JP2002327023A - Metal-containing monomer composition and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a monomer composition having low water absorption and excellent wet strength which gives an useful resin mainly for a filed of the building materials and to provide such resin. SOLUTION: A metal-containing monomer composition comprises a multivalent metal salt of a phosphate of an ethylenic unsaturated group-containing alcohol and other multivalent metal-containing ethylenic unsaturated monomer and/or an unsaturated monomer without multivalent metal and/or a polymerization initiator. The resin uses the composition for polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a metal-containing monomer composition and a resin, and more particularly to a resin useful in the field of construction materials such as structural materials, sound insulation materials, heat insulation materials and protection materials, and a metal-containing monolithic material giving such a resin. To a monomer composition.

[0002]

2. Description of the Related Art Conventionally, as a metal salt-containing resin, an ionomer resin (a resin obtained by kneading a metal salt into a carboxyl group-containing thermoplastic resin) or a super water-absorbing resin [carboxyl group-containing monomer (acrylic acid and / or In which a copolymer of a salt) and a crosslinkable monomer and / or polysaccharide is crosslinked with a polyvalent metal salt]. An ion-crosslinked resin foam obtained by reacting a carboxyl group (carboxylic acid) -containing copolymer with a metal carbonate (Japanese Patent Publication No. 2-11621)
Etc. have been proposed.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a monomer composition which gives a resin having low water absorption and excellent wet strength, and to provide such a resin.

[0004]

According to the present invention, a polyvalent metal salt (A1) of a phosphoric acid ester (A0) of an ethylenically unsaturated group-containing alcohol (a) and another polyvalent metal-containing ethylenically unsaturated monomer are provided. A metal-containing monomer composition comprising a monomer (A2) and / or a polyvalent metal-free unsaturated monomer (B) and / or a polymerization initiator (C); A metal-containing resin having a metal content of 1 to 70% by weight; a method for producing a metal-containing resin, which comprises polymerizing (A1) or (A1) with (A2) and / or (B). Provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The polyvalent metal constituting (A1) includes a divalent to tetravalent typical metal and a transition metal.
Typical metals include Group IIa (alkaline earth) metals (eg, magnesium, calcium, barium), Group IIIa metals (eg, aluminum, gallium) and Group IVa metals (eg, germanium, tin);
b metal (eg, copper), IIb metal (eg, zinc), IVb
Group metal (eg, titanium, zirconium) and Group VIII metal (eg, iron, cobalt, nickel).
Preferred are metals of groups IIa, IIIa, IVb and VIII, especially calcium, aluminum and titanium.

As (a) constituting (A0), an ethylenically unsaturated group-containing alcohol having a molecular weight of usually up to 300, which may have an ether bond and / or an ester bond, can be used. (A) includes alkenol,
(Poly) oxyalkylene monoalkenyl ether, unsaturated monocarboxylic acid hydroxyalkyl ester and unsaturated monocarboxylic acid polyoxyalkylene monoester are included, and examples include a hydroxyl compound represented by the following general formula (1). R (CO) rO (A-O) nH (1) In the general formula (1), R is an alkenyl group or a phenyl-substituted alkenyl group, A is an alkylene group, r is 0 or 1, n is 0 or 1-3 or Represents a larger integer. When n is 2 or more, n A's may be the same or different. When (A-O) n is composed of two or more types of AO, they may be randomly distributed or block-shaped. R represents a C (carbon number, the same applies hereinafter) alkenyl group of 2 to 8 or more, for example, a vinyl group, an isopropenyl group, a 1-propenyl group, a (meth) allyl group (representing an allyl group and a methallyl group. Use similar expressions), 1-, 2- and 3-butenyl, pentenyl, 2-methyl-2-butenyl, hexenyl, heptenyl, octenyl; and phenyl-substituted alkenyl, such as 2-phenylvinyl Groups. Preferred are vinyl, isopropenyl and allyl groups. The alkylene group A includes a C2-4 or more alkylene group such as ethylene group, 1,2- and 1,3-propylene group, 1,2-, 2,3-, 1,3-
And 1,4-butylene groups, and combinations of two or more of these. Preferred is an ethylene group, 1,2-
A propylene group and a 1,4-butylene group.

Specific examples of (a) include C2-8 alkenols, for example, vinyl alcohol, (meth) allyl alcohol, (iso) crotyl alcohol, methylvinylcarbinol, allylcarbinol, 1-butene-3- All, 2-buten-1-ol, hexenol, heptenol, octenol; alkylene oxide of the above alkenol (C2-4 or more, hereinafter abbreviated as AO)
Adduct (addition mole number 1 to 3 or more) [(poly)
AO adduct of oxyalkylene monoalkenyl ether]; unsaturated monocarboxylic acid [eg, (meth) acrylic acid, (iso) crotonic acid, cinnamic acid] (addition mole number 1 to 3)
Or more) [hydroxyalkyl esters and polyalkylene glycol monoesters]. Preference is given to allyl alcohol, (poly) oxyalkylene (C2-4, degree of polymerization 1-3) monovinyl ether, and especially AO adducts of (meth) acrylic acid (addition moles 1-3). AO includes ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter P).
O), 1,2-, 2,3-, 1,3- and 1,
4-butylene oxide, and a combination (random addition and / or block addition) of two or more thereof (for example, EO and PO) are included. Among (a), those in which r is 0 and R is a vinyl group, isopropenyl group or allyl group, and those in which r is 1 and R is a vinyl group or isopropenyl group are particularly preferred.

