JP3087871B2 - Method for producing macromonomer having hyperbranched structure - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a macromonomer, which is a material useful for making a polymer material multifunctional, and a macromonomer having a multibranched structure obtained by the production method of the present invention. A polymer having radical polymerizability and obtained by copolymerizing it with another radical polymerizable monomer is suitably used as a paint, coating agent, adhesive or the like.

[0002]

2. Description of the Related Art In order to achieve multifunctional polymer materials, attempts have been made to use graft copolymers for a long time. One means of obtaining a graft copolymer having a preferable structure is generally a macromonomer method. There is known a method called a method for producing a graft copolymer, in which a macromonomer which is a high molecular monomer is copolymerized with another monomer. Regarding the production of macromonomers as the raw materials for the synthesis of graft copolymers as described above, see Chapter 2, "Synthesis of Macromonomers (39-77)" by Yuya Yamashita, "Chemistry and Industry of Macromonomer", published by IPC Publishing Bureau.
P.), And many other methods have been proposed.

[0003] However, all conventionally known macromonomers are basically linear, and hyperbranched macromonomers are not known. The present invention relates to a graft copolymer having a large number of branch polymers, such as a graft copolymer obtained by a macromonomer method, having a structure in which a radical polymerizable group is introduced at one end of a trunk polymer chain, or a macromonomer, for example. For producing a macro-monomer having a multi-branched structure having a structure in which a radical polymerizable group is introduced into a molecular terminal of a multi-branched homopolymer obtained by a method of polymerizing Aimed to provide.

[0004]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, completed the present invention. That is, the present invention provides a linear macromolecule having a radical polymerizable group at one end of a molecule in the presence of a mercaptan compound having one type of functional group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group. Monomer and another radical polymerizable monomer undergo radical polymerization to obtain a polymer having the above functional group at the terminal of the molecule, and the polymer, an ethylenically unsaturated bond and a group reactive with the above functional group are formed. A method for producing a macromonomer having a multibranched structure, characterized by reacting a compound having the same with a compound having the same. Hereinafter, the present invention will be described in more detail.

[0005] In the present invention, a linear macromonomer (hereinafter, referred to as a raw material macromonomer) used as a raw material for synthesizing a macromonomer having a multibranched structure (hereinafter, referred to as a multibranched macromonomer) includes a (meta-method) ) Linear macromonomers having radically polymerizable groups such as acryloyl group, styryl group, allyl group, vinylbenzyl group, vinyl ether group, vinylalkylsilyl group, vinylketone group and isopenyl group. The preferred number average molecular weight of the moiety is from 1,000 to 30,000, more preferably from 1,000 to 10,000. The number average molecular weight is 1,
When the molecular weight is less than 000, the branched polymer chain in the obtained multi-branched macromonomer is too short, and characteristics unique to the multi-branched polymer are not exhibited. On the other hand, if it exceeds 30,000,
Poor copolymerizability of the raw material macromonomer with other radically polymerizable monomers.

The monomer constituting the polymer portion of the raw material macromonomer is preferably a radical polymerizable monomer.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
(Meth) acrylic acid esters such as lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, (anhydride) maleic acid, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, (meth) acrylamide, N-methylolacrylamide, polyfluoroacrylate, perfluoroalkyl acrylate, (meth) acryloyloxypropyltrimethoxy Silicone-containing (meth) acrylates such as silane, vinyl esters such as styrene, α-methylstyrene, (meth) acrylonitrile, vinyl acetate, and vinyl propionate Olefinic compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, butadiene, isoprene, isobutylene, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, vinylpyridine, vinylpyrrolidone and N-vinyl Carbazole and the like can be mentioned, and these can be used alone or in combination of two or more.

As a method for synthesizing the raw material macromonomer, for example, by living anion polymerization, when the above monomer is polymerized and reaches a desired molecular weight, it is reacted with a terminator having a radical polymerizable group such as a vinyl group. A reactive group such as a carboxyl group at the molecular terminal obtained by subjecting the above monomer to radical polymerization in the presence of a mercaptan-based radical chain transfer agent having a carboxyl group or the like (JP-A-51-125186). And a method of reacting a polymer having the above with glycidyl (meth) acrylate (Japanese Patent Publication No. 43-11224). Also,
In addition, a group transfer polymerization method (Japanese Unexamined Patent Publication No.
No. 62801) and an iniferter polymerization method. As the raw material macromonomer in the present invention, a macromonomer in which a (meth) acryloyl group having high radical polymerizability is introduced at a terminal of a polymer skeleton produced by a radical polymerization method or an anion polymerization method is preferable.

