinking method, etc., the present invention was achieved. That is, the present invention is as follows.

1. A diacetylene-containing polymer consisting of a repeating unit represented by the following structural formula (1) (where A represents hydrogen or a methyl group, and X represents hydrogen or a monovalent carbon having 1 to 6 carbon atoms) Indicates a hydrogen group,
R and R' each represent a divalent hydrocarbon group having 1 to 6 carbon atoms. ) 2. A diacetylene-containing polymer consisting of a repeating unit represented by the following structural formula (1) and a repeating unit represented by the following structural formula (2), and whose molar ratio (2)/(1) is 50150 or less. (However, A represents hydrogen or a methyl group, X represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
R and R' each represent a divalent hydrocarbon group having 1 to 6 carbon atoms. ) (However, A represents hydrogen or a methyl group, and Y represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms.) 3. From the repeating unit represented by the following structural formula (1) A crosslinked product consisting of a structural unit represented by the general formula (1') and (1°) obtained by reacting the diacetylene groups of a diacetylene-containing polymer.

+ CH2-C-)-(1') OOR +c-c=C-C+ R' OX 1←CH2-C R' OX (However, A represents hydrogen or a methyl group, and X represents hydrogen or carbon Indicates a number or 1 to 6 monovalent hydrocarbon groups,
R and R' represent a divalent hydrocarbon group having 1 to 6 carbon atoms. ) 4. A diacetylene-containing polymer consisting of a repeating unit represented by the following structural formula (1) and a repeating unit represented by the following structural formula (2), and whose molar ratio (2)/(1) is 50150 or less. A crosslinked product consisting of a repeating unit represented by structural formula (2) and a structural unit represented by general formula (1') and/or (1''), obtained by reacting diacetylene groups of.

(However, A represents hydrogen or a methyl group, and X and Y represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
R and R' represent a divalent hydrocarbon group having a carbon number of up to 6. ) In the present invention, A represents a hydrogen atom or a methyl group. X and Y represent hydrogen, a monovalent hydrocarbon group having 1 to 6 carbon atoms, and specific examples include CH3, C2H5, -C
3H7, -C,H9, -C5H,, -C6H,3,.
--\ -ku○〉 , C(CH3)3, -C(CH3)CH
2CH3, -CH (CI-13).

Examples include 1-no. Among these X, hydrogen and -CH3 are preferred from the viewpoint of ease of synthesis and high elasticity.
, -C2H5, -kuδ゛〉 are preferred. These +C-
C:C-C+R'OX-(-CH2-COOR+c=c-c=cR'0X (1'') is preferable.

R and R' represent divalent hydrocarbon groups having 1 to 6 carbon atoms, and specific examples include -CH2-, -C2H, -
1C3H6-1-C4H1l-1-C5H1-C6H
,. -Do◎'CH(CH3)-C(CH3)2- is mentioned. Of these R and R', -CH2-1-CH (C
) I3) -, -ghu>' are preferred.

The number average molecular weight of the diacetylene-containing polymer of the present invention is 2
000 to 1,000,000. Number average molecular weight is 200
Polymers having a relatively low molecular weight of about 0 to 300,000 are preferred in that they can increase the crosslink density of the crosslinked product. On the other hand, the number average molecular weight is 10,000 to 1,000,000
Polymers having a high molecular weight within the range of 2 are preferred in that the obtained crosslinked product has high toughness.

In order to have both high crosslink density and high toughness of the crosslinked product, the number average molecular weight should be in the range of 10,000 to 30,000.
0 is particularly preferred.

In the diacetylene-containing polymer of the present invention, the structural formula (
The molar ratio of the repeating unit of 2) to the repeating unit of structural formula (1) is 0/100 to 50,150. Since this repeating unit of structural formula (2) does not participate in crosslinking, it is preferable to reduce its content as much as possible. Generally, structural formula (2)
If the ratio of In order to easily introduce a diacetylene group and to increase the elastic modulus of the crosslinked product to the highest degree, it is preferably 0/100 to 30/70.

Specific examples of the structural formula (2) of the diacetylene polymer of the present invention include the following polymers.

There are blank spaces below. Therefore, it is not limited to a specific synthesis method.

An example is shown below.

QOH OC1 The diacetylene-containing polymer of the present invention can be easily synthesized by applying general organic synthesis methods.
±-(CH2 ooy cooRc=cc=cROX Polyacrylic acid chloride or polymethacrylic acid chloride and diacetylene diol HORC: CCECR'
Corresponding polymer (3) by reacting with OH
or can be obtained. The amount of ester groups introduced can be easily achieved by changing the diol charging ratio and synthesis conditions. Polymer (3) thus obtained is converted into polymer (4) by esterification using a conventional method. Furthermore, polymer (4) is converted into polymer (5) by etherification using a conventional method.
) is converted to In addition, polymers (3), (4), (
5) The acid chloride moiety contained therein can be converted to the corresponding carboxylic acid by reacting with a proton source such as water.