Preferred as (A0) are phosphoric acid monoesters and / or diesters of (a) [which may be a single (a) diester or a mixture of two (a) diesters]. Alternatively or together with them, a mixed diester of (a) and a saturated alcohol (a ') can be used. (A ′) may have an ether bond and / or an ester bond,
Saturated alcohols having a molecular weight of usually up to 300 can be used. In (a ′), R in the general formula (1) is H,
C1-8 or more alkyl group, cyclohexyl group, benzyl group, aryl group (phenyl group, tolyl group,
(R is an aryl group and r
Is 0, n is 1 or more). Specifically, alkanols such as methanol, ethanol, n- and i-propanol; alkylene glycols such as ethylene glycol, propylene glycol, 1,4
-Butanediol; their AO adducts (addition mole number 1
To 3 or more).

(A0) is a method of reacting (a) [or (a) and (a ')] with a known phosphorylation method, for example, a phosphorylating agent such as phosphorus oxychloride, phosphoric anhydride, polyphosphoric acid and the like. Then, it can be produced by phosphorylation. (A) and another (a) or (a)
The mixed diester with (a) may be a phosphoric acid ester of (a) and another mixture of (a) or (a '), or the monoester may be formed after forming the monoester of (a). It may be reacted with other (a), (a ′) or A 2 O to form a mixed diester.

Specific examples of (A0) include a phosphoric acid ester of (poly) oxyethylene monovinyl ether,
Phosphoric acid ester of EO and / or PO adduct of (meth) acrylic acid (addition mole number 1 to 3) is exemplified. The phosphorylated product is a phosphoric monoester of (a) and / or (a) [or (a) and (a).
')] Or a mixture mainly composed of these [preferably containing 70% or more, particularly 80% or more (the same applies hereinafter by liquid chromatography)]. In the phosphorylated product, the phosphoric acid monoester of (a) and / or (a) [or (a) and (a)
′)] In addition to the phosphoric diester, unreacted (a) and
By-products such as (a) phosphoric acid triesters of [or (a) and (a ')], condensed phosphoric acid (such as pyrophosphoric acid) esters of (a) [or (a) and (a')], and the like. But a small percentage (preferably 30% or less, especially 20% or less)
It may be contained. Above and below,% represents% by weight.

(A1) can be produced by reacting (A0) with a polyvalent metal alkoxide (b). As (b), a general formula: (R1O) xM [wherein
x is an integer of 2 to 4, M is a polyvalent metal (x-valent metal), R1
Is a C1-8 or higher alkyl group or C2-8
Or more alkenyl groups, and x R's may be the same or different]. The alkyl group for R1 includes linear and branched alkyl groups, and includes methyl, ethyl, n- and i-propyl, n-, i-, sec- and t-butyl, n- and i-amyl, hexyl. , Heptyl, octyl, 2-ethylhexyl and the like. As the alkenyl group,
The same as R in the general formula (1) can be mentioned. Specific examples include aluminum isopropoxide, aluminum ethoxide, and titanium isopropoxide.
The amount of (b) used depends on whether (A0) is a monoester, a diester or a mixture thereof, or the mixing ratio thereof. In the case of a diester, the equivalent of the hydroxyl group (-OH) of (A0) is 1 equivalent. It is usually 0.95 equivalent or more, preferably 0.98 to 1 equivalent, and in the case of a monoester, it can be changed in the range of 1/2 of the above equivalent to 2 to the above equivalent. In the case of a mixture, the amount is proportionally divided according to the mixing ratio. The above reaction can be carried out at room temperature or under heating by removing the alcohol to be eliminated.
(A1) includes one or a mixture of two or more polyvalent metal salts represented by the following general formula (2).

[0012]

Embedded image

In the general formula (2), x is an integer of 2 to 4, y is a positive integer not greater than x (an integer from 1 to x); M is a polyvalent metal (x-valent metal); A C1-8 alkyl group or a C2-8 alkenyl group; R2 is a residue of (a); R3 is a hydrogen atom or a residue of (a) or (a ') [an active hydrogen atom (a hydrogen atom of a hydroxyl group) Removed residue]. As the polyvalent metal, R1, (a) and (a '), those described above can be used. The molecular weight of R2 and R3 is usually 300 or less, preferably 200 or less, particularly 150 or less from the viewpoint of the flame retardancy of the polymer using (A1). When y is 2 or more, a plurality of R2 and R3 may be the same or different. For example, a mixed polyvalent metal salt of the phosphoric acid monoester (a) and the phosphoric acid diester (a) may be used.

As specific examples of the polyvalent metal salt represented by the general formula (2), each symbol in the formula is as follows:
3 is substituted by H, methyl group or hydroxyethyl group.

[Table 1] Above and below, s-Bt is a sec-butyl group, i-P
r represents an i-propyl group.

