JP2002173512A - Metal-containing monomer composition and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal-containing monomer composition excellent in mechanical strengths and water resistance, capable of readily producing molded products having complicate shape and useful as a heat-insulating material, a structural material, a protective material and a sound-insulating material, and a resin composition. SOLUTION: This monomer composition comprises [H2C=CH-COO-C2H4O]3- Al and methyl methacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel metal-containing monomer composition and a resin composition obtained by polymerizing the same.

[0002]

2. Description of the Related Art Conventionally, ionomer resins and superabsorbent resins have been known as metal salt-containing resins. In addition, an ion-crosslinked resin foam (Japanese Patent Publication No. 2-11621) for reacting a carboxylic acid-containing copolymer with a metal carbonate has been proposed.

[0003]

Among the metal salt-containing resins, the ionomer resin is obtained by kneading a metal salt with a carboxyl group-containing thermoplastic resin. However, since the kneaded resin has a high melting point, it is melted again during molding. After that, injection molding is required, and the energy cost required for molding is high. Further, the superabsorbent resin is excellent in water absorption, but has low strength at the time of water absorption, and is not suitable for the field of building materials intended by the present invention. on the other hand,
An ionic cross-linked resin foam for reacting a carboxylic acid-containing copolymer with a metal carbonate is obtained by dissolving a water-soluble α, β-unsaturated monomer or a water-soluble copolymer having a carboxyl group in water. It has ionic cross-linking by reacting a salt, which is obtained by polymerizing a water-soluble monomer, and is composed of structural units having high ionicity. Low strength. Further, since the resin obtained by the reaction contains moisture, a drying step is required, and the resin is greatly shrunk during drying.

[0004]

Means for Solving the Problems The present inventors have eagerly studied monomeric and resin compositions which can use simple molding equipment, have low water absorption and high strength upon water absorption, and do not require a drying step. As a result of the study, the present invention has been reached.

That is, the present invention relates to a metal-containing ethylenically unsaturated monomer (A) or (A) represented by the following general formula (1) and an ethylenically unsaturated monomer represented by the following general formula (2): It is a metal-containing monomer composition comprising B) and another ethylenically unsaturated monomer (C). Wherein M is a divalent to tetravalent metal, R ¹ is a hydrogen atom or a methyl group, R ² is —O— (R ⁴ O) n—, —COO— (R ⁴ O) n
^{-, -COO- (R 4 O)} n-CO-R 5 -COO-,
^{_{-CH 2 O-CO-R 5}} -COO- or -CH ₂ -O-
(R ⁴ O) n−, x is an integer of 2 to 4, y is an integer of 0 to 3 (where x ≧ y + 1), n is an integer of 1 to 8, and R ³ is 1 carbon atom.
To 12 alkyl groups or alkenyl groups, and R ⁴ has 2 carbon atoms.
An alkylene group of 4 to 4, R ⁵ represents an alkylene group having 2 to 4 carbon atoms, an alkenylene group having 2 to 4 carbon atoms or a phenylene group. ]

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), M is 2 to
Tetravalent polyvalent metals such as alkaline earth metals (eg, magnesium, calcium, barium), IIIa metals (eg, aluminum, germanium), IVa metals (eg, titanium, tin) and transition metals (eg, iron, cobalt, nickel, Copper, zinc). Of these, metals IIIa and IVa are preferred, and aluminum and titanium are particularly preferred.

The M content in the general formula (1) is usually at least 1% by weight, preferably 3 to 20% by weight, particularly preferably 5 to 1% by weight from the viewpoint of the strength of the polymer using this monomer.
5% by weight. The R ² of the general formula (1) R ² and general formula in (2) ^{in, -O- (R 4 O) n-} , -C
^{OO- (R 4 O) n-,} -COO- (R 4 O) n-CO-R 5
_{-COO-, -CH 2 O-CO-} R 5 -COO -, - C
H ₂ —O— (R ⁴ O) n— is exemplified. Here, n is 1
R ⁴ represents an alkylene group having 2 to ⁴ carbon atoms; R ⁵ represents an alkylene group having 2 to 4 carbon atoms; an alkenylene group having 2 to 4 carbon atoms; or a phenylene group.

