JPH02279764A - Compatibilizer for resin and resin composition - Google Patents

Abstract

PURPOSE:To improve impact resistance, flow characteristics, heat resistance and molding processability by polymerizing an arom. vinyl compd. in the presence of a chain transfer agent having a hydroxyl group. CONSTITUTION:A compatibilizer for a resin consisting of an arom. vinyl polymer having a hydroxyl group at least at one terminal thereof is obtd. by polymerizing an arom. vinyl compd. (e.g. styrene) in the presence of a chain transfer agent having a hydroxyl group (e.g. 2-mercaptoethanol). Then, a resin compsn. is obtd. by compounding 5 to 95wt.% resin having an affinity with an arom. vinyl polymer (e.g. polyphenylene ether), 95 to 5wt.% resin reactive with a hydroxyl group selected from polyesters, polyamides and maleic acid-modified polyolefin and 0.1 to 50wt.% compatibilizer.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to a compatibilizer for resins and a resin composition.

[Prior Art] Modification of resins has been actively studied using polymer blends, in which polymers having different properties are blended together. For example, a resin composition is known that is a polymer blend of polyphenylene ether and polyester using a styrene resin such as polystyrene (for example, JP-A-59-174G45).

[Problems to be Solved by the Invention] However, the conventional ones had problems such as a decrease in impact resistance.

[Means for Solving the Problems] The present inventors have arrived at the present invention as a result of studies to solve the above problems.

That is, the present invention provides a compatibilizing agent for a resin made of an aromatic vinyl polymer having a hydroxyl group at least at one end; This is a resin composition comprising a resin (b) and a compatibilizing agent (c) for a resin according to M water ring 1 or 2.

In the aromatic vinyl polymer having a hydroxyl group at at least one end of the present invention, the aromatic vinyl polymer includes:
Known polymers of aromatic vinyl compounds can be used. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, t-butylstyrene, dimethylstyrene, acetoxystyrene, hydroxystyrene, vinyltoluene, and chlorvinyltoluene. Furthermore, copolymers of the above-mentioned aromatic vinyl compounds and other known copolymerizable vinyl compounds can also be used. Other known copolymerizable vinyl compounds include (meth)acrylic acid, (
Examples include meth)acrylic acid ester and (meth)acrylonitrile. Among the aromatic vinyl polymers, preferred are polystyrene, styrene-(meth)acrylonitrile copolymer, and styrene-butadiene block copolymer.

The molecular weight of the aromatic vinyl polymer having a hydroxyl group at at least one end of the present invention is usually 800 to 3000 on a number average.
Go, preferably 1000 to GGOGO.

Known methods can be used to produce these aromatic vinyl polymers having a hydroxyl group at at least one end. For example, an aromatic vinyl compound is polymerized in the presence of a chain transfer agent that generates hydroxyl groups. Examples of the chain transfer agent having a hydroxyl group include mercaptan compounds such as 2-mercaptoethanol and thioglycerin. As the aromatic vinyl compound, those listed in the section of the aromatic vinyl polymer can be used. Examples of polymerization methods include solution polymerization, suspension polymerization, and emulsion polymerization in the presence of a radical initiator. Among these, the solution polymerization method is preferred (for example, Japanese Patent Publication No. 11224/1983).

In the resin composition of the present invention, the resin (a) having affinity with the aromatic vinyl polymer includes styrene resins (polystyrene, AS resin, ABS resin, AB resin,
S resin, AC8 resin, MBS resin, styrene-butadiene resin, HIPS, etc.), aromatic polyethers (polyphenylene ether, etc.), and mixtures of two or more of these resins.

Among these, polyphenylene ether, A
BS resin and mixtures thereof.

Examples of the resin (b) reactive with hydroxyl groups include polyester (polyethylene terephthalate, polybutylene terephthalate, polycarbonate, etc.), polyamide (B nylon, 6,6 nylon, 11 nylon, 12 nylon, etc.), polyimide, polyamideimide, malein. Acid-modified polyolefin (maleic acid-modified polypropylene, etc.)
and mixtures of two or more of these. Among these, preferred are polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyamide, maleic acid-modified polypropylene, and mixtures of two or more thereof.

The composition of the present invention can also contain other resins if necessary. Other resins include thermosetting resins (formaldehyde resin, phenol resin, amino resin, unsaturated polyester, epoxy resin, diallyl phthalate resin, silicone resin, thermosetting polyurethane, etc.)
, the following thermoplastic resins, such as polyolefin resins (
polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer,
Poly-4-methylpentene, polybutene, etc.), polyalkyl (meth)acrylate, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, ethylene-(
meth)acrylic acid copolymers, ionomer polyacetals, polyarylates, polysulfones, IJ ether sulfonds, elastomers (ethylene-propylene rubber, ethylene-acrylic acid ester copolymers, EPDM).

butadiene rubber, styrene-(hydrogenated) conjugated diene elastomer, polyester elastomer, polyamide elastomer, thermoplastic polyurethane, etc.).