As the raw material macromonomer, a commercially available macromonomer can be used. For example, a polymethyl methacrylate type macromonomer (AA-A) manufactured by Toagosei Chemical Industry Co., Ltd.
2, AA-6), polyisobutyl methacrylate type macromonomer (AW-6S), polybutyl acrylate type macromonomer (AB-6), polystyrene type macromonomer (AS-6), styrene-acrylonitrile copolymerization type macromonomer ( AN-6) and polydimethylsiloxane type macromonomers (AK-5, AK-30),
And a polystyrene type macromonomer (Macromer 13-KPSMA) manufactured by Sartomer.

In the present invention, as described above, in the presence of a mercaptan compound having one type of functional group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group, the above-mentioned raw material macromonomer and another radical polymerization are carried out. In the radical polymerization, a polymer having the above functional group at the end of a polymer chain formed of the other radical polymerizable monomer (hereinafter referred to as a prepolymer) is obtained by radically copolymerizing the reactive monomer. Need to get. As the other radically polymerizable monomer to be copolymerized with the raw material macromonomer, the radically polymerizable monomer mentioned as a monomer forming the polymer portion of the raw material macromonomer can be used, and its use ratio depends on the purpose. Can be appropriately selected depending on the multibranched macromonomer to be used, but is preferably 5 to 95% by weight, more preferably 30 to 70% by weight, based on the total amount of the raw material macromonomer and other monomers. It is.

The mercaptan compound used in the polymerization for obtaining the prepolymer includes a carboxyl group-containing compound such as mercaptoacetic acid and mercaptopropionic acid, a hydroxyl group-containing compound such as mercaptoethanol, and an amino group-containing compound such as aminoethanethiol. Is mentioned. These mercaptan compounds, by the action of the thiol group contained,
It acts as a chain transfer agent in radical polymerization, and as a result, at one end of a main chain of the obtained prepolymer, that is, a polymer chain formed of another monomer copolymerized with a macromonomer (hereinafter simply referred to as a main chain), A kind of functional group selected from a carboxyl group, a hydroxyl group or an amino group derived from the mercaptan compound is introduced.

The preferred amount of the mercaptan compound used is
For example, the amount of the raw material macromonomer is 30 to 70 in the copolymerization ratio of the raw material macromonomer and another radical polymerizable monomer.
When it is% by weight, it is 1 to 10 parts by weight per 100 parts by weight of the radical polymerizable monomer other than the macromonomer. The molecular weight of the prepolymer can be controlled by the amount of the mercaptan compound used, and the preferred number average molecular weight of the prepolymer in the present invention is 3,000 to 50,000.

As the polymerization initiator, azo initiators such as 2,2'-azobisisobutyronitrile and azobisdimethylvaleronitrile are preferred. When an organic peroxide is used, the mercaptan compound used as a chain transfer agent does not work effectively, and the purity of the obtained prepolymer is poor.
The preferred amount of the polymerization initiator to be used is, for example, a copolymerization ratio of the raw material macromonomer and another radical polymerizable monomer. When the amount of the raw material macromonomer is 30 to 70% by weight, other radicals other than the macromonomer are used. 0.2 to 7.0 parts by weight per 100 parts by weight of the polymerizable monomer, more preferably
It is 1.0 to 4.0 parts by weight. When the amount of the polymerization initiator used is 0.2
When the amount is less than 10 parts by weight, the polymerization conversion of the monomer and the macromonomer used is inferior. On the other hand, when the amount exceeds 7 parts by weight, the prepolymer contains a large amount of a polymer containing no carboxyl group.

As the polymerization medium, an organic solvent is preferable.
Benzene, toluene, xylene, ethyl acetate, butyl acetate, methoxymethyl acetate, ethoxyethyl acetate, dioxane, methyl ethyl ketone, methyl isobutyl ketone,
Examples include cyclohexane and N, N-dimethylformamide. The polymerization temperature may be about 70-100 ° C,
The polymerization time is usually 5 to 12 hours.

A prepolymer having one functional group selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group at one end of the main chain obtained by the above polymerization, a group reactive with the functional group and ethylene By reacting with a compound having an unsaturated bond (referred to as a compound for introducing an unsaturated bond), a macromonomer having a multibranched structure can be obtained. Examples of the unsaturated bond-introducing compound include a radical polymerizable monomer having a glycidyl group such as glycidyl (meth) acrylate, a radical polymerizable monomer having an isocyanate group such as 2-isocyanatoethyl (meth) acrylate, and (meth). A) a radical polymerizable monomer having a carboxyl group such as acrylic acid;
They are appropriately selected and used depending on the type of the functional group of the prepolymer. For example, a radical polymerizable monomer having a glycidyl group can be used for a prepolymer having a carboxyl group as a terminal functional group, and a radical polymerizable monomer having an isocyanate group can be used for a prepolymer having a hydroxyl group. Any of the above compounds can be used for the prepolymer having an amino group.