Polyacrylic acid chloride or polymethacrylic acid chloride can be synthesized by reacting polyacrylic acid or polymethacrylic acid with a chlorinating agent such as dionyl chloride, phosphorus pentachloride, or phosphorus trichloride. In addition, acrylic acid chloride or methacrylic acid chloride can be mixed with azobisisobutyronitrile (AIBN).
) or benzoyl peroxide.

Polymer (3) is polyacrylic acid chloride or polymethacrylic acid chloride and diacetylene diol HORC
It can be synthesized by a Schotten-Baumann reaction with mcc=cR' OH. The proportion of ester groups introduced into the resulting polymer can be adjusted to a desired amount by adjusting the charging ratio of polyacrylic acid chloride or polymethacrylic acid chloride and diacetylene diol. That is, when increasing the amount introduced, it is sufficient to simply increase the amount of diacetylene diol. Generally, the charging ratio of polyacrylic acid chloride or polymethacrylic acid chloride to diacetylene diol is 110.5 to 1/100.

This esterification reaction is usually carried out in an organic solvent. The organic solvent is preferably an organic solvent without active hydrogen, such as hexane, benzene, toluene, xylene, tetrahydrofuran, dioxane, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylformamide, acetone, and ethyl acetate. , pyridine, dimethylaniline, etc. are used. These solvents may be appropriately mixed and used depending on the case. There is no particular restriction on the amount of solvent used, but if the amount of solvent is small, the reaction system will gel. Generally, 0.1g to 100g of solvent is used for 1g of diacetylene diol.
Therefore, in order to prevent gelation, 1
g to 100 g. Furthermore, in order to capture the by-product hydrochloric acid, a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine, dimethylaniline, etc. may be present as necessary.

There are no particular restrictions on the reaction temperature and reaction time, but the reaction temperature is -10 to 150°C, the reaction time is 10 minutes to 2
day is preferred.

After the reaction, polymer (3) can be isolated by pouring it into a poor solvent.

By coexisting an alcohol such as methanol or ethanol with water as a poor solvent, unreacted acid chloride moieties are converted to carboxylic acids.

For the conversion into polymers (4) and (5), general esterification reactions and etherification reactions can be applied as they are.

For example, Moririn and Boyd, “Organic Chemistry (Part 1), (Part 2)
, (bottom) The method described in "Tokyo Kagaku Doujin, 3rd edition" can be applied as is.

Homopolymer consisting only of structural formula (1) + CH2
-C+ can be obtained by polymerizing the double bond of the monomer (6) having the structure: C00RC3cc=cR'ox CH2=CC00RCmiCC3CR'OX. In solution polymerization, diacetylene groups do not participate in the polymerization reaction. Therefore, the homopolymer can be easily obtained by applying a conventional radical polymerization or anionic polymerization method to the monomer (6).

The crosslinked product of the polymer of the present invention is an insoluble and infusible crosslinked product obtained by reaction (crosslinking) of diacetylene groups. Methods for crosslinking diacetylene groups include heating polymerization,
Examples include methods using photopolymerization and methods using pressure. These methods have already been disclosed by the present inventors, and can be applied as they are (Japanese Patent Application Laid-Open No. 62-267249, etc.).

The molecular structure of the crosslinked product can be determined by making full use of general analytical means such as infrared absorption spectra, NMR spectra, Raman spectra, and MS spectra. In the crosslinking reaction, there are two types of diacetylene groups: a case where the diacetylene group undergoes a topochemical reaction and a case where the diacetylene group undergoes random crosslinking. Corresponding.There is no problem with the physical properties of the resulting crosslinked product, such as mechanical properties such as strength and elastic modulus, but thermochromic properties and nonlinear optical properties of the crosslinked product are expected. In some cases, a crosslinked product containing a large amount of structural formula (1') is preferable.Furthermore, it is extremely difficult to react quantitatively the diacetylene groups in the crosslinked product.

Therefore, unreacted diacetylene groups may remain in the crosslinked product. However, since unreacted diacetylene groups reduce the weather resistance of the crosslinked product, the amount of unreacted diacetylene groups is preferably 30% or less, preferably 10% or less, based on the originally introduced diacetylene groups. .

The crosslinked body of the present invention exhibits a high degree of elastic modulus due to its high crosslink density. For example, the elastic modulus of epoxy resin, which is a typical thermosetting resin, is about 2 to 3 GPa, and the crosslinked product of the present invention has an elastic modulus of about 3 GPa or more, and by further optimizing the crosslinking conditions and molecular structure, It is also possible to exhibit an elastic modulus of GPa or higher.

