JPS63205311A - Manufacture of graft copolymer - Google Patents

Abstract

PURPOSE:To produce easily an uncolored graft copolymer suitable for coatings, etc. in high graft efficiency, by copolymerizing a macromonomer having a specific composition with a copolymerizable monomer. CONSTITUTION:A polymer (A) having an end carboxyl group (e.g., a polymer of methyl acrylate obtained by the polymerization using a polymerization initiator containing a free carboxyl group in the molecule, a chain transfer agent, etc.) and an unsaturated basic aziridine compound (B) (e.g., a compound of formula II or II), and at least one compound (C) selected from the group consisting of monoisocyanates, ketenes, and ketene dimers (e.g., propyl isocyanate or methylketene) are reacted to produce a macromonomer. Then, the resulting macromonomer and a copolymerizable monomer (e.g., acrylic acid) are copolymerized to yield the aimed graft copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing a graft copolymer. More specifically, the present invention relates to a method for producing a graft copolymer by which a colorless graft copolymer can be easily obtained with high graft efficiency.

<Prior art and problems to be solved by the invention> Conventionally, when obtaining a graft copolymer, a so-called macromonomer having a polymerizable unsaturated group at the end is used as a component constituting the graft chain, and The method of copolymerizing polymerizable monomers to form a chain is an extremely useful method for obtaining a tailor-mate graft copolymer depending on the purpose of use.

Several proposals have been made so far as methods for producing macromonomers used for this purpose. For example, a method (UK Patent No. 1,096,918),
A polymerizable monomer is polymerized in the presence of a chain transfer agent such as mercaptoethanol to obtain a polymer having terminal hydroxyl groups, which is modified with a polyisocyanate compound such as tolylene diisocyanate, and then reacted with 2-hydroxyethyl methacrylate. (U.S. Patent No. 3,689,593)
etc. are disclosed.

However, since these methods have low reaction efficiency, graft copolymers using these methods have extremely low graft efficiency. Furthermore, the reaction required to obtain the macromonomer requires a high temperature and a long time, and the obtained macromonomer and the graft copolymer using the same are disadvantageously colored significantly.

Accordingly, an object of the present invention is to provide a method for producing a graft copolymer that can easily produce a non-colored graft copolymer with high grafting efficiency.

<Means and effects for solving the problems> As a result of repeated research, the present inventors have found that by using macromonomers obtained by a specific method when producing a graft copolymer, 1. It has been found that the above object is achieved.

That is, the present invention provides a polymer (A) having a terminal carboxyl group (hereinafter referred to as a polymer prisoner), an unsaturated basic aziridine compound (B) and a monoisocyanate selected from the group consisting of ketenes and ketene dimers. A macromonomer (■) obtained by reacting the obtained at least one compound (0 (hereinafter referred to as compound (C)), and a polymerizable monomer that is copolymerizable with the macromonomer (I). The present invention relates to a method for producing a graft copolymer, which is characterized by copolymerizing a polymerizable monomer (■) (hereinafter referred to as a polymerizable monomer (II)).

The polymer prison used in the present invention can be easily produced by conventionally known methods. For example, a polymerizable monomer (a
) is obtained by polymerizing. The polymerizable monomer (a) used in this case is not particularly limited as long as it does not have a free carboxyl group in the molecule, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, etc. Acrylate, butyl (meth)acrylate, tert-butyl (meth)acrylate, 2
-Ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, trifluoroethyl (meth)
Acrylate, perfluorooctylethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, N, N-
(meth)acrylic acid esters such as dimethylaminoethyl (meth)acrylate and sulfoxyethyl (meth)acrylate; (meth)acrylic acid esters such as (meth)acrylamide, N-methylol (meth)acrylamide, and ) Acrylamide or its derivatives; diesters of unsaturated dibasic acids such as maleic acid dimethyl ester, maleic acid diethyl ester, maleic acid dipropyl ester, itaconic acid dimethyl'' ester, itaconic acid diethyl ester; (meth)acrylonitrile, etc. Unsaturated 2) IJ styrene, α
- Vinyl aromatics such as methylstyrene, α-chlorostyrene, and vinyltoluene; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl halides such as vinyl chloride and vinyl fluoride; Vinylidene chloride and vinylidene fluoride and olefins such as ethylene and propylene, and one or more of these may be used. Polymerizable monomer (
If a carboxyl group-containing monomer such as (meth)acrylic acid is used as a), the resulting macromonomer will not be polyfunctional and will gel during the production of the graft copolymer, which is not preferred. Examples of polymer prisoners other than those listed above include:
Examples include self-condensates of hydroxycarboxylic acid compounds such as p-hydroxybenzoic acid and 12-hydroxystearic acid, and polydimethylsiloxanes containing terminal carboxyl groups (trade name: PS402 Chisso ■m).