(A1) includes, in addition to the polyvalent metal salt represented by the general formula (2), a salt having a plurality of (two or more) polyvalent metals M [eg, y in the general formula (2) In which some or all of R3 are substituted with -M (O-R1) x-1, the following general formula (3) [wherein each symbol is the same as in general formula (2). In which the phosphate group is substituted with a condensed phosphoric acid (such as pyrophosphoric acid) group] and a small proportion (preferably 2
0% or less, especially 10% or less).

[0016]

Embedded image

The unsaturated bond content of (A1) (measured by iodine value measurement, the same applies hereinafter) is preferably 1 meq / g or more, more preferably 2 to 20 meq / g, particularly 3 to 1 from the viewpoint of polymerizability.
0 meq / g is preferred. The metal content (M content) of (A1) (according to the atomic absorption method, the same applies hereinafter) is 1% or more, and more preferably 3 to 2 from the viewpoint of the strength of the resin obtained by polymerizing it.
0%, particularly preferably 5 to 15%. The phosphorus content (P content) of (A1) is 1% or more, more preferably 2 to 30%, especially 5 to 20 from the viewpoint of flame retardancy of a resin obtained by polymerizing the same.
% Is preferred. In the reaction product of (A0) and (b), in addition to (A1), the polyvalent metal alkoxide of (a) or the phosphoric acid of (a) [or (a) and (a ')] By-products such as triesters may be contained in small proportions. The content of (A1) in the reaction product is preferably at least 70%, more preferably at least 80%, particularly preferably at least 90%.

Other metal-containing ethylenically unsaturated monomers (A
2) includes a polyvalent metal alkoxide of an unsaturated alcohol (A21), a polyvalent metal salt of a carboxyl group-containing unsaturated monomer (A22), and a polyvalent metal salt of a sulfo group-containing unsaturated monomer (A23). (A21), (A2
2) As the polyvalent metal constituting (A23), the same (M) as in (A1) can be used.

(A21) includes a polyvalent metal alkoxide of the ethylenically unsaturated group-containing alcohol (a).
Examples of (a) include the same compounds as those described as (a) constituting (A0), and a hydroxyl compound represented by the general formula (1). (A21) can be produced by reacting (a) with (b) represented by the general formula (R1O) xM. As (b), those similar to the ones mentioned in the above (A1) (aluminum isopropoxide, aluminum ethoxide, titanium isopropoxide and the like) can be mentioned. The amount of (b) used is usually 0.95 equivalent, preferably 0.98 to 1 equivalent, relative to 1 equivalent of the hydroxyl group of (a). The above reaction is
The removal can be carried out at room temperature or under heating by removing the alcohol to be eliminated.

As (A21), those represented by the following general formula (4) can be used. As specific examples, the following can be mentioned for each symbol in the formula. [R (CO) rO (A-O) n-] yM (-OR1) xy (4) [The symbols in the formula are the same as in the general formulas (1) and (2). ]

[Table 2] Above and below, Et represents an ethylene group.

The carboxyl group-containing unsaturated monomers constituting (A22) include ethylenically unsaturated mono- and polycarboxylic acids, partial esters of ethylenically unsaturated polycarboxylic acids, and ethylenically unsaturated group-containing alcohols (a). )) Dicarboxylic acid monoesters. Examples of unsaturated monocarboxylic acids include (meth) acrylic acid,
(Iso) crotonic acid, cinnamic acid; unsaturated polycarboxylic acids include unsaturated dicarboxylic acids such as maleic acid,
Fumaric acid, itaconic acid, citraconic acid, mesaconic acid; the partial ester is a monoalkyl (C1-8: the same as R1) ester of the dicarboxylic acid; the monoester of (a) is a dicarboxylic acid (C4
~ 6 or more alkanes or alkenedicarboxylic acids: for example succinic acid, glutaric acid, adipic acid,
And the above-mentioned (a) monoester.

As (A22), those represented by the following general formula (5) can be used. As specific examples, the following can be mentioned for each symbol in the formula. [R'O [(A-O) nCO-R4-COO] t-] yM (-OR1) xy (5) wherein R 'is R (CO) r-, R1-OCO-R4-
CO-, HOOC-R4-CO- or (R1O-) x-
1M-OCO-R4-CO-, R4 is a C2-4 alkylene group or a C2-8 alkenylene group (residue of the above alkane or alkenedicarboxylic acid), t is 0 or 1 (when r is 0, t is 1 ), And other symbols are the same as those in the general formulas (1) and (2). ]

[Table 3]

The sulfo group-containing unsaturated monomer constituting (A23) includes an ethylenically unsaturated group-containing sulfonic acid and an ethylenically unsaturated group-containing sulfate. Examples of the sulfonic acid include unsaturated monomeric alkene sulfonic acids (C2-8) such as vinyl sulfonic acid, (meth)
Allylsulfonic acid, isopropenylsulfonic acid; aromatic vinylsulfonic acid such as styrenesulfonic acid, α-
Methylstyrene sulfonic acid; a sulfo group-containing acrylic monomer [a sulfo group-containing (meth) acrylate or (meth) acrylamide optionally having a hydroxyl group], for example, a sulfoalkyl (C1-4) (meth) acrylate [Sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, 3- (meth) acrylamide- 2-hydroxypropanesulfonic acid, 2- (meth) acrylamide-2,2-dimethylethanesulfonic acid, etc.]; and alkyl (C1-18) (meth) allylsulfosuccinates such as propylallylsulfosuccinate.

