JP2701151B2 - Reactive graft copolymers useful as resin additives - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a reactive graft copolymer useful as a resin additive.

The graft copolymer can exhibit properties that cannot be obtained with other polymers, such as a homopolymer and a random copolymer, and is therefore used for various applications. The present invention relates to a graft copolymer having reactivity useful as a resin additive, and more particularly to a structure-regulated polymer having a polycaprolactone graft chain blocked by an epoxy group and a non-reactive terminal group in a molecule. And a graft copolymer.

<Prior art and its problems> Conventionally, graft copolymers obtained by reacting a monomer with a synthetic polymer or a natural polymer are generally used as a graft copolymer. However, such conventional general graft copolymers have the advantage that existing polymer compounds can be used, but on the other hand, many of the raw material polymer compounds are difficult to dissolve in a solvent, and thus the reaction is sometimes difficult. It is difficult to control the number or length of the graft chains due to the large number, and the grafting ratio is low, so that there are only limited structures and physical properties. There is a disadvantage that there is no one having.

Therefore, recently, a graft copolymer using a relatively high molecular weight monomer (hereinafter, referred to as a macromonomer) as a raw material has been studied. This graft copolymer is obtained by synthesizing a macromonomer having a controlled molecular weight and structure in advance, and copolymerizing the macromonomer with another vinyl monomer to incorporate the macromonomer into a polymer chain.

As a graft copolymer using such a macromonomer, a graft copolymer having a polyester chain at a branch portion has been proposed (Japanese Patent Publication No. Sho 54-44024, Japanese Patent Application Laid-Open No. 60-99158). These graft copolymers are obtained by first obtaining a polyester chain corresponding to a branch portion by polycondensation of a dibasic acid and glycol, ring-opening polymerization of polycaprolactone, or ring-opening polymerization of acid anhydride and alkylene oxide. Since the two terminal groups of these polyester chains are both hydroxyl groups or carboxylic acid groups, a macro group is obtained by reacting one of these terminal groups with various reactive agents to introduce a vinyl group. A monomer was synthesized, and the macromonomer was copolymerized with another vinyl monomer.

However, the conventional graft copolymer obtained by the above method has the following problems. 1) Since a macromonomer whose terminal group is a hydroxyl group or a carboxylic acid group is used, a gel having an unknown structure is easily generated, and it is difficult to regulate the structure. 2) When synthesizing a macromonomer,
Since by-products of bifunctional macromonomers having vinyl groups introduced at both ends are inevitable, and these bifunctional macromonomers are extremely difficult to remove by purification,
Eventually, the bifunctional macromonomer is involved in the copolymerization reaction, and as a result, a three-dimensional gel is remarkably formed and mixed.

The graft copolymer having the above-mentioned problems has various disadvantages when used as a resin additive which is the object of the present invention. That is, in the conventional graft copolymer,
Good dispersibility in the resin is not obtained, especially when the graft copolymer is melt-kneaded into a condensation polymer such as polyester resin, polycarbonate resin, polyamide resin, etc. Due to the action of the group, the coloring of the resin and the decrease in the viscosity occur, which obviously deteriorates the resin.

<Problems to be Solved by the Invention, Means for Solving the Problems> The present invention provides a graft copolymer having reactivity useful as a resin additive that solves the above-mentioned conventional problems.

In view of the above circumstances, the present inventors have found that the heat resistance is good, the resin has good dispersibility, and the resin is melt-kneaded with a resin such as a polyester resin, a polyamide resin, and a polycarbonate resin. As a result of intensive research to obtain a graft copolymer that does not cause deterioration of these resins, the structure of the polymer is restricted due to having a polycaprolactone graft chain blocked with an epoxy group and a non-reactive terminal group in the molecule. The graft copolymer was found to be correct and suitable.

That is, the present invention relates to a graft copolymer having reactivity useful as a resin additive, and has a structural unit I, a structural unit II and a structural unit III represented by the following formulas, respectively.
Wherein the structural unit I is 80 to 20% by weight of the whole, the structural unit II is 10 to 79% by weight of the whole, and the structural unit III is 1 to 2% by weight of the whole.
The present invention relates to a graft copolymer having 0% by weight and a molecular weight of 10,000 to 150,000.