Unsaturated basic aziridine compound (B
) is an unsaturated aziridine compound having one aziridine group and one polymerizable unsaturated group in one molecule, in which the nitrogen atom of the aziridine group in the compound exhibits basicity. The significance of using the unsaturated basic aziridine compound (B) is that it is possible to reliably introduce a polymerizable unsaturated group into the resulting macromonomer (I) due to its high reactivity with polymer particles.

That is, when an unsaturated aziridine compound in which the nitrogen atom of the aziridine group does not exhibit basicity is used, the reaction efficiency with the polymer prisoner is low, and therefore, even if a graft copolymer is produced using the obtained macromonomer, This results in inferior graft efficiency. Specific examples of the unsaturated basic aziridine compound B) include cH, =cn-N'q CH, =CH-CH2-N3, and the like.

In the present invention, the unsaturated basic aziridine compound (B)
is used to introduce a polymerizable unsaturated group into the polymer (3), and is 1.0 to 1.4 mol, particularly 1.0 to 1.4 mol, per 1.0 mol of free carboxyl groups of the polymer. Preferably, it is used in a proportion of 1.2 mol. The amount of unsaturated basic aziridine compound (B) used is 1.0 free carboxyl group.
If the amount is less than 1.0 mol, the resulting macromonomer (D) contains unreacted polymer particles, so the graft copolymer produced using it has a low grafting efficiency. , if the amount of unsaturated basic aziridine compound (B) used is large, exceeding 1.4 mol, unsaturated basic aziridine compound (B) obtained by ring-opening polymerization of the aziridine group.
A homopolymer of is produced as an impurity.

The compound (C) used in the present invention is at least one compound selected from the group consisting of monoisocyanates, ketenes, and ketene dimers, each represented by the following general formula.

Monoisocyanates R1-N-C=Oofc-
.

(However, R1 is an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, or a phenyl group, and R2 and R3
is hydrogen, an alkyl group having 1 to 8 carbon atoms, a cyclohexyl group, or a phenyl group. ) Applicable monoisocyanates include, for example, methyl isocyanate, ethyl isocyanate, propyl isocyanate, isopropylinocyanate, butyl isocyanate, 5ec-butyl isocyanate, octyl isocyanates, cyclohexyl isocyanate, phenyl isocyanate, and the like.

Applicable ketenes include, for example, ketene, methyl ketene, ethyl ketene, propyl ketene, butyl ketene, octyl ketene, dimethyl ketene, diethyl ketene, dipropyl ketene, dibutyl ketene, methyl ethyl ketene,
Examples include methylpropylketene, cyclohexylketene, and phenylketene.

Applicable ketene dimers include, for example, ketene dimer, methyl ketene dimer, ethyl ketene dimer,
Examples include propyl ketene dimer, butyl ketene dimer, dimethyl ketene dimer, diethyl ketene dimer, methyl ethyl ketene dimer, cyclohexyl ketene dimer, phenyl ketene dimer, and the like.

The significance of using the compound (Q) is to eliminate the basic amino group produced by the reaction between the polymer (5) and the unsaturated basic aziridine compound (B) without reducing the rate of the reaction, resulting in non-adhesive properties. The macromonomer (I) is obtained. For this purpose, monoisocyanates and ketenes are particularly preferred. Compound (Q is an unsaturated basic aziridine compound [F]) 1.0 mol It is preferably used in a proportion of 0.8 to 1.2 mol, particularly 0.9 to 1.1 mol.

If the amount of compound (C) used is less than 0.8 mol per 1.0 mol of unsaturated basic aziridine compound (B), non-adhesive macromonomer (I) cannot be obtained, and if it exceeds 1.2 mol. It is virtually meaningless even in large quantities.