The sulfuric ester includes the above-mentioned (a) or an AO adduct thereof [a hydroxyl compound represented by the general formula (1) (where n is an integer of 2 to 30 or more)] [for example, polyalkylene (C2-4 ) Glycol (polymerization degree 2
30) Mono (meth) acrylate: polyethylene glycol (hereinafter abbreviated as PEG) (molecular weight 300) mono (meth) acrylate, polypropylene glycol (hereinafter P)
PG) (molecular weight 500) mono (meth) acrylate, etc.], and polyoxyalkylene (C2-4) ether of dihydric phenol [AO (2-30)
Mol or more) adduct] unsaturated monocarboxylic acid [(meth) acrylic acid or the like] monoester [for example, a hydroxyl compound represented by the following general formula (6)]. RCOO (A-O) n-R5- (OA) m-OH (6) In the formula, R5 is a dihydric phenol residue (residue excluding a hydroxyl group), and n and m are a total of 2 to 30 or Further integers of 1 or more, R and A, are the same as in the general formula (1). Examples of the dihydric phenol constituting the residue Ar include monocyclic dihydric phenols such as hydroquinone, catechol and resorcin; and bisphenols such as bisphenol A, bisphenol F and bisphenol S
Is mentioned. The above-mentioned sulfate ester is obtained by reacting a hydroxyl compound represented by the general formula (1) or (6) with a known sulfate esterification method, for example, by reacting with a sulfating agent such as sulfuric anhydride, fuming sulfuric acid, etc.
Can be manufactured. A small proportion (preferably 20% or less, particularly 10% or less) of unreacted hydroxyl compounds may remain in the sulfated product.

As (A23), those represented by the following general formula (7) can be used. [R6-SO3-] yM (-OR1) xy (7) In the formula, R6 is a residue of a sulfonic acid containing an ethylenically unsaturated group (residue excluding -SO3H) or a general formula (1) or (6) Represents the residue of the hydroxyl compound (residue excluding the active hydrogen atom), and other symbols are the same as those in the general formula (2). When y is 2 or more, R6-SO
Part of 3- may be replaced with a residue of a hydroxyl compound represented by the general formula (1) or (6). Specific examples thereof include those in which each symbol in the formula is as follows, and those in which those vinyl groups are replaced with an isopropenyl group.

[Table 4]

(A22) and (A23) each represent a carboxyl group-containing unsaturated monomer or an ester-forming derivative thereof (an acid anhydride, a C1-4 alkyl ester,
Acid halide) and a sulfo group-containing unsaturated monomer,
It can be produced by reacting with the above (b). As (b), those similar to the ones described in the above (A1) can be mentioned. The amount of (b) to be used is generally 0.95 equivalent, preferably 0.98 to 1 equivalent, per 1 equivalent of carboxyl group or sulfo group. The above reaction can be carried out at room temperature or by heating as necessary to remove the eliminated alcohol, whereby the monomer can be obtained.

The unsaturated bond content of (A2) is preferably 1 meq / g or more, more preferably 2 to 20 meq / g, particularly preferably 3 to 10 meq / g, from the viewpoint of polymerizability. (A
The M content in 2) is usually 1% or more, preferably 3 to 20%, particularly 5 to 15%, from the viewpoint of the strength of the resin obtained by polymerizing the resin. (A1) and (A1)
Depending on the M content in 2), any one or both of the M contents may be outside the above range as long as the entire M content is within the following range.

The M content of the metal-containing ethylenically unsaturated monomer (A) comprising (A1) or (A1) and (A2) is preferably 1 from the viewpoint of the strength of the resin obtained by polymerizing the monomer. % Or more, more preferably 3 to 20%, especially 5%.
~ 15%. The content of (A1) in (A) is usually at least 10%, preferably at least 20%, particularly preferably at least 60%, from the viewpoint of the flame retardancy of the resin.

The unsaturated monomer containing no polyvalent metal (B) is not particularly limited as long as it undergoes addition polymerization, and (B1) an unsaturated hydrocarbon monomer, (B2) a hydroxyl group and / or an ether bond-containing monomer. Unsaturated monomer, (B3) nitrogen-containing unsaturated monomer, (B4) ester bond-containing unsaturated monomer, (B5) halogen-containing unsaturated monomer, (B6)
Ketone bond-containing unsaturated monomers, (B7) sulfur-containing unsaturated monomers, (B8) isocyanate group unsaturated monomers, and (B9) polyfunctional unsaturated monomers.
Examples of these include:

(B1) Unsaturated hydrocarbon monomer (C2-
36 or more): (B11) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene,
Octadecene, α-olefin (C20-36); alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene and the like; (B12) alicyclic vinyl hydrocarbon: cycloalkene ,
For example, cyclohexene; (di) cycloalkadiene, for example, (di) cyclopentadiene; terpene, for example, pinene, limonene; vinylcyclohexene, ethylidenebicycloheptene, etc .; (B13) aromatic vinyl hydrocarbon: styrene (hereinafter S)
t), α-methylstyrene, vinyltoluene,
2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, crotylbenzene, vinylnaphthalene, indene, and the like;

