JPH0370735A - Modified rigid polymer and molecular composite material - Google Patents

Abstract

PURPOSE:To provide the subject polymer homogeneously dispersed without causing self flocculation, having excellent compatibility with and good adhesivity to various resins and imparting high reinforcing effect and fatigue resistance to composite materials thereof by subjecting amide groups in a polymer to an N-substitution reaction with a specific compound. CONSTITUTION:The objective polymer comprises (A) at least 50wt.% of repeating units of the formula [R1-R4 are H, 1-20C alkyl (e.g. pentyl) and/or 2-20C aliphatic group or substituted aromatic group (e.g. styryl) having a polymerizable olefin group wherein at least 5% of the sum of R1-R4 is the polymerizable olefin and <=20% of the sum of the R1-R4 is H] and (B) <=15wt.% of other repeating units (e.g. aliphatic polyamide such as 6-nylon). The polymer component is compounded with a matrix in a weight ratio of 15:85 to 0.5:99.5 to provide a molecular composite material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a newly modified poly-phenylene phthalamide-based rigid polymer, a method for producing the same, and a molecular composite material using the rigid polymer.

(Prior art) In the past, the development of composite materials that mutually complement the properties of the constituent materials and create new effective functions by combining two or more types of materials has been actively conducted. Glass fiber, carbon fiber, useful as reinforcement and reinforcing fiber for coalescence.
Regarding composites with so-called high-strength fibers such as aramid fibers, a wide range of performance improvements, such as elastic modulus, heat distortion temperature, and electrical properties, have been reported and studied.

The present inventors N-alkylated the aramid bonds of a polyphenylene tele-7 talamide-based rigid polymer according to Japanese Patent Application Laid-open No. 61-227508, and converted the modified rigid polymer into a polymethyl methacrylate resin matrix (IJ Lux). A dental material consisting of a molecular composite material that is uniformly dispersed inside is proposed.

(Problems to be Solved by the Invention) However, even when the organic polymer and the modified polyaramid are combined, the properties of the composite materials are still significantly different, such as compatibility and adhesiveness. Poor interfacial affinity and sufficient combined effect J! In addition to being unable to exhibit KT, it also has the essential drawbacks of inevitably deteriorating some of the physical properties inherent to organic polymers, such as toughness, and furthermore, the value conversion is opaque, water resistance, There were also problems in terms of solvent resistance.

(Means for Solving the Problems) In view of the above-mentioned current situation, the present @ Akishya et al. have conducted intensive studies to solve the above-mentioned problems, and as a result, we have developed a completely aromatic polyamide, that is, an amide bond (-CONH-). A newly modified polyphenylene 7-talamide by introducing a functional group having a double bond at the N-position of a long-chain polyaramid, at least 85% of which is directly connected to two aromatic rings. We found the lK at which a rigid rigid polymer based on the matrix resin can be obtained, and furthermore, the modified rigid polymer was found to The present invention was completed based on the discovery that a transparent new composite material with excellent physical and chemical properties can be obtained by the jm structure.

In other words, the present invention provides a modified rigid polymer having at least an SOS of repeating units represented by the following structural formula (1)... (2) A carbon number having an alkyl group and/or an olefin group having polymerization activity. A molecular composite material exhibiting 2 to 20 aliphatic groups or substituted aromatic groups, and in which a core-modified polyaradide-based rigid polymer is uniformly dispersed in a matrix of R1e R, "I" and an organic resin. A composition is provided.

The rigid polymer of the present invention may consist entirely of repeating units represented by the structural formula (■), but it may also contain other repeating units as long as it does not exceed 50%. It is preferable that the number of repeating units is 15% or less, and more preferably 10% or less. This kind of repetition 1,1
Examples of the polyamide include aliphatic polyamides such as 6-nylon and 6-nylon.

R1 + R1i R1* R4 in one combination (3) is hydrogen, an alkyl group having 1 to 20% carbon atoms, preferably 5 to 20 carbon atoms, and or an aliphatic group having 2 to 20 carbon atoms having an olefinic group having polymerization activity. Alternatively, the aliphatic group having an olefin group preferably has 2 to 8 carbon atoms, and the substituted aromatic group having an olefin group preferably has 8 to 10 carbon atoms. Examples of the alkyl group include a pentyl group, hexyl group, octyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, and octadecyl group, and the alkyl group may be linear or branched. Good too. Examples of aliphatic groups having an olefinic group include allyl group, 2-methylallyl group, and n-butyl group. Examples of substituted aromatic groups having an olefinic group include styryl group and styryl-substituted methyl group. Examples include groups.