The macromonomer (I) in the present invention comprises an unsaturated basic aziridine compound (B) and a compound (Q) in a polymer matrix.
Preferably from room temperature to 200'C1, preferably from 40 to
It is obtained by reaction at a temperature of 110°C.

The reaction can be selected from various methods, for example, a method may be used in which the polymer prisoner, the unsaturated basic aziridine compound 03+, and the compound (C) are reacted all at once. Although the method of reacting the polyaziridine compound (B) with the compound (B) and then reacting the compound (Q) is also possible, the latter method is preferable.In addition, the viscosity of the polymer (5) is high during the reaction, and stirring etc. If control is difficult, an appropriate diluent may be used to make the reaction proceed smoothly. Diluents that can be used include polymeric particles, unsaturated basic aziridine compound (I3), and compound (0 to 0). There are no particular restrictions on the diluent as long as it is inert and capable of dissolving or dissolving these three substances. Typical diluents include aromatic hydrocarbons such as benzene, toluene, xylene, and chlorobenzene; dioxane; Ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone; Esters such as ethyl acetate and butyl acetate; Glycol ethers; Carpitols; Alcohols; Water 4
= can be mentioned. Furthermore, polymerizable monomers having no functional organs other than polymerizable unsaturated groups, such as styrene, acrylonitrile, methacrylonitrile, acrylamide, vinyl acetate, acrylic esters, and methacrylic esters, can also be used. Furthermore, in order to more fully carry out the present invention, it is preferable to introduce oxygen into the reaction system or to incorporate a known polymerization inhibitor such as hydroquinone, methoquinone, or phenothiazine.

In the production method of the present invention, the graft copolymer is obtained by copolymerizing the macromonomer (I) with one or more polymerizable monomers (II). Polymerizable monomer (n
) can be used without particular restriction as long as it can be copolymerized with the macromonomer (I). For example, the polymerizable monomer (a) used in the production of the polymer matrix can be used as it is, and (meth)
Polymerizable monomers containing free carboxyl groups such as acrylic acid, crotonic acid, itaconic acid, maleic acid or half esters thereof can also be used. For copolymerization, known polymerization methods such as solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization can be employed, but some methods that take advantage of the ease of polymerization operation and the characteristics of graft copolymers can be used. Considering the various uses, it is most advantageous to rely on the solution polymerization method. It goes without saying that conventional additives such as chain transfer agents can be added during copolymerization.

<Effects of the Invention> According to the production method of the present invention, a simple operation of simply copolymerizing the macromonomer (I) and the polymerizable monomer (II) is performed, and thermal adhesion and grafting efficiency are achieved. It is possible to obtain a graft copolymer with a high By appropriately selecting the composition and amount of the macromonomer (I) to form the graft chain and the polymerizable monomer (II) to form the main chain, a tailor-mate graft copolymer can be prepared according to the purpose of use. It is possible to manufacture it at will. Therefore, the graft copolymer obtained by the production method of the present invention can be used in a wide range of applications, such as coating agents, adhesives, fiber treatment agents, surface treatment agents, and surfactants.

<Examples> Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to the following Examples. Incidentally, parts and parts in the examples mean parts by weight and % by weight, respectively.

Reference Example 1 Toluene 97.5 was added to a four-loaf flask equipped with a stirrer, reflux condenser, dropping funnel, thermometer and inert gas inlet tube.
The temperature was raised to 80° C. while blowing nitrogen gas. Methyl methacrylate 1 prepared in advance
A mixture of 0.00 parts of thioglycolic acid, 1 part of thioglycolic acid, and 0.3 parts of azobisisobutyronitrile (hereinafter referred to as AIBN) was added dropwise through the dropping funnel over a period of 3 hours. After the dropwise addition was completed, 2 parts of AIBNo dissolved in 4 parts of toluene were added, and the reaction was further carried out for 3 hours to complete the polymerization, thereby obtaining a 50% toluene solution of the polymer (I) having a terminal carboxyl group. The acid value of this polymer (I) is 0.110 mm/i
'/g.