(B2) Unsaturated monomer containing hydroxyl group and / or ether bond: (B21) Unsaturated monomer containing hydroxyl group: (a) and its AO adduct [hydroxyl compound represented by formula (1) n is an integer of 2 to 30 or more) [alkenol, (poly) oxyalkylene monoalkenyl ether, unsaturated monocarboxylic acid hydroxyalkyl ester and unsaturated monocarboxylic acid polyoxyalkylene monoester], for example, 2-hydroxyethylpropenyl Ether, 2-hydroxyethyl acrylate (hereinafter abbreviated as HEA), 2-hydroxyethyl methacrylate (hereinafter abbreviated as HEMA), hydroxypropyl (meth) acrylate, polyethylene glycol (hereinafter abbreviated as PEG) mono (meth) acrylate Rate, polypropylene glycol monoacrylate; hydroxyl compound represented by the general formula (6) [unsaturated monocarboxylic acid monoester of polyoxyalkylene ether of dihydric phenol], for example, PO (2) of bisphenol A
To 30 mol) adduct; unsaturated polyol (2 to 7 or more valent, for example, alkenediol (2-butene-
Monoalkenyl (C2-8) of trihydric or higher hydric alcohol (glycerin, pentaerythritol, sorbitol, sucrose, etc.)
Or more) ethers [such as sucrose (meth) allyl ether]; hydroxystyrene, propargyl alcohol and the like;

(B22) Unsaturated monomer containing ether bond: (B221) Unsaturated monomer containing epoxy group: for example, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide, etc .; (B222) poly Oxyalkylene chain-containing unsaturated monomer: (poly) oxyalkylene (C2-4, polymerization degree 1
30 or more) alkyl (C1-20) ether [AO (EO, PO, etc.) adduct of alkanol], such as methyl alcohol EO 10 mol adduct (meth) acrylate, lauryl alcohol EO 30 mol adduct (meth) acrylate, etc .; (B223) Other ether bond-containing unsaturated monomers: vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2- Butoxyethyl ether, 3,4-
Dihydro-1,2-pyran, 2-butoxy-2′-vinyloxydiethylether, vinyl-2-ethylmercaptoethylether, phenoxystyrene and the like;

(B3) Nitrogen-containing unsaturated monomer: (B31) Amino group-containing vinyl monomer: Amino group-containing unsaturated hydrocarbon: alkenylamine such as (meth)
Allylamine, crotylamine, and amino group-containing styrenic monomers such as N, N-dimethylaminostyrene; amino group-containing (meth) acrylates: mono- and di-alkyl (C1-4) aminoalkyl (C2-4)
(Meth) acrylates such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth)
Heterocyclic amino group-containing (meth) acrylate [morpholinoalkyl (meth) acrylate] such as acrylate, t-butylaminoethyl (meth) acrylate, and the like, for example, morpholinoethyl (meth) acrylate, and methyl α
-Acetaminoacrylate; an amino group-containing (meth) acrylamide, such as N-aminoethyl (meth) acrylamide; a heterocyclic amino group-containing monomer, such as 4-vinylpyridine, 2-vinylpyridine, vinylimidazole, N-vinylpyrrole, and the like; (B32) Amide group-containing vinyl monomer: (meth) acrylamide, N-methyl (meth) acrylamide, N
-Butyl acrylamide, diacetone acrylamide,
N-methylol (meth) acrylamide, cinnamamide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone, etc .; (B33) nitrile group Containing vinyl monomer: (meth)
Acrylonitrile, N-cyanoacrylate and the like;

(B4) Unsaturated monomer containing ester bond: (B41) (meth) acrylate: alkyl (C
1 to 50) (meth) acrylates, for example, methyl acrylate, methyl methacrylate (hereinafter abbreviated as MMA),
Ethyl acrylate, ethyl methacrylate (hereinafter EM)
A), propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, eicosyl (meth) acrylate; cyclo (B42) Other unsaturated carboxylic acids [monocarboxylic acids such as (iso) crotonic acid, cinnamic acid, vinyl benzoic acid, etc. alkyl, aralkyl and aryl (meth) acrylates such as cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate and the like. , Alkoxy (C1-4) substituted acrylic acid; polycarboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid] ester: alkyl (C1-50) ester For example, ethyl α-ethoxy acrylate, methyl 4-vinylbenzoate, dimethyl fumarate, dimethyl maleate and the like;

(B43) Saturated carboxylic acid [monocarboxylic acid (C1-20) such as formic acid, acetic acid, propionic acid,
Butyric acid, alkoxy (C1-4) acetic acid, benzoic acid; unsaturated ester [vinyl ester, dicarboxylic acid (C2-20 such as oxalic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid)] Meta)
Allyl ester, isopropenyl ester, vinyl phenyl ester], for example, vinyl formate, vinyl acetate, isopropenyl acetate, vinyl propionate,
Vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, diallyl phthalate, diallyl adipate, acetoxystyrene, etc .;