``1 p R1* R1* R4 does not need to contain hydrogen, but from the viewpoint of soluble acid sites, there is no particular problem as long as H is less than 20% of the total of R1゜Rs #Rs and R4. , preferably 10% or less.

The modified poly-phenylene phthalamide-based rigid polymer obtained by substituting a functional group having a double bond at the N-position in the present invention can be used, for example, in the following
For polyaramid-based rigid polymers having 50% or more of repeating units of the total... ■ Aliphatic or substituted aromatic having 2 to 20 carbon atoms containing an olefin group that increases polymerization activity in the presence of an alkali metal hydride. It can be produced by reacting group halide compounds.

In this case, the halide compound may be directly reacted with, but since the N-substitution reactivity of wholly aromatic boric acid is generally low, the hydrogen at the N-position is partially substituted with a predetermined amount of alkyl group in advance. Afterwards, the desired t is reacted with the halide compound in the presence of an alkali metal hydride in a strong polar solvent.
It is suitable for carrying out modification of t conversion rate.

Dimethyl sulfoxide is a strong polar solvent.

N-methylpyrrolidone, dimethylacedeamide.

hexitemethylphosphoramide, N, N, N,'
Although N'-tetramethylurea and the like are used, dimethyl sulfoxide is particularly preferred.

As the halide compound having an olefin group having polymerization activity t', aliphatic halides or substituted aromatic halides having 2 to 20 carbon atoms are preferably used because they have good reactivity. -Specific examples include chlorodecane, chloromethylpropene, chlorobutene, chloromethylstyrene, chlorostyrene, bromobutene, bromostyrene, vinyl chloroacetate, and the like. Further, the alkyl halide compound necessary for partial substitution with an alkyl group in advance is not particularly limited, but alkyl halides having 5 to 20 carbon atoms are good in terms of compatibility with the matrix resin and adhesiveness. Specific examples include chlorodecane, chlorododecane, chlorooctadecane%10 mohexane, bromooctane, bromodecane, bromododecane, bromotetradecane, bromopentadecane, and the like. There is no problem whether the alkyl group #i is linear or branched. The resulting modified poly-7-enylene-7-talamide preferably has a weight average molecular weight in the range of 1,000 to 550.000,
It dissolves not only in solvents such as chloroform, tetrahydrofuran, and carbon tetrachloride, but also in polymerizable monomers such as methyl methacrylate and styrene, and in some cases dissolves in acrylic acid, methacrylic acid, etc., and has various thermoplastic and thermosetting properties. Improved compatibility and affinity with side fats and gums, and has a wide range of properties.

It can be used as a reinforcing material to strengthen Trix resin. For example, specific examples of thermoplastic resins include polyacrylate, polymethacrylate, polymethyl methacrylate, methyl methacrylate-styrene copolymer,
Examples include polystyrene, styrene-acrylonitrile copolymer, polyacrylonitrile, and styrene-acrylonitrile-butadiene copolymer resins, among which (meth)acrylic resin is a molecular composite with the above-mentioned modified polyphenylene phthalamide. This is particularly advantageous because material #+ can be formed. These monofunctional (co)
In addition to polymers, depending on the purpose of use, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)ac, rylate, triethylene glycol di(methanoacrylate, polyethylene glycol di(meth) Acrylates, 1,4-butanediol di(meth)acrylate), 1,5-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, glycerin di(meth)acrylate and the following- (In the formula, R- is H or a methyl group, %p is an integer of 1 to 20.) (In the formula, R- is H or a methyl group, and p is an integer of 1 to 20.) Polyfunctional compounds such as bisphenol A diglycidyl (meth)acrylates, urethane di(meth)acrylates, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, bisphenol A di(meth)acrylate etc. Can be used. When used as the above-mentioned (meth)acrylic resin t-polymer, its weight average molecular weight is preferably in the range of 5,000 to 2,000,000.

The weight ratio of the matrix component to the modified rigid polymer component according to the present invention is 85=15 to 99.5:
(L5. Preferably, it is in the range of 94:6 to 99:1. If the ratio of the rigid polymer component is higher than this, it becomes difficult for the tfff component to be uniformly dispersed in the matrix tree W#, When the ratio decreases, the reinforcing effect becomes insufficient.

In order to produce a composite material using the modified rigid polymer of the present invention as a reinforcing material, there are two methods: starting from a matrix resin monomer, mixing it with a polymer, or an intermediate method. By starting from a matrix resin monomer or a mixture of a monomer and a polymer, and polymerizing and curing the monomer components using a polymerization initiator, it is possible to obtain a composite material with more uniform molecular dispersion. This is especially preferable because it can be done.