Next, 203 parts of a 50% toluene solution of the polymer (I) obtained by the above reaction was charged into a similar four-bottle flask.
After raising the temperature to 0°C, 26.9 parts of a 5.7% toluene solution of monoisocyanate [“Additive TI” manufactured by Sumitomo Chemical Co., Ltd.] was added, and further 2-(I-aziridinyl)ethyl methacrylate [“Chemitite MZ”] was added. -11'' manufactured by Nippon Shokubai Kagaku Kogyo ■] was added to 27.1 parts of toluene solution of Section 6.4 and reacted at 70°C for 5 hours to form the macromonomer (I).
A solution of was obtained. The reaction rate determined by tracking the acid value in this reaction was 98%.

Reference Example 2 In Reference Example 1, a self-condensate of 12-hydroxystearic acid (degree of polymerization: 30, hereinafter referred to as polymer (2)) was used instead of polymer (I), and toluene was used as the solvent. A solution of macromonomer (2) was obtained by repeating the same operation as in Reference Example 1, except that n-hexane was used in all cases. In this reaction, the reaction rate determined in the same manner as in Reference Example 1 was 96%.

Reference Example 3 In Reference Example 1, 50 parts of methyl methacrylate was used instead of 100 parts of methyl methacrylate as a polymerizable monomer.
and perfluorooctylethyl acrylate [“FA
Polymer (3) was prepared by repeating the same operation as in Reference Example 1, except that methyl ethyl ketone was used instead of toluene as a solvent. % methyl ethyl ketone solution was obtained, and the same operation as in Reference Example 1 was repeated to obtain the macromonomer (
A solution of 3) was obtained. In this reaction, the reaction rate determined in the same manner as in Reference Example 1 was 98%.

Comparative Reference Example 1 In a flask similar to that used in Reference Example 1, 203 parts of a 50% toluene solution of the polymer (I) obtained in Reference Example 1, 1 part of triethylbenzylammonium chloride as a reaction catalyst, and a polymerization inhibitor were added. After adding 0.05 part of methoquinone as an ingredient and raising the temperature to 110°C, 56.1 parts of a 2.8% toluene solution of glycidyl methacrylate was added and heated to 110°C.
The mixture was reacted for 4 hours to obtain a solution of comparative macromonomer (I). In this reaction, the reaction rate determined in the same manner as in Reference Example 1 was 34%, and no improvement in the reaction rate was observed even if the reaction time was longer than this.

Comparative Reference Examples 2 to 3 In Comparative Reference Example 1, the polymer (I) obtained in Reference Example 2 was used instead of the 50% toluene solution of Polymer (I).
A comparative macromonomer was obtained by repeating the same operation as in Comparative Reference Example 1, except that 50% n-hexane solution of 2) and 50% methyl ethyl ketone solution of polymer (3) obtained in Reference Example 3 were used. (2) and comparative macromonomer (
A solution of 3) was obtained. In this reaction, the reaction rates determined in the same manner as in Reference Example 1 were 34% and 35%, respectively.

The same operation was repeated except that 1 part of 2-mer-7-recaptoethanol was used in the raft of 1 part of thioglycolic acid used in the production of polymer (I) in Reference Example 1 to obtain a product having a terminal hydroxyl group. A 50% toluene solution of the polymer was obtained.

The hydroxyl value of this polymer was 0.110 meq/y.

Next, a 50% toluene solution of the polymer having terminal hydroxyl groups obtained by the above reaction was placed in a four-bottle flask.
0.05 part of dibutyltin dilaurate and 1.3 parts of 2,4-tolylene diisocyanate were added and reacted at 80°C for 1.5 hours. Next, 0.97 parts of hydroxyethyl methacrylate was added and the reaction was further carried out at 110°C for 1 hour to obtain a comparative macromonomer (
A solution of 4) was obtained. In this reaction, the reaction rate determined by tracking the hydroxyl value was 55%, and no improvement in the reaction rate was observed even if the reaction time was longer than this.

Example 1 In a four-bottle flask equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer, and an inert gas inlet tube, a solution of 40 ml of the macromonomer (I) obtained in Reference Example 1 in toluene was added.
Prepare part OO and 40 parts of n-butyl acrylate,
The temperature was raised to 80°C. From the dropping funnel, AIBNo dissolved in 6 parts toluene, A I BN' oi dissolved in 3 parts
2 parts were further added, and the mixture was aged for 3 hours and then cooled to obtain a colorless and transparent graft polymer fl'lo) toluene solution. This was applied onto a glass plate using a bar coater, and the toluene was evaporated using a hot air dryer to give a thickness of 0.045.
A coating film of mm was obtained. The film obtained by peeling this coating from the glass plate was free of turbidity, pliable, and strong.