〔Example〕

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to the Examples.

The amount of carboxylic acid was determined by titration with sodium hydroxide.

The number average molecular weight Mn was measured using gel permeation chromatography and determined as a standard polystyrene equivalent molecular weight.

Example l Polyacrylic acid (number average molecular weight 15000) 1.25g
was dissolved in thionyl chloride 2 (W) and heated at 70°C for 8 hours. After the reaction, excess thionyl chloride was distilled off under reduced pressure.

The obtained polyacrylic acid chloride was mixed with anhydrous dioxane 70%
7 rLl, diacetylene diol HORC3CC=CR'OH was added to this solution, and the mixture was reacted at 70°C for 24 hours. After the reaction, the reaction product was poured into a large amount of pure water, and the precipitated white polymer was isolated by centrifugation.

The yield, analysis value, and amount of carbonic acid of the produced polymer were determined as follows.
Shown in the table. Also, the number average molecular weight is 2000.10000
A similar study was conducted using polyacrylic acid or polymethacrylic acid of 0.500000.1000000, but the composition of the produced polymer was not substantially changed.

From this point of view, it was found that the size of the molecular weight has almost no effect on the reactivity of polymer reactions.

Example 2 In the polymer synthesis of No. 2 in Table 1 of Example 1, 50 mA' of methanol, ethanol, pentanol, hexanol, and phenol were added before pouring into a large amount of water, and the mixture was further heated at 60°C for 1 hour. heated for an hour. Thereafter, the reaction product was poured into a large amount of pure water, and the precipitated white polymer was isolated by centrifugation. The results are shown in Table 2. The structure of the obtained polymer was confirmed by infrared absorption spectrum and NMR spectrum.

Example 3 1.00 g of the polymer obtained in Example 2 was neutralized with 0.05N sodium hydroxide, isolated, and thoroughly dried. After drying, disperse the neutralized polymer in dry dioxane and add 0.8 g of sodium hydride.
The reaction was allowed to proceed at 0°C for 3 hours. Furthermore, chlorinated alkyl 20- was added to the mixture, and the mixture was reacted at 60°C for 3 hours. After the reaction, the reaction product was poured into a large amount of a mixed solvent of water and methanol, and the polymer was thoroughly washed and dried. The results are shown in Table 3.

The structure of the obtained polymer was determined by the infrared absorption spectrum and NM
Confirmed by R spectrum.

Example 4 0.1 mol of 2.4-hexadiyn-1,6-diol and 0.05 mol of methacrylic acid chloride were added to 507 nl of a mixed solvent of tetrahydrofuran-triethylamine (1.1).
The reaction was carried out at 60°C for 3 hours. After the reaction, the precipitated salt was removed and the solvent was distilled off, followed by treatment with a silica gel column. The obtained half ester CH2= C-C00CCI
(3 H2C=cc3CCH20H was polymerized using AIBN as a polymerization initiator. (50°C, 18 hours, in a sealed tube). After the reaction, the reaction product was poured into a large amount of methanol, and CH3-←CH2-C→"C00CH2C= CC=CCH20H was obtained in 68% yield.

IR (cm'): 3450.2956.215
When the number average molecular weight of 5.1737 was examined, it was found to be 23,800 in terms of standard polystyrene. The resulting polymer was etherified in the same manner as described in Example 3.

Whether methyl chloride, ethyl chloride, methyl chloride, or pexyl chloride is used as the chlorinated alkyl, the polymer CH corresponds almost quantitatively.

1← CL-C-+V COOCH2CmiCC=CCH20X was obtained. In the infrared absorption spectrum of the obtained polymer, the absorption of hydroxyl group at 3450 cm-' disappeared.

From this, it was confirmed that etherification was sufficiently progressing.

Example 5 Example 4 was repeated except that acrylic chloride was used instead of methacrylic chloride. In exactly the same way, we have been able to obtain the corresponding polymers.

1,000 CH2-CH(ha)-1 COOCI(2C3CC:CCH20HIR(am'
): 3400.2943.2155.1737 155 Example 6 The polymer obtained in Example 1 was placed in a mold with a diameter of 20 mm and compressed at 10 atm and 150° C. for 1 hour.

All of the obtained samples exhibited a glossy black color.

None of the samples were soluble in common organic solvents. Furthermore, when the solid-state NMR spectrum was measured, the absorption based on diacetylene groups around 80 ppm that was observed before crosslinking disappeared, and in its place, absorption based on double bonds was newly observed around 120 ppm. Similar results were also observed in the Raman spectrum, indicating that diacetylene groups were crosslinked and new double bonds were formed.

From the above results, the structure of these crosslinked bodies is -H CH2-C-sr OOR +C=CC=CCL R'OX It turned out that it was.