(B5) Halogen-containing unsaturated monomer: vinyl chloride, vinyl bromide, vinylidene chloride, (meth) allyl chloride, mono- and di-chlorostyrene, chloroprene, etc .; (B6) Ketone bond-containing unsaturated monomer: vinyl (B7) Sulfur-containing unsaturated monomer: p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide, etc .; (B8) isocyanate group Unsaturated monomer: isocyanatoethyl (meth) acrylate, m-isopropenyl-
α, α-dimethylmethylbenzyl isocyanate and the like;

(B9) Polyfunctional unsaturated monomer: (B91) Polyvinyl hydrocarbon monomer, for example, divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, etc .; (B92) Ether bond-containing polyfunctional unsaturated monomer: 2
-8 or more polyhydric alcohols [alkane polyols which may have an ether bond, such as alkylene (C2-6) glycols (ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, etc.), Glycerin, trimethylolpropane, pentaerythritol, sorbitol, their intramolecular or intermolecular dehydrates (such as sorbitan, polyglycerin, dipentaerythritol),
Sugars (such as sucrose); and their AO (1 to 30 mol or more) adduct]
8 or more: vinyl, (meth) allyl, etc.] ethers such as poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, Tetramethallyloxyethane, etc.], sucrose poly (meth) allyl ether, etc .;

(B93) Ester bond-containing polyfunctional unsaturated monomer: a polyunsaturated carboxylic acid ester of a polyhydric alcohol having 2 to 8 or more (as described above) [such as poly (meth) acrylate], for example, ethylene glycol di ( (Meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, PEG di (meth) acrylate, etc .; alkenyl unsaturated carboxylate [C2-8 or more: vinyl,
[B94) Other polyfunctional unsaturated monomers: bis (meth) acrylamides such as N, N'-methylene-bis (meth) acrylamide; divinyl ketone, divinyl sulfide etc.

Of (B), it is preferable that the HLB value is 1
It is 0 or less, especially 8 or less. In the present invention, HL
The B value is a value calculated by Oda's HLB (“Introduction to New Surfactants”, P197, Sanyo Chemical Industries, Ltd.). Of these, preferred are (B1) and (B1)
4), more preferably (B13) and (B41)
In particular, St and MMA.

The polymerization initiator (C) includes a peroxide-based polymerization initiator (C1), an azo-based polymerization initiator (C2) and the like, and includes the following. Further, the redox polymerization initiator may be formed by using (C1) and the reducing agent (C3) in combination. Further, two or more of (C1) to (C3) may be used in combination. (C1) includes (C11)
Oil-soluble peroxide-based polymerization initiator: acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, diisopropylperoxydicarbonate,
Di-2-ethylhexyl peroxydicarbonate,
2,4-dichlorobenzoyl peroxide, t-butyl peroxybivalate, 3,5,5-trimethylhexanonyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionitrile Peroxide, succinic acid peroxide, acetyl peroxide, t-butylperoxy-
2-ethylhexanoate, benzoyl peroxide (hereinafter abbreviated as BPO), parachlorobenzoyl peroxide, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t-butylperoxylaurate, cyclohexanone Peroxide, t
-Butyl peroxyisopropyl carbonate, 2.5
-Dimethyl-2,5-dibenzoylperoxyhexane, t-butylperoxyacetate, t-butylperoxybenzoate, diisobutyldiperoxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2, 5-di-t-butylperoxyhexane, t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide, pinane hydroperoxide, 2, 5-dimethylhexane-2,
And (C12) a water-soluble peroxide-based polymerization initiator: hydrogen peroxide, peracetic acid, ammonium persulfate, sodium persulfate, and the like; and (C2) includes (C2)
1) Oil-soluble azo polymerization initiator: 2,2′-azobisisobutyronitrile (hereinafter abbreviated as AIBN), 1,1′-azobiscyclohexane 1-carbonitrile, 2,2′-
Azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile and the like; and (C22) a water-soluble azo polymerization initiator:
Examples include azobisamidinopropane salts and azobiscyanovaleric acid (salts); examples of (C3) include ferrous salts, sulfites, hydroxylamine, and hydrazine. Preferred are (C11) and (C2
1), especially BPO and AIBN.

The metal-containing monomer composition of the present invention contains (A)
A composition comprising 1) and (C), and (A1) and (A2)
And / or a composition consisting of (B) and optionally (C). In the metal-containing monomer composition of the present invention, the content of (C) is preferably 0.01 to 5 parts, particularly 0.1 to 2 parts, per 100 parts of the monomer. Above and below, parts refer to parts by weight. (A1) and (A
In the metal-containing monomer composition of the present invention comprising 2) and / or (B), the content of (A1) is usually 5% or more based on the total weight of the monomers. More than 50% 6
0% or more, particularly preferably 80% or more. The content of (B) is preferably 95% or less, more preferably 40% or less, particularly preferably 20% or less.

The metal-containing monomer composition of the present invention may contain various additives, for example, inorganic fillers such as carbon black, titanium oxide and bentonite, dyes and pigments; polymers such as PEG, cellulose and starch; , Chelates, surfactants; stabilizers such as weathering stabilizers (for example, ultraviolet absorbers) and antioxidants (for example, hindered phenols and hindered amines) can be appropriately added. The amount of these additives is not particularly limited, but is usually preferably 85% based on the quality of the obtained resin composition.
The content is more preferably 70% or less, particularly preferably 20% or less.