When a prepolymer having a terminal carboxyl group is reacted with a radical polymerizable monomer having glycidyl, the preferred amount of the radical polymerizable monomer having glycidyl is 0.1% of the carboxyl group in the prepolymer. 90 to 1.5 equivalents. If it is less than 0.90 equivalent, the glycidyl group is too small relative to the amount of the carboxyl group at the end of the prepolymer, and a large amount of unreacted prepolymer remains. On the other hand, when it exceeds 1.5 equivalents, side reactions other than the reaction with the prepolymer terminal occur, and it is difficult to obtain a highly purified multibranched macromonomer.

For the reaction between the prepolymer having a terminal carboxyl group and the radical polymerizable monomer having glycidyl, a tertiary amine, a quaternary ammonium salt or a quaternary phosphonium salt is preferably used as a catalyst. The preferred amount used is 0.1 per 100 parts by weight of the prepolymer.
0 to 3.0 parts by weight.

The catalyst is preferably a quaternary ammonium salt or a quaternary phosphonium salt which has catalytic activity even under mild conditions. Specific examples include triethylbenzylammonium chloride, trimethylcetylammonium bromide, trimethylbenzylammonium chloride, and tetrabutylammonium. And quaternary ammonium salts such as bromide, triphenylbutylphosphonium bromide, tetrabutylphosphonium bromide and tetraethylammonium chloride. Particularly preferred are tetrabutylammonium bromide and tetrabutylphosphonium bromide. Reaction temperature is 60 to 130
It is preferable to add 10 to 500 ppm of a radical polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether as a polymerization inhibitor to the reaction solution, and to ventilate with air or oxygen gas.

Prepolymer having hydroxyl group and 2
For the reaction with a radical polymerizable monomer having an isocyanate group such as isocyanateethyl (meth) acrylate, a tertiary amine or an organic tin compound such as dibutyltin dilaurate or dibutyltin diacetate can be used as a catalyst. In addition, the reaction can be carried out by heating to 80 to 120 ° C without a catalyst. A prepolymer having a terminal amino group can also be used to synthesize a hyperbranched macromonomer by the above method.

The multibranched macromonomer obtained according to the present invention is, for example, hydrophilic / hydrophobic with respect to each of the side chains derived from the raw material macromonomer and the main chain composed of other radically polymerizable monomers. In order to obtain the relationship of adhesiveness, adhesiveness / release property or hard / softness, the molecule can be designed, and by copolymerizing such a multi-branched macromonomer with another radical polymerizable monomer, Further, a polymer having a highly branched structure can be easily synthesized. The polymer thus obtained has a low solution viscosity despite its high molecular weight, and thus is suitable as a solution-type coating material having a high solid content and a low viscosity.

[0020]

The present invention will now be described more specifically with reference to examples. Note that “parts” in each example is “parts by weight”.
And the number average molecular weight (Mn) and weight average molecular weight (Mw) are values in terms of polystyrene measured by gel permeation chromatography. <Example 1> In a flask equipped with a stirrer, a cooling pipe, a thermometer, a nitrogen introducing pipe, and a dropping funnel, 30 parts of methyl methacrylate (abbreviated as MMA), 150 parts of toluene, and a methacryloyl-based polyMMA macromonomer at one end [Toa] AA-2 manufactured by Synthetic Chemical Industry Co., Ltd., Mn = 1500, Mw =
2800] A mixture of 70 parts of mercaptoacetic acid and 1.0 part of mercaptoacetic acid (abbreviated as TGA) was charged into a flask, and heated to 80 ° C. while passing nitrogen gas through. 2 in 50 parts of toluene
2'-azobisisobutyronitrile (abbreviated as AIBN)
Of the initiator solution in which 0.75 part was dissolved, 40 parts were added dropwise over 2 hours and polymerization was continued for 1 hour. Then, 10 parts of the remaining initiator solution was added, and polymerization was continued at 85 ° C for 3 hours. To obtain a prepolymer solution. The conversion of MMA was 98.8%. A part of the prepolymer solution was purified by precipitation with methanol and dried, and the acid value of the dried product was 5.8 mgKOH / g.
Mn and Mw were 9400 and 77000, respectively.

