JPH01292014A - Graft copolymer useful as a resin additive and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title copolymer outstanding in heat resistance, causing no deterioration of a resin when melt-kneaded therewith, by copolymerization between a polycaprolactone derivative of vinyl polymerization nature containing specific non-reactive terminal group and a specific vinyl monomer. CONSTITUTION:A copolymerization is carried out, in the presence of a polymerization initiator, between (A) 80-20wt.% of a polycaprolactone derivative of vinyl polymerization nature containing non-reactive terminal group of a formula I [R<1> is H or CH3; R<2> is aliphatic or alicyclic hydrocarbon, or -(CmH2mO)rR<5> (R<5> is 1-18C-hydrocarbon; m is 2; r is 1-5); n is 6-90], (B) 10-80wt.% of a vinyl monomer of formula II (R<3> is the same as R<1>; R<4> is CH3 or C2H5), and (C) 0-40wt.% of another vinyl monomer, thus obtaining the objective copolymer constituted mainly of 80-20wt.% of structural unit of formula III and 10-80wt.% of structural unit of formula IV with a total of the units III and IV accounting for >=60wt.% of the whole polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a graft copolymer useful as a resin additive and a method for producing the same.

Graft copolymers can exhibit properties that cannot be obtained with other polymers, such as homopolymers and random copolymers, so they are used in a variety of applications.The present invention can be used as a resin additive. The present invention relates to useful graft copolymers, particularly structurally controlled graft copolymers having polycaprolactone chains capped with non-reactive end groups in the branches, and methods for their preparation.

<Prior art and its problems> Conventionally, in the production of graft copolymers, a method has been adopted in which a synthetic polymer or a natural polymer is reacted with a monomer to form a graft. This type of conventional method has the advantage of being able to use existing polymers, but has the problem that many of the raw material polymers are difficult to dissolve in solvents, making the reaction difficult in many cases. Also, in this type of conventional method, 1
In essence, it is difficult to control the number or length of graft chains, and the grafting rate is low, making it difficult to obtain a graft copolymer with the desired structure and physical properties. .

Recently, a method of producing a Dalat copolymer using a monomer (hereinafter referred to as macromonomer) having a higher molecular weight than conventional monomers has been studied. In this method, a macromonomer with a controlled molecular weight and structure is synthesized in advance, and then the macromonomer is copolymerized with other vinyl monomers and incorporated into a polymer chain to create a graft copolymer. This is a method of manufacturing.

As an example of a graft copolymer using such a macromonomer, a graft copolymer having a polyester chain in a branch portion has been disclosed (Japanese Patent Publication No. 44024/1986; Japanese Patent Publication No. 60/99158).

According to these, the polycondensation reaction of a dibasic acid and a glycol, the ring-opening polymerization of polycaprolactone, or the ring-opening polymerization of an acid anhydride and an alkylene oxide are exemplified as methods for obtaining a polyester chain, which is a branch part. There is. The two terminal groups of these polyester chains are originally hydroxyl groups or carboxylic acid groups, and macromonomers are obtained by reacting various reactive agents with one of these terminal groups and introducing a vinyl group. The macromonomer is copolymerized with other vinyl monomers to produce a graft copolymer.

However, this conventional method has the following problems. Mac9 whose terminal group is a hydroxyl group or carboxylic acid group
Since a monomer is used, a gel-like substance with an unknown structure is likely to be produced, and it is difficult to produce a graft copolymer with a controlled structure.2) In particular, when a macromonomer is obtained by the method exemplified above, The by-product of bifunctional macromonomers with vinyl groups introduced at both ends is unavoidable, and it is extremely difficult to remove these bifunctional macromonomers by purification. The macromonomer is involved in the copolymerization reaction, and as a result, a three-dimensional gel-like material is significantly produced.

Graft copolymers produced by such known methods have various drawbacks when used as resin additives, which is the object of the present invention. That is, graft copolymers produced by known methods do not have good dispersibility in resins.
When melt-kneaded into condensation polymers such as polycarbonate resins and polyamide resins, the resin becomes colored and its viscosity decreases due to the action of the aforementioned terminal groups such as hydroxyl groups and carboxylic acid groups, which clearly deteriorates the resin. It is.

<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention provides a new graft copolymer and a method for producing the same that solves the conventional problems as described above.