In the general formula (1), Ethylenically unsaturated monomer (B) represented by general formula (2)
Specific examples of (poly) oxyalkylene-monovinyl ether; (poly) oxyalkylene-mono (meth) allyl ether; (poly) oxyalkylene-mono (meth) acrylate; dicarboxylic acid monoesters of the above; ) Dicarboxylic acid monoesters of allyl alcohol. The former is a residue obtained by removing a hydrogen atom from. Among these, it is preferable from the viewpoint of water resistance.

Specific examples of the monomer (A) represented by the general formula (1) include the following. _{[H 2 C = CH-O} -C 2 H 4 O] 4 -Ti [H 2 C = CH-COO-C 2 H 4 O] 3 -Al [H 2 C = CH-COO- (C 2 H 4 _{O) 2] 3 -Al [H} 2 C = C (CH 3) -COO-C 2 H 4 O] 3 -Al [H 2 C = C (CH 3) -COO-C 2 H 4 O] 4 - _{Ti [H 2 C = CH-} COO-C 2 H 4 OCO-C 2 H 4 CO
_{O] 3 -Al [H 2 C} = CH-CH 2 -OCO-C 6 H 4 COO] 3 -A
_{l [H 2 C = CH-} OC 2 H 4 O] 3 -Ti (OC 4 H 9) [H 2 C = CH-COO-C 2 H 4 O] 2 -Al (OC
_{4 H 9) [H 2 C} = CH-COO- (C 2 H 4 O) 2] 2 -Al (OC 3
_{H 7) [H 2 C =} C (CH 3) -COO-C 2 H 4 O] 2 -Al (O
_{C 4 H 9) [H 2} C = C (CH 3) -COO-C 2 H 4 O] 3 -Ti (O
_{C 3 H 7) [H 2} C = CH-COO-C 2 H 4 OCO-C 2 H 4 CO
_{O] 2 -Al (OC 4 H} 9) [H 2 C = CH-CH 2 -OCO-C 6 H 4 COO] 2 -A
l (OC ₃ H ₇ )

The monomer (A) represented by the above general formula (1)
Examples of the method for producing (a) include a method in which a polyvalent metal alkoxide is reacted with (B) to distill off the released alcohols. As the polyvalent metal alkoxide, a compound represented by the formula M (O
R ³ ) z {z is an integer of 2 to 4, and specific examples thereof include aluminum isopropoxide, aluminum ethoxide, diisopropoxy-aluminum butoxide, and titanium isopropoxide.
The amount of the polyvalent metal alkoxide to be used is generally 95% by weight or more, preferably 98 to 100% by weight, based on the hydroxyl group or carboxyl group of (B). The monomer (A) can be obtained by heating the reaction to room temperature or, if necessary, distilling off the eliminated alcohol. It is usually necessary to add 50 to 1000 ppm of a polymerization inhibitor to the monomer (A). Examples of the polymerization inhibitor include commonly used polymerization inhibitors, and specific examples include hydroquinone and methoxyhydroquinone.

The other vinyl monomer (C) has an HLB value (calculated by the Oda method) of 10 or less, and includes, for example, an aromatic compound having 8 to 10 carbon atoms such as styrene, α-methylstyrene, and vinyltoluene. A monomer; an olefin having 2 to 5 carbon atoms such as butadiene, ethylene, propylene, and isoprene;
Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth)
Alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms such as acrylate; acrylonitrile;
Vinyl acetate, vinyl chloride and polyfunctional vinyl monomers (2 to 6 functional, molecular weight 150 to 1000); dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like. These monomers may be used in combination of two or more kinds. Preferably, an aromatic monomer having 8 to 10 carbon atoms and 1 to 1 carbon atoms
An alkyl (meth) acrylate having an alkyl group of 8, particularly preferably styrene and methyl methacrylate. In addition, (meth) acrylate means acrylate or methacrylate. [(A) + (B)] /
The weight ratio of (C) is usually 5/95 to 99/1, preferably 60/40 to 99/1, and more preferably 80/20 to 99/1. The weight ratio of (A) / (B) is usually 10/0 to 2/8, preferably 10/0.
0 to 4/6.