To 300 parts of the above prepolymer solution, 1.7 parts of glycidyl methacrylate (abbreviated as GMA) and 0.9 parts of tetrabutylammonium chloride were added, and the mixture was reacted at 90 ° C. for 6 hours while blowing air to form a multibranched polymer. Macromonomers were synthesized. M of the obtained macromonomer
n and Mw were 9500 and 81000, respectively.

Example 2 Instead of TGA, 2.5 parts of 3-mercaptopropionic acid (abbreviated as MPA) and AIBN were used.
Except that it is 1.0 part, the acid value is 16.1 mg in the same manner as in Example 1.
A prepolymer having KOH / g, Mn = 3000 and Mw = 20400 was obtained, and then macromonomerization was carried out with 3.7 parts of GMA in the same manner as in Example 1. Mn = 3200 and Mw = 1
9000 hyperbranched macromonomers were obtained.

Example 3 50 parts of MMA, methacryloyl group type styrene / acrylonitrile copolymer macromonomer at one end [AN-6, Mn manufactured by Toagosei Chemical Industry Co., Ltd.]
= 6000, Mw = 13000] 50 parts and MPA0.
A prepolymer was obtained in the same manner as in Example 1 using 7 parts, and then subjected to macromonomerization using 1.0 part of GMA and 0.9 part of tetrabutylphosphonium bromide.
A hyperbranched macromonomer was obtained. This Mn is 17000
Met.

Example 4 60 parts of MMA, 10 parts of 2-hydroxyethyl methacrylate, methacryloyl group type polydimethylsiloxane macromonomer at one end [AK-30, manufactured by Toagosei Chemical Industry Co., Ltd., Mn = 25000] 30
And 1.5 parts of TGA were dissolved in a mixed solvent of 50 parts of toluene and 50 parts of methyl ethyl ketone, and the mixture was polymerized under the reflux of the solvent in the same manner as in Example 1 to obtain a prepolymer solution. Next, 2.5 parts of GMA and 0.9 part of tetrabutylphosphonium chloride were used to carry out a macromonomerization reaction to obtain a multibranched macromonomer. This Mn
Was 7100.

Reference Example 1 In a flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen inlet tube and a dropping funnel, 20 parts of the multibranched macromonomer obtained in Example 1, 20 parts of 2-hydroxyethyl methacrylate, 50 parts of n-butyl methacrylate, 10 parts of styrene, 150 parts of butyl acetate and 1 part of AIBN were charged, and the mixture was heated to 90 ° C. while passing nitrogen gas to carry out polymerization for 6 hours. During the polymerization, after 4 hours, 0.5 parts of AIBN was added. After the polymerization was completed, the n-butyl methacrylate in the reaction solution was analyzed by gas chromatography to find that the polymerization rate of n-butyl methacrylate was 98.7%. According to measurement by gel permeation chromatography, the obtained polymer had Mn = 19,400 and Mw = 47,600, and the amount of unreacted multibranched macromonomer was determined by the charged macromonomer. Was found to be 5% by weight.

Reference Example 2 Polymerization was carried out in the same manner as in Reference Example 1, except that 20 parts of the multibranched macromonomer obtained in Example 4 was used. By the above polymerization, Mn = 15,200
As a result, a polymer having an Mw of 42,000 was obtained, and the ratio of the unreacted macromonomer was 4% by weight.

[0027]

According to the present invention, as described above, the physical properties of the side chain and the main chain, that is, the main chain composed of the side chain derived from the raw material macromonomer and other radical polymerizable monomers are, for example, hydrophilic. A multi-branched macromonomer having a structure having a relationship such as hydrophilicity / hydrophobicity, adhesiveness / release property, or hard / softness can be easily produced. Furthermore, by copolymerizing the branched macromonomer with another radical polymerizable monomer, the resulting highly branched polymer has a low solution viscosity despite its high molecular weight. It is suitable as a solution type paint, coating agent, adhesive or the like having a high solid content and a low viscosity. Further, the polymer is characterized in that shrinkage is extremely small when crosslinked and cured by melamine, isocyanate or the like.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-1-245001 (JP, A) JP-A-60-13802 (JP, A) JP-A-3-221513 (JP, A) JP-A-1- 132601 (JP, A) JP-A-58-59202 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 8/00 C08F 299/00

Claims (1)

(57) [Claims] 1. A linear macromonomer having a radical polymerizable group at one end of a molecule in the presence of a mercaptan compound having one kind of functional group selected from the group consisting of a hydroxyl group, a carboxyl group and an amino group. And radical polymerizing other radical polymerizable monomers to obtain a polymer having the above functional group at the terminal of the molecule, and having both the polymer, an ethylenically unsaturated bond and a group reactive with the above functional group. A method for producing a macromonomer having a multibranched structure, comprising reacting a compound with a compound.