However, in view of the above circumstances, the present inventors have developed a material that has good heat resistance and does not cause deterioration of resins such as polyester resins, polyamide resins, and polycarbonate resins when melt-kneaded with these resins. As a result of intensive research to obtain a graft copolymer, the core portion has polycaprolactone chains blocked with non-reactive end groups. The present invention was achieved by discovering that a graft copolymer with a regulated structure is suitable and that the graft copolymer can be industrially advantageously produced.

In other words, the present invention provides a structural unit work and a structural unit shown by the following formulas, respectively.
, the constituent unit work is 80 to 20% by weight of the whole, the constituent unit II is 10 to 80% by weight of the whole, and the constituent unit work + constituent unit II is 60% by weight or more of the whole. A graft copolymer having the following principle, and a vinyl polymerizable polycaprolactone derivative represented by the following general formula A having a non-reactive end group in an amount of 8θ to 20% by weight.
, 10 to 80 vinyl monomers represented by the following general formula B
% by weight and other vinyl monomers at a ratio of 0 to 40% by weight in the presence of a polymerization initiator.

I υ J General formula B: GH2-C-GOOR4 [R1, R3, H or C throughout each formula) 13R2; carbon number 1-18
aliphatic or alicyclic hydrocarbon group or +CaH2*0
) rR5 (here, R5: a hydrocarbon group having 1 to 18 carbon atoms, m: 2 or 3, r: 1 to 5) R4; CH3 or C2H3 n; 6 to 901 structural unit in the graft copolymer of the present invention The vinyl polymerizable polycaprolactone derivative represented by the general formula A (hereinafter referred to as macromonomer A), which is the raw material for I, undergoes a ring-opening addition reaction between a -hydric alcohol and ε-caprolactone, followed by an α,β-union reaction. It can be obtained by esterification or transesterification using saturated monocarboxylic acids or ester-forming derivatives thereof. The ring-opening addition reaction between the -hydric alcohol and ε-caprolactone can be carried out in the presence of a catalyst such as tetrabutoxythi, thanate or dibutyltin dilaurate.

Specific examples of the above-mentioned -hydric alcohols include primary alcohols.

1) Direct aliphatic alcohols; methanol, ethanol, n-butanol, n-octanol, octadecyl alcohol, etc. 2) Branched aliphatic alcohols; isopropanol, 2-ethylhexanol, isotridecyl alcohol, etc. 3) Other fats Group or alicyclic alcohol: benzyl alcohol, cyclohexanol, etc. 0 or more 1) to 3)
Fulkylene oxide adducts of alcohols; methyl cellosolve, butyl cellosolve, ethyl carbitol,
butyl carbitol, etc. 5) Fullylene oxide adducts of phenols substituted with phenol or hydrocarbon groups; ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, polyoxyethylene (5 mol) nonylphenyl ether, ethoxylated-p -phenylphenol, ethoxylated-3,6-sibutylphenol, etc.

In the fullylene oxide adducts 4) and 5), the alkylene oxide includes ethylene oxide or propylene oxide, and the number of moles of these alkylene oxides added is 1 to 5 moles.

Further, specific examples of the α,β-unsaturated monocarboxylic acids or their ester-forming derivatives include acrylic acid, methacrylic acid, acrylic acid chloride, methacrylic acid chloride, methyl acrylate, methyl methacrylate, etc. .

The esterification reaction or transesterification reaction using these can be carried out in the presence of a radical polymerization inhibitor and an acidic catalyst such as sulfuric acid or p-toluenesulfonic acid.

The preferable molecular weight range of the macromonomer A thus obtained is 800 to 10,000, and the more preferable molecular weight range is 1,000 to 8,000.

Specific examples of the vinyl monomer represented by general formula B (hereinafter referred to as vinyl monomer B), which is a raw material for structural unit II in the graft copolymer of the present invention, include methyl methacrylate, methyl acrylate, , ethyl methacrylate, and ethyl acrylate.These can be used alone or in combination of two or more.

In the graft copolymer of the present invention, the structural unit I and the structural middle ■! A specific example of a vinyl monomer (hereinafter referred to as vinyl monomer C) which may contain other structural units and is a raw material for such other structural units is acrylonitrile.

Butyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methoxyethyl methacrylate, vinyl acetate, methyl vinyl ether,
Examples include vinyl monomers having no hydroxyl group or carboxylic acid group, such as phenyl vinyl ether, and among them, acrylonitrile is advantageous.