The metal-containing monomer composition of the present invention comprises (A) and (C), or (A), (B) and (C), and is optionally used simultaneously with polymerization using a polymerization initiator. A molded product, a plate, a sheet, a film, a rod, a cylinder, and the like can be obtained by pouring into a mold having the following shape and heating as necessary. These can also adopt well-known processing methods, such as cast molding, injection molding, and transfer molding. The polymerization temperature is usually from 0 to 140 ° C, preferably from room temperature to 90 ° C. Examples of the polymerization initiator include the following peroxide-based polymerization initiator (a) and azo-based polymerization initiator (b). or,
The redox-based polymerization initiator (c) may be formed by using the peroxide-based polymerization initiator (a) and the reducing agent in combination. Further, two or more of (a) to (c) may be used in combination. The amount of the polymerization initiator to be used is 0.05 to 5.0 parts by weight, preferably 0.5 to 5.0 parts by weight, based on 100 parts by weight of all monomers.
1.0 part by weight. Moreover, you may add a chain transfer agent to the metal-containing monomer composition of this invention as needed. Examples of the chain transfer agent include n-butyl mercaptan and lauryl mercaptan. The amount of the chain transfer agent to be used is 0 to 10 parts by weight, preferably 0 to 1 part by weight, based on 100 parts by weight of all monomers.

(A) Peroxide-based polymerization initiator (a1) Oil-soluble peroxide-based polymerization initiator: acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate , 2,4-dichlorobenzoyl peroxide, t
-Butyl peroxybivalate, 3,5,5-trimethylhexanyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile peroxide, succinic acid peroxide, acetyl Peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylau Rate, cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5
-Dibenzoyl peroxyhexane, t-butyl peroxy acetate, t-butyl peroxy benzoate,
Diisobutyl diperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5
-Dimethyl-2,5-di-t-butylperoxyhexane, t-butylcumyl peroxide, t-butylhydroperoxide, di-t-butylperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, pinanhydro Peroxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cumene peroxide, etc. (a2) water-soluble peroxide-based polymerization initiator: hydrogen peroxide, peracetic acid, ammonium persulfate, sodium persulfate, etc. (b ) Azo-based polymerization initiator: (b1) Oil-soluble azo-based polymerization initiator: 2,2′-azobisisobutyronitrile, 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-azobis- 4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis-2,4- Dimethylvaleronitrile, etc. (b2) Water-soluble azo polymerization initiator: azobisamidinopropane salt, azobiscyanovaleric acid (salt), etc.

The metal-containing monomer composition of the present invention contains an inorganic filler, carbon black, titanium oxide, PEG, dye / pigment, chelate, fat, oil, surfactant, bentonite,
Cellulose, starch, a weathering stabilizer and the like can be appropriately blended. These amounts are not particularly limited, but are generally 85% by weight or less, preferably 70% by weight or less, particularly preferably 20% by weight, based on the quality of the obtained resin composition, based on the resin monomer composition. % Or less. The resin composition of the present invention can be used as a structural material, a sound insulating material, a heat insulating material, a protective material, and the like.

[0015]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. In the following, “parts” and “%” are based on weight, respectively.