Comparative Example 1 In Example 1, the same procedure as in Example 1' was repeated except that the solution of the comparative macromonomer (I) obtained in Comparative Reference Example 1 was used instead of the solution of the macromonomer (I). A toluene solution of comparative graft copolymer (I) was obtained. This solution was cloudy and separated into two layers upon standing.

This was shaken and coated on a glass plate using a bar coater, and the toluene was evaporated using a hot air dryer to obtain a coating film with a thickness of 0.045 mm. The film obtained by peeling this coating from the glass plate was cloudy and weak.

Comparative Example 2 In Example 1, the procedure was exactly the same as in Example 1, except that the solution of the comparative macromonomer (4) obtained in Comparative Reference Example 4 was used instead of the solution of the macromonomer (I). The mixture was returned to obtain a toluene solution of comparative graft copolymer (2). This solution was cloudy and separated into two layers upon standing. In addition, the film obtained in the same manner as Comparative Example 1 was cloudy;
It was weak.

Example 2 and Comparative Example 3 In Example 1, the solution of macromonomer (2) obtained in Reference Example 2 and the comparative macromonomer (2) obtained in Comparative Reference Example 2 were used instead of the solution of macromonomer (I), respectively.
), the same procedure as in Example 1 was repeated except that n-hexane was used instead of toluene and methyl methacrylate was used instead of n-butyl acrylate to prepare a graft copolymer. (2) and a comparative graft copolymer (3) solutions were obtained. Graft copolymer (2)
The solution maintained a stable dispersion state, and the film obtained from this solution in the same manner as in Example 1 was free of turbidity, pliable, and strong. On the other hand, in the solution of the comparative graft copolymer (3), a solid content insoluble in n-hexane was produced and sedimented when left standing.

Example 3 and Comparative Example 4 In Example 1, the solution of macromonomer (3) obtained in Reference Example 3 and the comparative macromonomer (3) obtained in Comparative Reference Example 3 were used instead of the solution of macromonomer (I), respectively.
), the same operation as in Example 1 was repeated except that methyl methacrylate was used instead of n-butyl acrylate and methyl ethyl ketone was used instead of toluene to obtain a fluorine-containing polymer component in the graft chain. Graft copolymer (3) and comparative graft copolymer (
A solution of 4) (hereinafter, both are collectively referred to as a fluorine-based graft copolymer) was obtained. Graft copolymer (3)
The solution is a stable dispersion state that exhibits fluorescence, whereas
The solution of comparative graft copolymer (4) was strongly cloudy and tended to separate if left standing. A solution of these fluorine-based graft copolymers was added to an acrylic paint resin [“Arocet 5220” manufactured by Nippon Shokubai Chemical Co., Ltd.] at a non-volatile content ratio of 0.
．． A resin composition solution was prepared by blending the resin compositions in amounts of 1%, 0.3%, and 0.5%. A solution of these resin compositions was applied onto a glass plate using a bar coater and dried at room temperature for one day. The contact angle of the resulting coating film with respect to water and liquid paraffin was measured, and the results were used as reference data. The results are shown in Table 1 together with the results for the acrylic paint resin itself.

Table 1 1) Contact angle: The contact angle of water or liquid paraffin to the coating surface was measured using a goniometer complete contact angle measuring device.

As is clear from the results in Table 1, the coating film obtained from the resin composition blended with the graft copolymer (3) obtained by the production method of the present invention exhibited excellent water and oil repellency.

Claims (1)

[Claims] 1. The polymer (A) having a terminal carboxyl group contains an unsaturated basic aziridine compound (B) and at least one member selected from the group consisting of monoisocyanates, ketenes, and ketene dimers. A graft copolymer characterized by copolymerizing a macromonomer (I) obtained by reacting a compound (C) with a polymerizable monomer (II) having copolymerizability with the macromonomer (I). Method for producing polymers.