[However, R ¹ , R ³ , R ⁵ ; H or CH ₃ R ² ; an aliphatic or alicyclic hydrocarbon group having 1 to 18 carbon atoms or C _m H _2m O) _r R ⁶ R wherein R ⁶ A hydrocarbon group having 1 to 18 carbon atoms, m; 2 or 3,
r; 1 to 5｝ R ⁴ ; C ₆ H ₅ , COOCH ₃ or COOC ₂ H ₅ X; COO or CH _{2 On} ; 6 to 90] In the graft copolymer of the present invention, it is a raw material of the structural unit I. Is a vinyl polymerizable polycaprolactone derivative represented by the following general formula A (hereinafter referred to as macromonomer A).

[However, R ¹ , R ² , and n are the same as those in the above-mentioned structural unit I] The macromonomer A is a ring-opening addition reaction between a monohydric alcohol and ε-caprolactone, and is followed by an α, β-unsaturated monoester. It is obtained by an esterification reaction or a transesterification reaction using a carboxylic acid or an ester-forming derivative thereof. The ring-opening addition reaction between a monohydric alcohol and ε-caprolactone can be performed in the presence of a catalyst such as tetrabutoxytitanate or dibutyltin dilaurate.

Specific examples of the above monohydric alcohol include the following.

1) linear aliphatic alcohols; methanol, ethanol,
n-Butanol, n-octanol, octadecyl alcohol, etc. 2) Branched aliphatic alcohols; isopropanol, 2-ethylhexanol, isotridecyl alcohol, etc. 3) Other aliphatic or alicyclic alcohols; benzyl alcohol, cyclohexanol, etc. 4) Alkylene oxide adducts of alcohols 1) to 3) above; methyl cellosolve, butyl cellosolve,
Ethyl carbitol, butyl carbitol, etc. 5) Alkylene oxide adduct of phenol or phenol substituted with a hydrocarbon group; ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, polyoxyethylene (5 mol) nonyl phenyl ether, ethoxy In the alkylene oxide adducts of 4) and 5), ethylene oxide or propylene oxide is mentioned as the alkylene oxide, and the number of moles of these alkylene oxides is added. Is 1 to 5 mol.

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 and the like. Can be

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 preferred molecular weight of the macromonomer A thus obtained is in the range of 800 to 10,000, more preferably 1000 to 8000.

In the graft copolymer of the present invention, the raw material of the structural unit II is a vinyl monomer represented by the following general formula B (hereinafter, referred to as vinyl monomer B).

[However, R ³ and R ⁴ are the same as in the case of the structural unit II] Specific examples of the vinyl monomer B include styrene, α-methylstyrene, methyl methacrylate, methyl acrylate, ethyl methacrylate, and ethyl acrylate. . These can be used alone or in a mixture.

In the graft copolymer of the present invention, the raw material of the structural unit III is a vinyl monomer represented by the following general formula C (hereinafter, referred to as vinyl monomer C).

[However, R ⁵ and X are the same as those in the case of the structural unit III.] Specific examples of the vinyl monomer C include glycidyl methacrylate, glycidyl acrylate, and allyl glycidyl ether. These can be used alone or in a mixture.

The ratio of each structural unit forming the graft copolymer of the present invention is as follows: structural unit I / structural unit II / structural unit III = 80 to 20/10
~ 79/1 ~ 20 (% by weight), preferably 69 ~
It is in the range of 30/30 to 69/1 to 15 (% by weight). If the ratio is outside the above range, the performance exhibited by the graft copolymer, for example, the expression of dispersibility becomes insufficient.

As described above, the graft copolymer of the present invention is synthesized using the macromonomer A, the vinyl monomer B, and the vinyl monomer C. In this synthesis, ordinary methods such as solution polymerization, emulsion polymerization and suspension polymerization can be applied. The molecular weight of the graft copolymer of the present invention to be synthesized is 10,000 to 15,000.
The range is 0.

The graft copolymer of the present invention is extremely useful as a resin additive. For example, it is useful as a dispersant that can form a stable polymer blend when two or more synthetic resins that are incompatible with each other are mixed, and in this case, the synthetic resins do not deteriorate. .

Hereinafter, the configuration and effects of the present invention will be more specifically described with reference to examples and the like, but the present invention is not limited to the examples.

<Examples and the like> As exemplified below, graft copolymers of Examples and Comparative Examples were synthesized, and the results are shown in Tables 1 and 2 below.