Production Example 1 20 g of 2-hydroxyethyl acrylate, 204.2 g of aluminum isopropoxide (trade name: AIPD, manufactured by Kawaken Fine Chemical Co., Ltd.), and 0.06 g of hydroquinone were charged into a 1 L 4-necked kolben, and air was blown for 1 m.
Heat to 80 ° C. while blowing into the liquid at a flow rate of 1 / min. When the temperature reached 80 ° C., the inside of the Kolben was depressurized to remove 180 g of the desorbed isopropyl alcohol to obtain 472.2 g of a light yellow transparent solid monomer (1) having the following structure. _{[H 2 C = CH-COO} -C 2 H 4 O] 3 -Al

Production Example 2 480 g of 2-hydroxyethyl methacrylate, 226.8 g of titanium isopropylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.06 g of hydroquinone were charged into a 1 L four-necked kolben, and air was supplied at a flow rate of 1 ml / min. 8 while blowing inside
Heat to 0 ° C. When the temperature reached 80 ° C., the inside of the Kolben was depressurized to remove 180 g of the desorbed isopropyl alcohol, and a light yellow transparent solid monomer (2) 52 having the following structure was obtained.
6.8 g were obtained. _{[H 2 C = C (CH} 3) -COO-C 2 H 4 O] 4 -Ti

Production Example 3 174 g of allyl alcohol, 444 g of phthalic anhydride and 0.1 g of hydroquinone were charged into a 1 L 4-necked kolben,
80 ° C while blowing air into the liquid at a flow rate of 1 ml / min
And react for 4 hours. Then cool to 30 ° C,
204.2 g of aluminum isopropoxide (trade name: AIPD, manufactured by Kawaken Fine Chemical Co., Ltd.) was charged,
Heat to 80 ° C. while blowing air at 1 ml / min. When the temperature reached 80 ° C., the inside of the Kolben was depressurized to remove 180 g of the desorbed isopropyl alcohol, and 642.3 g of a pale yellow transparent solid monomer (3) of the following structural formula was obtained.
I got _{[H 2 C = CH-CH} 2 -OCO-C 6 H 4 COO] 3 -A
l

Production Example 4 174 g of allyl alcohol, 444 g of phthalic anhydride and 0.1 g of hydroquinone were charged into a 1 L 4-necked kolben,
80 ° C while blowing air into the liquid at a flow rate of 1 ml / min
And react for 4 hours. Then cool to 30 ° C,
Diisopropoxy-aluminum butoxide (trade name:
AMD, manufactured by Kawaken Fine Chemical Co., Ltd.) 218.2 g
And heated to 80 ° C. while blowing air into the liquid at a flow rate of 1 ml / min. When the temperature reached 80 ° C., the inside of the Kolben was depressurized to remove 180 g of the desorbed isopropyl alcohol to obtain 656.3 g of a pale yellow transparent viscous liquid mixture (4) of a monomer of the following structural formula (4). The viscosity is 500 mPa · s (80 ° C) and the acid value is 46 mgKOH /
g. _{[H 2 C = CH-CH} 2 -OCO-C 6 H 4 COO] 2 -Al (OC 4 H 9) 83.3 _{wt% [H 2 C = CH-} CH 2 -OCO-C 6 H 4 COOH 16.7 wt%

The compositions, symbols, etc. of the raw materials used in the examples and comparative examples are as follows. St: Styrene MMA: Methyl methacrylate ACN: Acrylonitrile EMA: Ethyl methacrylate AIBN: Azobisisobutyronitrile BPO: Benzoyl peroxide VA-041: 2,2′-azobis [2- (5-methyl-2-imidazoline-2) -Yl) propane)] dihydrochloride (manufactured by Wako Pure Chemical Industries) Al-AA: aluminum acrylate (30% aqueous solution, manufactured by Asada Chemical Co., Ltd.) Ca-AA: calcium acrylate (30% aqueous solution,
HEA: 2-hydroxyethyl acrylate HEMA: 2-hydroxyethyl methacrylate

Examples 1 to 9 and Comparative Examples 1 to 7 A monomer composition and a polymerization initiator (AIBN or B
PO) at a predetermined ratio, and put the mixture in a closed container.
Heated to 0 ° C. Polymerization started after 10 to 20 minutes, and a resin composition was obtained after 30 minutes. The quality of the obtained resin composition is shown in Tables 1 and 2.