The content ratio of each of the intermediate constituents forming the gelafoot copolymer of the present invention is: structural unit units / structural units / other structural units =
The range is 80-20/10-8010-40 (each % by weight), preferably 70-30/30-7010-2
5 (each weight %). Outside the above range,
The function of the produced graft copolymer, such as dispersibility, becomes insufficient.

As described above, the graft copolymer of the present invention is synthesized using macromonomer A, vinyl monomer B, and vinyl monomer C if necessary. For this synthesis, ordinary methods such as solution polymerization, emulsion polymerization, or suspension polymerization can be applied.The molecular weight of the graft copolymer of the present invention to be synthesized is:
It is preferably 5000 or more, and toooo to 15
More preferably, the range is 0,000.

The graft copolymer of the present invention is extremely useful as a resin additive. For example, when two or more synthetic resins that are incompatible with each other are mixed, a dispersing agent that can form a stable polymer blend V. It is useful as

Hereinafter, the configuration and effects of the present invention will be explained in more detail through examples, but the present invention is not limited to these examples.

<Examples, etc.> Graft copolymers of each example and each comparative example were synthesized as illustrated below, and the results are shown in Tables 1 and 2 below.
They are summarized in the table.

- Example 1 - Synthesis of macromonomer A-1 50 g of ethyl cellosolve and tetrabutyl titanate I
After charging 150 g into a flask and purging the inside with nitrogen,
Heated to ℃. And (-caprolactone 2200
After adding g dropwise over 1 hour, the reaction was continued at 150°C for 2 hours to obtain a caprolactone adduct (hydroxyl value: 14.4).

Next, 250 g of the caprolactone adduct obtained above, 8.0 g of methacrylic acid, 250 g of toluene, and 0.0 g of sulfuric acid were added.
Charge 5g and 0.1g of hydroquinone into a flask,
The mixture was heated under reflux for 8 hours to carry out an esterification reaction. After the contents were cooled to 60° C., the sulfuric acid was neutralized with sodium hydrogen carbonate, and the salt produced by the neutralization was dissolved by adding wood. The aqueous layer and toluene layer are separated, and the toluene layer is dehydrated and solvent removed under reduced pressure to obtain the macromonomer.
A-1 (acid value 0.4, hydroxyl value 1.1, molecular weight 397
0) was obtained (molecular weight is a polystyrene equivalent value determined by GPC method, the same applies hereinafter).

...Synthesis of Graft Copolymer A-1 30 g of the above macromonomer A-1, 30 g of methyl methacrylate, and 90 g of toluene were placed in a flask, and the inside was purged with nitrogen, followed by heating. When the internal temperature reached 70°C, 10 ml of a lO% toluene solution of azobisisobutyronitrile was gradually added and the reaction was carried out for 2 hours. to precipitate the copolymer. After washing the precipitated white precipitate three times with methanol room+,
The graft copolymer A-1 was synthesized by vacuum drying at 70°C. The graft copolymer A-1 had a methyl methacrylate content of 43ffiM% and a molecular weight of 23,000.

・Example 2 ・・Synthesis of macromonomer A-2 By the same operation as in Example 1, n-octatool 13
0 g was reacted with 2052 g of ε-caprolactone to obtain a caprolactone adduct (hydroxyl value 26, l).Next, the caprolactone adduct was reacted with methacrylic acid to form macro-7mer-2 (acid value 0.6). .Hydroxyl value 1.0
, molecular weight 2220) was obtained.

...Synthesis of graft copolymer A-2 By the same operation as in Example 1, macromonomer A-2
and 30 g of methyl methacrylate,
Graft copolymer A-2 was synthesized. Graft copolymer A-2 had a methyl methacrylate content of 48% by weight and a molecular weight of 45,000. Example 3 Synthesis of macromonomer A-3 By the same procedure as in Example 1, 46 g of phenylcarpitol was added. 2090 g of 6-caprolactone was reacted to obtain a caprolactone adduct (hydroxyl value 8.9).Next, the caprolactone adduct dimethacrylic acid was reacted to obtain macromonomer A-3 (acid value 0.3, hydroxyl value 0.7
, molecular weight 6400).