Example 1 Synthesis of Macromonomer A-1 50 g of ethyl cellosolve and 1 g of tetrabutyl titanate
Was charged into a flask, the inside of which was replaced with nitrogen, and then heated to 150 ° C. After dropping 2200 g of ε-caprolactone 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, 0.5 g of sulfuric acid and 0.1 g of hydroquinone were charged into a flask, and heated under reflux for 8 hours to carry out an esterification reaction. Then, after cooling the content to 60 ° C., the sulfuric acid was neutralized with sodium hydrogen carbonate, and the salt generated by the neutralization was dissolved by adding water. Separate the aqueous layer and the toluene layer, dehydrate the toluene layer under reduced pressure,
The solvent was removed to obtain macromonomer A-1 (acid value: 0.4, hydroxyl value: 1.1, molecular weight: about 3970) (the molecular weight is the value in terms of polystyrene by the GPC method, the same applies hereinafter).

合成 Synthesis of graft copolymer P-1 30 g of the above-mentioned macromonomer A-1, 20 g of methyl methacrylate, 10 g of glycidyl methacrylate and 90 g of toluene were charged in a flask, the inside of which was replaced with nitrogen, and heated. When the internal temperature reached 70 ° C., 50 ml of a 2% toluene solution of azobisisobutyronitrile was gradually added, and the reaction was carried out for 5 hours. Next, the reaction solution was cooled to room temperature, and poured into 500 ml of methanol to precipitate a copolymer. The precipitated white precipitate is methanol 100ml
, And vacuum-dried at 70 ° C to synthesize a graft copolymer P-1. The graft copolymer P-1 is
33% by weight of structural unit II made from methyl methacrylate corresponding to vinyl monomer B, oxygen content of oxirane
The molecular weight was 2.02% by weight and the molecular weight was about 22,000.

Example 2 Synthesis of Graft Copolymer P-2 30 g of macromonomer A-1 obtained in Example 1, 27 g of methyl methacrylate, and 3 g of glycidyl methacrylate
Using the same procedure as in Example 1, a graft copolymer P-2 was synthesized. The graft copolymer P-2 has a content of 41% by weight of the constitutional unit II made of methyl methacrylate corresponding to the vinyl monomer B, and an oxirane oxygen content of 0.54.
% By weight, molecular weight about 27,000.

Example 3 Synthesis of Macromonomer A-2 According to the same operation as in Example 1, n-octanol 13
205 g of ε-caprolactone was reacted with 0 g to obtain a caprolactone adduct (hydroxyl value 26.1). Then, the caprolactone adduct is reacted with methacrylic acid to give a macromonomer A-2 (acid value 0.6, hydroxyl value 1.0, molecular weight about 2220).
I got

合成 Synthesis of graft copolymer P-3 By the same operation as in Example 1, macromonomer A-
2, 30 g of methyl methacrylate, and 3 g of glycidyl methacrylate were reacted to synthesize a graft copolymer P-3. The graft copolymer P-3 is composed of a structural unit II made from methyl methacrylate corresponding to the vinyl monomer B.
Was 47% by weight, oxirane oxygen content was 0.5% by weight, and molecular weight was about 33,000.

Example 4 Synthesis of Macromonomer A-3 In the same manner as in Example 1, 46 g of phenylcarbitol was reacted with 2090 g of ε-caprolactone to obtain a caprolactone adduct (hydroxyl value 8.9). Next, the caprolactone adduct was reacted with methacrylic acid to give a macromonomer A-3 (acid value 0.3, hydroxyl value 0.7, molecular weight of about 640).
0).

合成 Synthesis of graft copolymer P-4 By the same operation as in Example 1, macromonomer A-
30 g of styrene, 20 g of styrene, and glycidyl methacrylate
By reacting 10 g, a graft copolymer P-4 was synthesized. The graft copolymer P-4 had a content of the structural unit II of styrene corresponding to the vinyl monomer B of 35% by weight, an oxirane oxygen content of 2.15% by weight, and a molecular weight of about 35,000.

Example 5 By the same operation as in Example 1, macromonomer A-
30 g of styrene, 27 g of styrene, and allyl glycidyl ether
By reacting 3 g, a graft copolymer P-5 was synthesized. The graft copolymer P-5 had a content of the structural unit II of styrene corresponding to the vinyl monomer B of 42% by weight, an oxirane oxygen content of 0.7% by weight, and a molecular weight of about 26,000.