The composition of the resin composition of the present invention is based on weight (a
) is usually 5-959A, (b) is usually 95-5% (c)
is usually 0.1 to 50%, preferably 1 to 15%, and other resins are usually 0 to 30%, preferably 0 to 60%.

The resin composition of the present invention can be produced by mixing a resin compatibilizer and a resin using various known mixers. Examples of various known mixers include extruders, Brabender kneaders, and Banbury mixers.

[Example] The present invention will be further explained with reference to the following example, but the present invention is not limited thereto. In the following description, parts and %
Means parts by weight and % by weight, respectively.

The characteristics of the molded products described in Examples and Comparative Examples were evaluated by the following method.

(1) Impact strength: ASTM D258 notched,
3.2s-thickness (2) Heat distortion temperature: ASTM D848 (3) Fluidity The fluidized bed, so-called spiral flow length (thickness 2-) during injection molding using a two-volume mold was measured.

Example 1 Styrene 20g% in a flask equipped with a stirrer, reflux condenser, two dropping funnels, thermometer and gas inlet
Xylene sol, 2-mercaptoethanol 0.1
I prepared g. Styrene Rots 2-mercaptoethanol (1,1
I prepared 5g. The other dripping funnel (Dripping funnel 2
) were charged with 1.2 g of azobisisobutyronitrile and 20 g of tetrahydrofuran. The temperature inside the flask is 80.
℃, and the contents were added dropwise from dropping funnel 1 over a period of 3 hours and from dropping funnel 2 over a period of 4 hours while maintaining the temperature at 80° C. under a nitrogen stream. After the completion of dripping, another 2 hours 80
The temperature was maintained at ℃. The solvent was distilled off to obtain 119 g of polystyrene having terminal hydroxyl groups (hereinafter abbreviated as 1'S-011), which is a compatibilizer for resins of the present invention. Molecular weight 24001
The hydroxyl value was 23.

Example 2 Styrene I Sg, in a flask equipped with a stirrer, reflux condenser, two dropping funnels, thermometer and gas inlet
Acrylonitrile 51! , ethylene dichloride so
g% 0.1 g of 2-mercaptoethanol was charged. - 55g of styrene in the dropping funnel (dropping funnel) 1)
1 Acrylonitrile 25g% 2-mercaptoethanol O, 15g were charged. Add 1.2 g of 7zobisisobronitrile to the other dropping funnel (dropping funnel 2).
20g of tetrahydrofuran was charged. The temperature of the liquid in the flask was set to 80°C, and the contents were added dropwise from dropping funnel 1 over 3 hours and from dropping funnel 2 over 4 hours while maintaining the liquid temperature at 80°C under a nitrogen stream. After the dropwise addition was completed, the temperature was maintained at 80°C for another 2 hours. After distilling off the solvent, 98 g of styrene having a terminal hydroxyl group, which is a compatibilizer for resins of the present invention,
Acrylonitrile copolymer (hereinafter abbreviated as AS-01+)
I got it. The molecular weight was 120 Go, and the hydroxyl value was 5.

Example 3 Styrene 60 g, n
- 500 g of hexane, n-butyllithium (as amount of active lithium) 0.002! #Prepared. In the dropping funnel, 1,3-butadiene'0g1n-hexane 25
0g was charged. Inside the autoclave under nitrogen atmosphere 55
℃ and polymerized for 4 hours, the contents were added dropwise from the dropping funnel, and polymerized at 70℃ for 5 hours. Furthermore, 5 g of ethylene chlorohydrin was added to stop the polymerization. The polymerization rate of this seven-layer monomer was 98.8%. After distilling off the solvent, 97 g of a styrene-butadiene block copolymer (hereinafter referred to as
(abbreviated as R-Oll) was obtained. The molecular weight was 43,000° and the hydroxyl group was 411.2.

Example 4 30 g of styrene was placed in an autoclave equipped with a stirrer, a reflux condenser, two dropping funnels, a thermometer and a gas inlet.
, 250 g of n-hexane, and 0.0025 t of n-butyllithium (as the amount of active lithium) were charged. One dropping funnel was charged with 40 g of 1,3-butadiene and 250 g of n-hexane, and the other dropping funnel was charged with 30 g of styrene and 250 g of n-hexane. The autoclave was heated to 55°C under a nitrogen atmosphere and polymerized for 4 hours.
Furthermore, drip the contents from 1 (dropping row) and 4 at 7G”C.
After polymerization for a period of time, the contents were added dropwise from the dropping funnel 2 and polymerized at 70° C. for 4 hours. Furthermore, 5 g of ethylene chlorohydrin was added to stop the polymerization. Distill the solvent 9
8 g of styrene, butadiene, styrene block copolymer having terminal hydroxyl groups (
(hereinafter abbreviated as 5BS-011) was obtained. molecule fi4100
0. There was a hydroxyl group ai of 1.2.