Any known compound can be used as the polymerization initiator, but in the case of separate thermal curing, substances that can decompose and initiate polymerization upon heating, such as benzoyl peroxide, cumene hydroperoxide, 7-butyl hydroperoxide, dicumyl peroxide, acetyl peroxide, i
Examples include oxidized lyloylzobisisobutyronitrile. In addition, when polymerizing and curing at room temperature, for example,
Combinations of peroxide and amines, peroxide and sulfuric acid/acids, or peroxide and cobalt compounds can be used. When using a combination of polymerization initiators, divide the m-parabolite of the present invention into two parts, mix peroxide in one part, and mix amines, sulfinic acids, or cobalt compounds in the other part.
Can be used in combination.

In addition, when carrying out polymerization and stalking by light irradiation such as ultraviolet rays and night light, a % photosensitizer, such as bean, is used.

It is preferable to use ci/methyl ether, benzoin ethyl ether, ben/impropyl ether, a combination of camphor quinone and amines, and the like.

The amount of the polymerization initiator to be used can be determined as appropriate, but t% (L01 to 10% by weight is appropriate) based on the entire mixture.

Also, for producing the composite material of the present invention.

For example, in the case of a polymer resin matrix, conventionally known molding techniques such as extrusion molding, injection molding, pressure molding, blow molding, etc. can also be applied.

For the composite material of the present invention, an inorganic filler, a colorant, a polymerization inhibitor, and ultraviolet kneading are further added as necessary. The performance evaluation of the cured composite material was carried out by the method shown below.

[Bending strength]

The test piece was a cylinder of 25×4sgφ, and a three-point bending method using 20 snowflakes was used.

[Indirect tensile (diametral) strength]

The test piece was a cylinder of 6 x 6 mφ, and an indirect tensile test method was used that takes advantage of the fact that when compressive force is applied in the diametrical direction, tensile stress is generated in the direction perpendicular to the compressive force, and the value is calculated using the following formula. do.

[Pressure a9IJ degrees] The test piece is a 6 x 4 cylinder φ, and the value is calculated from the compressive load until the test piece breaks according to the following formula.

[Water absorption]

The test piece was a cylinder of 10 x 1-φ, and was measured after being stored in water at 37°C for 7 days.

[Acetone swelling degree]

The test piece was 1 ml of jox and measured after being stored at room temperature for 24 hours.

Example 1 Put 350- dimethyl nylphooxide into a 500-separable flask, add 704 mol of sodium hydride (LO0704) under a gas stream of 70 to 700 g while stirring.
After maintaining the temperature at 5°C for 40 minutes, it was cooled with a room temperature thermometer and the poly(
P-phenylene-5,4'-oxydiphenylene tele7
176 moles of talamide (hereinafter abbreviated as PPOT) α00 were added and stirred for 4 hours. Next, 100,352 moles of bromooctane (n-octyl bromide) were added, and after stirring for an additional 16 hours, the reaction mixture was poured into a large excess of water, and the precipitated product was separated, thoroughly washed with water, and then dissolved in ethanol. Wash with 50~60℃ (
N-octyl-poly(p-phenylene-3,4'-oxydiphenylene-7-talamide) with a degree of substitution of 50 molar
= (hereinafter abbreviated as -0at -P POT) was obtained.

Next, 150 mg'i of dimethyl sulfoxide was placed in the same separable flask as described above, and 552 mol of sodium hydride CLOO was added under a nitrogen gas flow. After cooling, 0 ct-PPOT (LOO 176 mol) was added and stirred for 4 hours. Then, chloromethylstyrene (LOO 552 mol tm, t) was added for an additional 16 hours.
After mixing, the reaction mixture was poured into a large excess of water, and the precipitated product was separated and thoroughly washed with water, followed by washing with ethanol and drying at 50 to 60°C to obtain the desired reformed product. IJ (P-phenylene-3,4'-oxydiphenylene-7-thalamidon: (hereinafter 00t-M
8-P POT)t″ was obtained.

As a result of qualitative quantitative analysis of the **proportion of methylstyrene groups for the Oct-MS-PPOT by FT-NMR (Figure 1), a double bond peak was observed at 4.9 to 5.8 ppm. From the resonance ratio of the number of protons of the main chain and side chain phinidine groups to the number of 70) atoms at the N position, the ratio of octyl groups to methylstyrene groups is approximately 1:1, as desired. It was confirmed that a modified product was produced.