In the method for producing a metal-containing resin of the present invention,
The polymerization of the monomer [(A1) or (A1) with (A2) and / or (B)] can be carried out by a usual method. Any of bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization and reversed phase suspension polymerization may be used, but bulk polymerization is preferred. Any of random polymerization, block polymerization, and graft polymerization may be used, but random polymerization is preferred. The polymerization can be carried out with heating if necessary. The polymerization temperature is usually 0 to 120 ° C, preferably room temperature to 90 ° C. The polymerization is preferably carried out using (C),
Instead of (C), other polymerization means, for example, thermal polymerization, photopolymerization, or radiation polymerization can be used. The metal-containing monomer composition of the present invention is preferably cast using (C) into a mold of an arbitrary shape simultaneously with polymerization and, if necessary, by heating, to obtain a molded product, plate, sheet, film, rod, or cylinder. Etc. can be obtained. These can also adopt well-known processing methods, such as cast molding, injection molding, and transfer molding.

The metal-containing resin obtained by polymerizing the metal-containing monomer composition of the present invention is usually 1 to 70%, preferably 5 to 50%
M content of usually 1 to 20%, preferably 1 to 10%
P content. The obtained metal-containing resin is a three-dimensionally cross-linked, insoluble, infusible solid resin, having low water absorption (water absorption of 1% or less according to JIS K7209) and high flame retardancy (JIS K7201-1976). Has an oxygen index of 30 to 50).

[0045]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.

Production Example 1 224 g of HEA, 153.3 g of phosphorus oxychloride, and 0.4 g of pyridine were charged into a 1 L four-necked kolben and reacted at 110 ° C. for 6 hours while capturing liberated hydrochloric acid. After washing with a sodium aqueous solution and separating into an oil layer and an aqueous layer, the oil layer is taken out and the phosphoric acid diester (A
0-1) [Consisting of 82% of diester and 18% of triester (by liquid chromatography; the same applies hereinafter)] 3
26 g were obtained. (A0-1) 326 g, aluminum isopropoxide (trade name: AIPD, manufactured by Kawaken Fine Chemical Co., Ltd.) 204.2 g, and hydroquinone 0.06
g was charged into a 1 L 4-necked kolben, and heated to 80 ° C. while blowing air into the liquid at 1 ml / separation. When the temperature reached 80 ° C., the inside of the Kolben was depressurized to remove 180 g of the desorbed isopropyl alcohol, and a pale yellow viscous liquid metal-containing ethylenically unsaturated monomer consisting of the monomer (A1-1) [ Unsaturated bond content 5.8 meq / g, M content 6.9
%, P content 9.0% (by iodine value measurement, atomic absorption spectrometry; the same applies hereinafter)] of 350.2 g.

Preparation Example 2 260 g of HEMA, 153.3 g of phosphorus oxychloride and 0.6 g of pyridine were charged into a 1 L four-necked kolben and reacted at 110 ° C. for 6 hours while trapping liberated hydrochloric acid. After washing with a sodium aqueous solution and separating into an oil layer and an aqueous layer, the oil layer is taken out, and phosphoric acid diester (A0-2) (diester 85% and triester 18%)
354 g). (A0-2) 354 g and titanium isopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) 283.9
g and hydroquinone 0.06 g were charged into a 1 L four-necked kolben, and 80 ° C. while blowing air into the liquid at 1 ml / min.
Heat to When the temperature reached 80 ° C., 240 g of the isopropyl alcohol desorbed was removed by depressurizing the inside of the Kolben, and the metal-containing ethylenically unsaturated monomer (unsaturated bond content: 5.25) composed of the monomer (A1-2) was removed. (0 meq / g, M content 11.1%, P content 8.0%), 379.9 g.

Production Example 3 Allyl alcohol (174 g) and phosphorus oxychloride (153.3)
g and 0.8 g of pyridine in a 1L 4-necked kolben,
After reacting at 100 ° C. for 10 hours while capturing the liberated hydrochloric acid, the reaction product is washed with an aqueous sodium hydrogen carbonate solution, separated into an oil layer and an aqueous layer, and then the oil layer is taken out to obtain the phosphoric diester (a3) (83% diester). And triester 17
%). (A3) 268 g of mono-sec-butoxyaluminum diisopropoxide (trade name: AMD, manufactured by Kawaken Fine Chemical Co., Ltd.) 2
Charge 18.2 g, and heat to 80 ° C while blowing air into the liquid at 1 ml / separation. When the temperature reached 80 ° C., the inside of the Kolben was depressurized to remove 120 g of the desorbed isopropyl alcohol, and the metal-containing ethylenically unsaturated monomer (unsaturated bond content of 9) composed of the monomer (A1-3) was removed. 0.7 milliequivalents / g, M content 11.6%, P content 1
(5.6%) 366.2 g were obtained.