Example 5 Polybutylene terephthalate (trade name 14(11-X)
06 Manufactured by Toshi ■, hereafter abbreviated as PBT) 70 parts, modified polyphenylene ether (trade name: Noryl 731J1)
Made by Engineering Plastics ■ Modified PP
E) 30 parts, Test pieces were obtained by injection molding at an injection pressure of 801) kg/am'' and a mold temperature of 80''C, and their properties were evaluated. In addition, after the test piece was fractured in liquid nitrogen, the fracture surface was observed with an electron microscope and the dispersed particle size was measured.
I-ness was evaluated. The characteristics evaluation results are shown in Table 1.

Comparative Example I The same operation as in Example 5 was performed except that PS-OH was not used. , the characteristics evaluation results are shown in Table 1.

Examples 6 to 24 The same operations as in Example 5 were carried out by changing the combinations of compatibilizers and blended resins to obtain resin compositions of the present invention.

The characteristics evaluation results are shown in Table 1.

In addition, the meanings of abbreviations other than PBT and modified PPE for resins in the table below are PA-6 (trade name tlBE nylon 10).
13B manufactured by Ube Kosan Fu), PA-8,B (trade name Leona 130O5 manufactured by Asahi Kasei ■), ABS (trade name TOYOLAC 500 manufactured by Higashi Kasei).

PC (Product name: Tubarex 7025A Mitsubishi Kasei C″J
Made by J).

It is HA-containing PP (trade name: Atmer QBOIO, manufactured by Mitsui Petrochemical Industries, Ltd.).

Comparative Examples 2 to 5 The same operation as in Example 5 was carried out by changing the combination of resins to be blended, except that no compatibilizing agent was used. Table 1 shows the characteristics evaluation results.

Example 25 A resin composition of the present invention was obtained by blending 880 parts of PA-1, 40 parts of ABS, and 15 parts of PS-01 using a twin-screw extruder at a cylinder temperature of 230'C. This composition was further heated at a cylinder temperature of 240°C and an injection pressure of 800 kg/cy.
a2, test pieces were obtained by injection molding at a mold temperature of 80°C, and their properties were evaluated. The results are shown in Table 2.

Comparative Example 6 The same operation as in Example 25 was performed except that ps-on was not used, and the characteristics evaluation results are shown in Table 2.

, Examples 26 to 48 The same operation as in Example 25 was carried out by changing the combination of compatibilizer and blended resin to obtain resin compositions of the present invention. The characteristics evaluation results are shown in Table 2.3.

Comparative Examples 7 to 11 The same procedure as in Example 25 was repeated except that no compatibilizing agent was used, except that the combination of resins to be blended was changed, and the characteristics evaluation results are shown in Tables 2 and 3.

[Effects of the Invention] The compatibilizer and resin composition of the present invention have the following effects.

The compatibilizing agent of the present invention has the effect that resins can be blended together without deteriorating the physical properties of the resin such as impact resistance and fluidity. In addition, the resulting resin composition has several excellent properties that cannot be obtained alone, such as impact resistance, fluidity,
Has heat resistance and moldability.

When modifying resins using conventional polymer blends,
It is necessary to increase the compatibility between resins by some method, but in many cases, the compatibility is insufficient and the impact resistance decreases, so that the modification effect of polymer blends cannot be achieved. This is not the case with products.

Claims (1)

[Scope of Claims] 1. A compatibilizer for resins comprising an aromatic vinyl polymer having a hydroxyl group at least at one end. 2. Aromatic vinyl polymer is polystyrene, styrene-
(meth)acrylonitrile copolymer and styrene-
selected from the group consisting of butadiene block copolymers (
The compatibilizing agent for resins according to claim 1, which is a co)polymer. 3. Resin (a) that has affinity with aromatic vinyl polymers,
A resin composition comprising a resin (b) reactive with hydroxyl groups and a compatibilizer for resins (c) according to claim 1 or 2. 4, (a) is polyphenylene ether and/or A
The resin composition according to claim 3, which is a BS resin. 5. The resin composition according to claim 3, wherein (b) is a resin selected from the group consisting of polyester, polyamide, and maleic acid-modified polyolefin. 6. 5 to 95% of (a) based on the weight of the resin composition;
The resin composition according to claim 3, 4 or 5, containing 95 to 5% of (b) and 0.1 to 50% of (c).