[0022]

[Table 1]

[0023]

[Table 2]

Tensile breaking strength: (kgf / mm ² ): JI
Flexural strength: (kgf / mm ² ): Conforms to JIS K7203 Flexural modulus: (kgf / mm ² ): JIS K7203
Tensile when compliant water in fracture strength: (kgf / mm ^2): measured after 24 hours immersion in water, flexural strength when compliant water to ^{JISK7113: (kgf / mm 2)} : measured after 24 hours immersion in water, conforming to JIS K7203 Water absorption Elasticity at time: (kgf / mm ² ): Measured after immersion in water for 24 hours, in accordance with JIS K7203 Water absorption: (%): In accordance with JIS K7209 Dry dimensional shrinkage: (%): In accordance with JIS K7114

[0025]

The metal-containing monomer composition of the present invention has better compatibility than the conventional water-soluble metal acrylate monomer and hydrophobic unsaturated monomer. Further, in obtaining the resin composition of the present invention, a simple method such as ordinary radical polymerization and ultraviolet irradiation may be used, and the investment is small. The metal-containing unsaturated monomer composition and the resin composition obtained in the present invention have a low water absorption and a high strength at the time of water absorption. Further, a drying step is not required, and the energy cost is low. Also, large-scale production equipment such as a kneading / injection molding machine is not required, and production can be easily performed only with a simple mixer and a heating furnace. Stable production is possible even for complicated shapes simply by pouring into a mold and heating.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Takeshi Furuta 11-1 Hitotsubashi Honcho, Higashiyama-ku, Kyoto Sanyo Kasei Kogyo Co., Ltd. F-term (reference) 4J027 AB32 AC09 AJ02 BA02 BA03 BA04 BA05 BA06 BA07 CB03 4J100 AA02R AA03R AB02R AB03R AB04R AC03R AE09Q AE18Q AG04R AL03R AL04R AM02R AP01P AS02R AS03R BA02P BA02Q BA04P BA12P BA15P CA01 CA05 DA22 DA37 DA49 DA51 JA67

Claims (7)

[Claims] 1. A metal-containing ethylenically unsaturated monomer (A) or (A) represented by the following general formula (1) and an ethylenically unsaturated monomer (B) represented by the following general formula (2): A metal-containing monomer composition comprising another ethylenically unsaturated monomer (C). Wherein M is a divalent to tetravalent metal, R ¹ is a hydrogen atom or a methyl group, R ² is —O— (R ⁴ O) n—, —COO— (R ⁴ O) n—, —COO— ^{(R 4 O) n-CO} -R 5 -COO-, -CH 2 O-CO-R 5 -COO- or ^{_{-CH 2 -O- (R 4 O)}} n-, x is an integer from 2 to 4, y is an integer of 0 to 3 (where x ≧ y +
1), n is an integer of 1 to 8, R ³ is an alkyl or alkenyl group having 1 to 12 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, R ⁵ is an alkylene group having 2 to 4 carbon atoms, Carbon number 2
4 to 4 alkenylene groups or phenylene groups. ] 2. The metal-containing monomer composition according to claim 1, wherein (A) is obtained by reacting (B) with a polyvalent metal alkoxide and distilling off released alcohols. 3. The metal-containing monomer composition according to claim 1, wherein M in the general formula (1) is an alkaline earth metal, a IIIa metal, an IVa metal or a transition metal. 4. The metal-containing monomer composition according to claim 1, wherein the M content in the general formula (1) is 1% by weight or more. 5. The metal-containing monomer composition according to claim 1, wherein the weight ratio of [(A) + (B)] / (C) is 5/95 to 99/1. 6. (C) is at least one monomer selected from the group consisting of an aromatic monomer having 8 to 10 carbon atoms and an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms. The metal-containing monomer composition according to any one of claims 1 to 5. 7. A resin composition obtained by polymerizing the metal-containing monomer composition according to claim 1.