Furthermore, the amount of hydrogen attached to the N position was far less than 10.

Example 2 Oct obtained in Example 1 for methyl methacrylate
-M S -P P OT 1 ] [Amount boosted and benzoyl peroxide (L 5% by weight) was dissolved, [The mixture was sealed in a glass tube and heated at 60° C. for 24 hours, followed by joOc, 2
Polymerization was carried out by heating for 4 hours. This one has a bending strength of 1806
kgf/eat”, indirect tensile strength 410 to 9f1511
”, Compressive strength 129t kgt/cn?, Water absorption amount a
The cured product had an excellent transparency of 62η/- and acetone swelling of 175.

For comparison, only methyl methacrylate was used without adding the Oct-M S -P P OT.

The cured product obtained by polymerization under similar conditions has a bending strength of 168
7 kgt/'cpn', indirect tensile strength 376 kgf
/cm”.

Compressive strength 1225 kgf/ctl, water absorption α74η/
- and acetone swelling degree ■.

Example 5 Example 2 except that the amount of Oct -M S -P P OT used in Example 2 was increased by t-13 weight.
A cured product was prepared in exactly the same manner. This one has bending strength +
889 qf/cm”, indirect tensile strength 408 klil
f/cm”, compression strength R132j klf/at?,
9Et water lit (L64 da/-) and acetone swelling degree 116, and the cured product had good transparency.

Real π Example 4 Oct -M S -P P OTO in Example 2
A cured product was produced in the same manner as in Example 2 except that the amount was increased to 6 weight flies. This one has a bending strength of 189
0 kgf/c+++”, indirect tensile strength 401 to 9f/
cm", compressive strength of 1240 kgf/crg", water absorption CL of 65 cm/-, and degree of acetone swelling of 66%, and the transparency of the cured product was also good.

(Effects of the Invention) As explained above, according to the present invention, the modified wholly aromatic polyamide-based rigid polymer is characterized in that the amide group in the polymer is As a result of the substitution reaction, the cohesive force between the rigid and rigid polymers is significantly reduced, and the strong hydrogen bonds between the conventional aromatic polyamide molecules are blocked. Disperses extremely uniformly without self-agglomeration when mixed with a synthetic resin. Furthermore, by using the modified rigid polymer, it is possible to significantly improve the compatibility and adhesion with each AAL resin. The favorable performance of the rigid-rigid molecule is utilized in a composite material reinforced with the modified polymer, resulting in advantages such as high reinforcing effect, extended service life, and improved fatigue resistance. For example, various boards, I
Molding materials such as I5 pipes and artificial marble, various composite resins, adhesives, resin teeth (artificial l1l), resins for denture bases, rebase materials, resins for inlays, dental materials such as implant materials, various thermoplastics and thermosetting materials sex material,
Various nameplates, cover materials, general display boards, stickers-1 various marks, reflective plates, various decorative boards, protective materials, etc., each a
[Suitable as a modifying material for w fat.

[Brief explanation of drawings]

FIG. 1 shows the F'l'-NMI'L spectrum of Oct-MS-PPOT obtained in Example 1.

Claims (1)

Scope of Claims: (1) A modified rigid polymer having at least 50% of its total repeating units represented by the following structural formula [1]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼... [1] (In the formula, R_1, R_2, R_3 and R_4 have hydrogen, an alkyl group having 1 to 20 carbon atoms, and/or an olefin group having polymerization activity. It represents an aliphatic group or a substituted aromatic group having 2 to 20 carbon atoms, and at least 5% of the total of R_1, R_2, R_3 and R_4 is a group having an olefin group having polymerization activity, R_1, R_2, R_3 and 20% or less of the total R_4 is hydrogen) Poly-phenylene phthalamide having at least 50% of the total repeating units represented by the following structural formula [2]▲There are mathematical formulas, chemical formulas, tables, etc.▼... [2] After partially substituting a part of the hydrogen in the aramid bond with an alkyl group having 1 to 20 carbon atoms in advance, the unsubstituted aramid group is replaced with an alkali metal or an alkali metal hydride in a strong polar solvent. metal salt, then
2. The method for producing a modified rigid polymer according to claim 1, which comprises reacting an aliphatic or substituted aromatic halide compound having 2 to 20 carbon atoms and having an olefin group having polymerization activity. (3) A composite material in which the modified rigid polymer according to claim 1 is molecularly dispersed in an acrylic or methacrylic resin matrix.