...Synthesis of graft copolymer A-3 By the same operation as in Example 1, macromonomer A-3
and 30 g of methyl methacrylate,
Graft copolymer A-3 was synthesized. Graft copolymer A-3 had a methyl methacrylate content of 44% by weight and a molecular weight of 29,000. Example 4 Synthesis of graft copolymer A-4 Macromonomer A was synthesized by the same procedure as in Example 1. -1
, 25 g of methyl methacrylate, and 15 g of acrylonitrile were reacted to synthesize graft copolymer A-4. Graft copolymer A-4 had a methyl methacrylate content of 36% by weight, an acrylonitrile content of 21% by weight, and a molecular weight of 30,000.

- Example 5 - Synthesis of macromonomer A-5 By the same operation as in Example 1, 1330 g of (-cabrolactone) was reacted with 90 g of phenol ethylene oxide (4 mol) adduct, and the caprolactone adduct (hydroxyl value 13, 3 ) was obtained.Next, the caprotictone adduct was reacted with methacrylic acid to obtain macromonomer A-5.
(Acid value 0.5, hydroxyl value 0.6, molecular weight 4300) was obtained.

...Synthesis of graft copolymer A-5 Macromonomer A-5 was prepared in the same manner as in Example 1.
and 30 g of methyl methacrylate,
Graft copolymer A-5 was synthesized. The graft copolymer A-5 had a methyl methacrylate content of 45% by weight and a molecular weight of about 40,000. Comparative Example 1 Synthesis of the graft copolymer R-1 Macromonomer A-5 was synthesized by the same procedure as in Example 1. -1
and 51 g of methyl methacrylate,
A graft copolymer R-1 was synthesized. The graft copolymer R-1 had a methyl methacrylate content of 84% and a molecular weight of 33,000.
Then, the caprolactone adduct was reacted with methacrylic acid to obtain macromonomer R-2. Macromonomer R-2 has a molecular weight of 500 and an average number of added moles of ε-caprolactone of 3.
Met.

... Synthesis of graft copolymer R-2 By the same operation as in Example 1, macromonomer R-2
and 30 g of methyl methacrylate,
Graft copolymer R-2 was synthesized. Graft copolymer R-2 had a methyl methacrylate content of 47% by weight and a molecular weight of 18,000.

φ Comparative Example 3 Synthesis of Macromonomer R-3 25 g of hydroxyethyl methacrylate, Ig of tetrabutyl titanate and 0.2 g of hydroquinone were placed in a flask, the inside of the flask was purged with nitrogen, and then heated to 150°C. Then, after dropping 750 g of ε-caprolactone over 1 hour, the reaction was continued at 150°C for 2 hours, and macromonomer R-3 (hydroxyl value 15.2, molecular weight 3700
) was obtained.

... Synthesis of Graft Copolymer R-3 By the same operation as in Example 1, 90 g of toluene was used as a solvent, and 30 g of macromonomer R-3 and 30 g of methyl methacrylate were reacted. At the end of the reaction,
The reaction solution in which formation of a gel-like substance was observed was cooled to room temperature, and poured into 500 ml of methanol to precipitate a copolymer.

The precipitated white precipitate was washed three times with methanol 1001 and then vacuum dried at 70°C to synthesize graft copolymer R-3. Graft copolymer R-3 swelled in toluene, but was insoluble, so its molecular weight could not be measured.

- Comparative Example 4 - Synthesis of Macromonomer R-4 148 g of phthalic anhydride, 100 g of phosphoric anhydride, and 130 g of ethylene glycol were charged in a flask.
The reaction was carried out at ℃ for 2 hours. Then, the reaction product was heated to 200° C. to perform condensation to obtain a polyester (acid value: 17, hydroxyl value: 20).

Next, the above polyester was cooled to 160°C, 8 g of maleic anhydride was added thereto, and the mixture was reacted for 1 hour to form a macromonomer R-4 (having carboxyl groups at both ends).
An acid value of 36 and an average molecular weight of 3030) were obtained.

...Synthesis of graft copolymer R-4 100 g of the above macromonomer R-4, 7 g of styrene
0 g and 300 g of xylene were charged into a flask and dissolved. This was heated to 80° C., 1 g of benzoyl peroxide was added while nitrogen was introduced, and the reaction was continued for 6 hours. Then, the contents were subjected to the same operations as in Example 1 to synthesize graft copolymer R-4. When graft copolymer R-4 was dissolved in toluene, insoluble matter was found in a portion thereof, so the molecular weight of the graft copolymer R-4 was not measured.