Example 6 Synthesis of Macromonomer A-4 In the same manner as in Example 1, ε-caprolactone 1 was added to 90 g of a phenol ethylene oxide (4 mol) adduct.
After reacting 330 g, a caprolactone adduct (having a hydroxyl value of 13.
3) got. Then, the caprolactone adduct was reacted with methacrylic acid to give a macromonomer A-4 (acid value of 0.1.
5, hydroxyl value 0.6, molecular weight about 4300).

合成 Synthesis of graft copolymer P-6 By the same operation as in Example 1, macromonomer A-
4 30g, styrene 27g, glycidyl methacrylate
By reacting 3 g, a graft copolymer P-6 was synthesized. The graft copolymer P-6 had a content of the structural unit II of styrene corresponding to the vinyl monomer B of 43% by weight, an oxirane oxygen content of 0.48% by weight, and a molecular weight of about 21,000.

Comparative Example 1 Synthesis of Macromonomer C-1 25 g of hydroxyethyl methacrylate, 1 g of tetrabutyl titanate and 0.2 g of hydroquinone were charged into a flask, the inside of which was replaced with nitrogen, and heated to 150 ° C. Then, after 750 g of ε-caprolactone was added dropwise over 1 hour, the reaction was continued at 150 ° C. for 2 hours, and the macromonomer C-
1 (hydroxyl value 15.2, molecular weight about 3700) was obtained.

合成 Synthesis of graft copolymer R-1 By the same operation as in Example 1, 90 g of toluene was used, 30 g of macromonomer C-1 and 25 g of styrene were used.
g and 5 g of glycidyl methacrylate were reacted. At the end of the reaction, the formation of a gel was observed. The reaction solution was cooled to room temperature and poured into 500 ml of methanol to precipitate a copolymer. The precipitated white precipitate was methanol 10
After washing three times with 0 ml, vacuum drying was performed at 70 ° C. to synthesize a graft copolymer R-1. Graft copolymer R-1
Although swelled in toluene, but was insoluble, its molecular weight could not be measured.

Comparative Example 2 Synthesis of Macromonomer C-2 148 g of phthalic anhydride, 100 g of succinic anhydride and 130 g of ethylene glycol were charged into a flask and reacted at 150 ° C. for 2 hours. Then, the reaction product was heated to 200 ° C. to carry out condensation to obtain a polyester (acid value 17, hydroxyl value 20).

Then, the polyester was cooled to 160 ° C., 8 g of maleic anhydride was added thereto, and the mixture was reacted for 1 hour to obtain a macromonomer C-2 having a carboxyl group at both terminals (acid value: 36, average molecular weight: about 3030). Obtained.

合成 Synthesis of graft copolymer R-2 100 g of the above macromonomer C-2 and 70 g of styrene
g, glycidyl acrylate 10 g and xylene 300 g,
The above was charged into a flask and dissolved. This was heated to 80 ° C., 1 g of benzoyl peroxide was added while introducing nitrogen, and the reaction was continued for 6 hours. Then, the same operation as in Example 1 was performed on the contents to synthesize a graft copolymer R-2. When the graft copolymer R-2 was dissolved in toluene, insolubles were recognized, and thus the molecular weight of the graft copolymer R-2 was not measured.

Comparative Example 3 Synthesis of Graft Copolymer R-3 By the same operation as in Example 1, macromonomer A-
7g, 1 g of methyl methacrylate, and 2 g of glycidyl methacrylate were reacted to synthesize a graft copolymer R-3. The graft copolymer R-3 is a vinyl monomer B
Structural unit made from methyl methacrylate equivalent to
The II content was 84% by weight, the oxirane oxygen content was 0.39% by weight, and the molecular weight was about 35,000.

Comparative Example 4 Synthesis of Macromonomer C-3 Ethyl cellosolve 90 was obtained in the same manner as in Example 1.
g was reacted with 342 g of ε-caprolactone to obtain a caprolactone adduct (hydroxyl value 131). Next, the caprolactone adduct was reacted with methacrylic acid to obtain a macromonomer C-3. Macromonomer C-3 has a molecular weight of about
The average number of added moles of 500 and ε-caprolactone was 3.