Comparative Production Example HEA (448 g) and aluminum isopropoxide (trade name: AIPD, manufactured by Kawaken Fine Chemical Co., Ltd.) 20
4.2 g and 0.06 g of hydroquinone are charged into a 1 L four-necked kolben, and heated to 80 ° C. while blowing air into the liquid at 1 ml / min. 180 g of isopropyl alcohol desorbed by reducing the pressure inside the Kolben when the temperature reaches 80 ° C
And the metal-containing ethylenically unsaturated monomer (unsaturated bond content: 6.3 meq /
g, M content: 5.7%).

Examples 1 to 6 and Comparative Examples 1 and 2 According to the formulation (parts) shown in Table 5, a monomer and a polymerization initiator were mixed, placed in a closed vessel and heated to 80 ° C. 10
Polymerization started after about 20 minutes, and a resin was obtained after 30 minutes. The monomer (A22-1) used in Comparative Example 2 was aluminum acrylate (20% aqueous solution) [manufactured by Asada Chemical Co., Ltd.]. Table 6 shows the physical properties of the obtained resin.

[0051]

[Table 5]

[0052]

[Table 6]

Tensile breaking strength (kgf / mm2): JIS
Flexural strength (kgf / mm2): compliant with JIS K7203 Flexural modulus (kgf / mm2): compliant with JIS K7203 Wet tensile breaking strength (kgf / mm2): measured after immersion in water for 24 hours, compliant with JIS K7113 Wet flexural strength (kgf / mm2): Measured after immersion in water for 24 hours, in accordance with JIS K7203 Wet flexural elasticity (kgf / mm2): Measured after immersion in water for 24 hours, in accordance with JIS K7203 Water absorption (%): In accordance with JIS K7209 Compliant Dry dimensional shrinkage (%): Compliant with JIS K7114 Oxygen index (O.I.): Compliant with JIS K7201

[0054]

The metal-containing monomer composition of the present invention has better compatibility than the conventional water-soluble metal acrylate monomer and hydrophobic unsaturated monomer. In producing the metal-containing resin by polymerizing the metal-containing monomer 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 resin obtained in the present invention has a low water absorption and a high wet strength. It also has better flame retardancy than conventional metal-containing resins. 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. Therefore, the contained metal resin of the present invention is easy to produce and is useful as a heat insulating material, a structural material, a protective material, and a sound insulating material.

Claims (13)

[Claims] 1. A polyvalent metal salt (A1) of a phosphoric acid ester (A0) of an ethylenically unsaturated group-containing alcohol (a).
And another polyvalent metal-containing ethylenically unsaturated monomer (A2) and / or a polyvalent metal-free unsaturated monomer (B) and / or a polymerization initiator (C). Metal monomer composition. 2. (a) is represented by the following general formula (1):
The composition of claim 1. R (CO) rO (A-O) nH (1) wherein R is an alkenyl group having 2 to 8 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, r is 0 or 1, n is 0 or Represents an integer of 1 or more. ] 3. The composition according to claim 2, wherein R is a vinyl group, an isopropenyl group or an allyl group. 4. The composition according to claim 1, wherein (A1) is represented by the following general formula (2). Embedded image [Wherein, x is an integer of 2 to 4, y is a positive integer not greater than x; M is a polyvalent metal; R1 is an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms; R3 represents a hydrogen atom or a residue of (a) or a saturated alcohol. ] 5. The method according to claim 1, wherein (A2) is at least one selected from the group consisting of a polyvalent metal alkoxide of an unsaturated alcohol, a polyvalent metal salt of a carboxyl group-containing unsaturated monomer, and a polyvalent metal salt of a sulfo group-containing unsaturated monomer. The composition according to any of claims 1 to 4, which is a seed. 6. A polyvalent metal having a group IIa, IIIa, IVa or I
A composition according to any of claims 1 to 5, which is a Group b, IIb, IVb or VIII metal. 7. (A1) or (A1) and (A2)
The composition according to any one of claims 1 to 6, wherein the metal content is 1% by weight or more. 8. The composition according to claim 1, comprising (A1) in an amount of 5 to 100% by weight based on the total weight of the monomers. 9. (B) is an unsaturated hydrocarbon monomer, an unsaturated monomer containing a hydroxyl group and / or an ether bond, a nitrogen-containing unsaturated monomer, an unsaturated monomer containing an ester bond, an unsaturated monomer containing a halogen, and an unsaturated monomer containing a ketone bond. The composition according to any one of claims 1 to 8, wherein the composition is one or more selected from the group consisting of a saturated monomer, a sulfur-containing unsaturated monomer, an isocyanate group unsaturated monomer, and a polyfunctional unsaturated monomer. 10. The composition according to claim 1, wherein (B) has an HLB value of 10 or less. 11. The method according to claim 11, wherein (C) is added in an amount of 0.1 to 100 parts by weight of the monomer.
The composition according to any one of claims 1 to 10, which contains from 01 to 5 parts by weight. 12. A metal-containing resin obtained by polymerizing the composition according to claim 1 and having a metal content of 1 to 70% by weight. 13. A polyvalent metal salt (A1) of a phosphate (A0) of an ethylenically unsaturated group-containing alcohol (a).
Or production of a metal-containing resin characterized by polymerizing (A1) with another polyvalent metal-containing ethylenically unsaturated monomer (A2) and / or a polyvalent metal-free unsaturated monomer (B). Method.