Similar results were also observed for the polymers obtained in Example 2 and Example 3.

The obtained crosslinked body was cut into rod shapes and subjected to a bending test. All test pieces exhibited a linear SS kerf, and had an elastic modulus of 3.8 to 6.6 GPa or more and a strength of 100 MPa or more. For comparison, 5. under the same conditions.
When the physical properties of the cured products obtained by curing 7-dodecadiin-1,12-noolne acrylate and 5.7-todecadiin-112-7olne methacrylate were measured, the elastic modulus was 7.8 GPa and 7°, respectively. The strength was about 80 MPa.

This result shows that the crosslinked product of the present invention has excellent toughness.

Example 7 0.1 mol of 5,7-dodecadiin-1,12-diol and 0.05 mol of methacrylic acid chloride were mixed in a mixed solvent of tetrahydrofuran-triethylamine (1°1) 50-
The reaction was carried out at 60°C for 3 hours. After the reaction, the precipitated salt was removed, the solvent was distilled off, and the mixture was treated with a silica gel column. The obtained half ester CH,,=CC00(CH
2) 4C3CC-=C(CH2)40H was polymerized using AIBN as a polymerization initiator (50°C for 18 hours in a sealed tube). After the reaction, pour the reactant into a large amount of methanol and convert CH3 + CH2-C-h;-COO(CH2LCmiCC30(CH2)40H to
Obtained in a yield of 9g. IR (cm'): 342
], 2155°The number average molecular weight was determined to be 15400 in terms of standard polystyrene. The resulting polymer was etherified in the same manner as described in Example 3.

As the chlorinated alkyl, methyl chloride, ethyl chloride, methyl chloride, or hexyl chloride was used. In each case, almost quantitatively corresponding polymers CH3 fcH2-C-h COO(CH2), CECCEC(CH2) 40X were obtained. . In the infrared absorption spectrum of the structure of the obtained polymer, the absorption of the hydroxyl group at 3421 cm' disappeared.

From this, it was confirmed that etherification had progressed sufficiently.

The thus obtained polymer was irradiated with γ-rays at 30 MRad. The obtained crosslinked product exhibited a blue color and was substantially insoluble and insoluble in ordinary organic solvents. When the Raman spectrum and solid-state NMR spectrum of the obtained crosslinked product were measured, it was found that the diacetylene group was converted to an en-yne structure.

CH3 -fcH2-C → "Coo(CH2)4 Shishi C-C3c-c + < CH2) 40X NMR (ppm): 124 (C=C), 80 (
C=C) Raman shift (cm-'): 2100 (
C1:C), 1540 (c:=c) Thus, by appropriately selecting the molecular structure, it is possible to topochemically react diacetylene groups on the side chains.

[Effects of the Invention] The diacetylene-containing polymer of the present invention provides an extremely strong crosslinked product due to the high reactivity of the diacetylene groups. Furthermore, the obtained crosslinked product also has high toughness. Therefore, the diacetylene-based polymer of the present invention can be used as an isotropic, high-strength, high-modulus material.

Patent applicant: Asahi Kasei Industries, Ltd.

Claims (1)

[Claims] 1. A diacetylene-containing polymer consisting of a repeating unit represented by the following structural formula (1). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, A represents hydrogen or a methyl group, X represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
R and R' represent a divalent hydrocarbon group having 1 to 6 carbon atoms. ) 2. Diacetylene consisting of a repeating unit represented by the following structural formula (1) and a repeating unit represented by the following structural formula (2), and whose molar ratio (2)/(1) is 50/50 or less. Containing polymer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (However, A represents hydrogen or a methyl group, X represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms,
R and R' represent a divalent hydrocarbon group having 1 to 6 carbon atoms. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(2) (However, A represents hydrogen or a methyl group, and Y represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms.) 3. Crosslinking consisting of structural units represented by general formula (1') and/or (1'') obtained by reacting diacetylene groups of a diacetylene-containing polymer consisting of repeating units represented by structural formula (1) below. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1') ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1'') (However, A is hydrogen, or represents a methyl group, X represents hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R,
R' represents a divalent hydrocarbon group having 1 to 6 carbon atoms. ) 4. Diacetylene consisting of a repeating unit represented by the following structural formula (1) and a repeating unit represented by the following structural formula (2), and whose molar ratio (2)/(1) is 50/50 or less. A crosslinked product consisting of a repeating unit represented by structural formula (2) and a structural unit represented by general formula (1') and/or (1''), obtained by reacting diacetylene groups of a containing polymer. ▲Math. , chemical formulas, tables, etc. ▼ (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1') ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1 (However, A represents hydrogen or a methyl group, X and Y represent hydrogen or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R and R' have 1 to 6 carbon atoms. )