合成 Synthesis of graft copolymer R-4 By the same operation as in Example 1, macromonomer C-
30 g of styrene, 27 g of styrene, and glycidyl methacrylate
By reacting 3 g, a graft copolymer R-4 was synthesized. The graft copolymer R-4 had a content of the structural unit II of styrene corresponding to the vinyl monomer B of 48% by weight, an oxirane oxygen content of 0.54% by weight, and a molecular weight of about 31,000.

Comparative Example 5 Synthesis of Graft Copolymer R-5 By the same operation as in Example 1, macromonomer A-
21 g of styrene, 20 g of styrene, and glycidyl methacrylate
By reacting 20 g, a graft copolymer R-5 was synthesized.
The graft copolymer R-5 had a content of the structural unit II of styrene corresponding to the vinyl monomer B of 32% by weight, an oxirane oxygen content of 3.37% by weight, and a molecular weight of about 21,000.

-Evaluation example as resin additive Polycarbonate (Panlite L-12 manufactured by Teijin Chemicals Limited)
25) 60 g, 40 g of polybutylene terephthalate (Tuppet made by Mitsubishi Rayon Co., Ltd.) and 3 g of the graft copolymer of the present invention or a comparative graft copolymer were charged into a small experimental kneader and kneaded at 250 ° C. for 4 minutes. Next, a sheet having a thickness of 2 mm was formed using a hot press machine. At the same time, the same operation was carried out for the one without the addition of the graft copolymer to form a sheet (blank). The time from the start of kneading to the time when the torque reaches the maximum value (time in Table 3) was measured by the torque curve at the time of kneading.
For each kneaded sample, the intrinsic viscosity of the orthochlorophenol solution at 35 ° C. was measured, and Δη was calculated by the following equation.
Was calculated and evaluated. Further, for each sheet, the degree of coloring was visually observed, the glass transition point (Tg in Table 3) derived from polycarbonate was measured by DSC, and the dispersion state was evaluated by the following method. The results are shown in Table 3. The reduction in the time from the start of kneading until the torque reaches the maximum value and the decrease in the glass transition point derived from polycarbonate indicate that the dispersibility is improved accordingly.

算出 Δη Calculation and Evaluation Criteria Δη = ｛(η−η ₀ ) / η ₀ ｝ × 100 [η is the intrinsic viscosity of the sample η ₀ is the intrinsic viscosity of the blank] Δη ≦ −4; 0 <Δη ≦ 5; good (good physical properties, moldability and fluidity of resin) 5 <Δη; not good (poor moldability and fluidity of resin) (4) Evaluation of dispersion state The sheet was immersed in chloroform for 5 minutes at room temperature to etch the surface. The surface state of the sheet after the etching treatment is observed by a scanning electron microscope,
The homogeneity of the dispersion state and the shape and size of the dispersion system were examined. In this case, the homogeneity was evaluated as follows. That is, a state in which the dispersion state was greatly improved compared to the blank and the state was fine and homogeneously dispersed was regarded as good, and a state in which there was no difference from the blank was regarded as defective.

<Effects of the Invention> As is clear from the results of each table, the present invention described above has good heat resistance and has two or more types having different compatibility with each other without causing deterioration of the resin. When kneading the above resin, there is an effect of exhibiting excellent dispersion performance with respect to the resin.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location C08F 220: 12 212: 08 216: 14) (C08L 69/00 67:00 55:00)

Claims (5)

(57) [Claims] 1. A graft copolymer having reactivity useful as a resin additive, comprising a structural unit I, a structural unit II and a structural unit III represented by the following formulas, respectively. 80 to 20% by weight, constituent unit II is 10 to 79% by weight, and constituent unit III is 1 to 20% by weight
And a graft copolymer having a molecular weight of 10,000 to 150,000. [However, R ¹ , R ³ , R ⁵ ; H or CH ₃ R ² ; an aliphatic or alicyclic hydrocarbon group having 1 to 18 carbon atoms or C _m H _2m O) _r R ⁶ R wherein R ⁶ A hydrocarbon group having 1 to 18 carbon atoms, m; 2 or 3,
^{r; 1~5) R 4; C} 6 H 5, COOCH 3 or COOC ₂ H ₅ X; COO or CH ₂ O n; 6~90] 2. The structural unit I is: The graft copolymer according to claim 1, which is: 3. The structural unit II is: The graft copolymer according to claim 1 or 2, wherein 4. The structural unit II is: The graft copolymer according to claim 1 or 2, wherein 5. The structural unit III comprises: The graft copolymer according to claim 1, 2, 3, or 4.