Table 1 Table 2 Evaluation examples as resin additives 100g of polycarbonate for injection molding, 30g of nylon-6 for injection molding, 3g of graft copolymers of each example or comparative example, small size for experiment Load it into the mixer, 2
The mixture was kneaded at 50°C for 4 minutes.

Next, a sheet with a thickness of 2 mm was molded using a hot press machine. In addition, the same operation was performed on a sheet without the addition of the graft copolymer to form a sheet (blank), and the sheet properties and dispersion state were evaluated as shown below, and the results are shown in Table 3. It was shown to.

... Evaluation of sheet properties The presence or absence of pores in the sheet and the degree of coloration of the sheet were observed with the naked eye. In addition, the degree of difficulty in breaking the sheet was examined by bending the sheet with both hands, and the strength was evaluated.

...Evaluation of the dispersion state The sheet was immersed in chloroform for 5 minutes at room temperature, and the surface was etched. After the etching process, the surface state of the sheet was observed using a scanning electron II microscope, and the homogeneity of the dispersion state and the shape and diameter of the dispersed particles were examined. In this case, homogeneity was evaluated as follows.

In other words, the dispersion state is greatly improved compared to the blank,
Those in which the particles were homogeneously dispersed in a fine spherical shape were considered good, and those with no difference from the blank were judged to be defective.

Table 3 <Effects of the Invention> As is clear from the results in Table 6, the present invention described above has good heat resistance, does not particularly cause deterioration of the resin, and has different compatibility with each other. It has the effect of exhibiting excellent dispersion performance for the resins when two or more resins are kneaded.

Patent applicant: Takemoto Yushi Co., Ltd. Agent: Hiroshi Yama, Patent Attorney

Claims (1)

[Claims] 1. Contains a structural unit I and a structural unit II each represented by the following formula, with the structural unit I accounting for 80 to 20% of the total weight, and the structural unit II accounting for 10 to 80% of the total weight. % by weight, and a graft copolymer in which structural unit I + structural unit II accounts for 60% by weight or more of the total weight. Constituent unit I: ▲ Contains mathematical formulas, chemical formulas, tables, etc.▼ Constituent unit II: ▲ Contains mathematical formulas, chemical formulas, tables, etc.▼ [However, R^1, R^3; H or CH_3 R^2; Number of carbons 1~ 18 aliphatic or alicyclic hydrocarbon groups or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ {Here, R^5; Hydrocarbon group having 1 to 18 carbon atoms, m;
2 or 3, r; 1-5} R^4; CH_3 or C_2H_5 n; 6-90] 2. The graft copolymer according to claim 1, wherein the structural unit I is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Combined. 3. The graft copolymer according to claim 1 or 2, wherein the structural unit II is: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 4. Structural unit I is 80 to 20% by weight of the whole, structural unit II is 20 to 80% by weight of the whole, and structural unit I + structural unit II is 100% by weight of the whole. The graft copolymer described. 5. The structural unit III represented by the following formula is 0 to 40 of the total
The graft copolymer according to claim 1, 2 or 3, containing % by weight. Structural unit III: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ 6. 80 to 20% by weight of a vinyl polymerizable polycaprolactone derivative represented by the following general formula A having a non-reactive end group, and the following general formula B. 10 to 10 of the vinyl monomers shown
80% by weight and 0-40% by weight of other vinyl monomers
A method for producing a graft copolymer, comprising copolymerizing in the presence of a polymerization initiator at a ratio of . General formula A: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula B: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, R^1, R^3; H or CH_3 R^2; Number of carbons 1 ~ 18 aliphatic or alicyclic hydrocarbon groups or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ {Here, R^5; Hydrocarbon group having 1 to 18 carbon atoms, m;
2 or 3, r; 1 to 5} R^4; CH_3 or C_2H_5 n; 6 to 90] 7. The graft copolymer according to claim 6, wherein the general formula A is Method of manufacturing coalescence. 8. The method for producing a graft copolymer according to claim 6 or 7, wherein general formula B is methyl methacrylate. 9. 80 to 20% by weight of the vinyl polymerizable polycaprolactone derivative represented by general formula A, 20 to 80% by weight of the vinyl monomer represented by general formula B, and the total of both is 1.
9. The method for producing a graft copolymer according to claim 8, wherein the copolymerization is carried out at a ratio of 0.00% by weight. 10. The method for producing a graft copolymer according to claim 6, 7 or 8, wherein 0 to 40% by weight of acrylonitrile is copolymerized as the other vinyl monomer.