JPH04218517A - Multielement copolymer and resin modifier or resin compatibilizing agent using the same - Google Patents

Abstract

PURPOSE:To obtain a new indene-containing multielement copolymer, consisting essentially of a polymerization component in inexpensive naphtha oil and maleimide, capable of designing the melting temperature for a desired value and useful as a modifier, etc., for imparting heat resistance to thermoplastic resins. CONSTITUTION:A multielement copolymer is composed of (A) a polymerization component, composed of an 8-11C aromatic hydrocarbon and containing indene as a main polymerization component in naphtha oil and (B) maleimide (preferably N-phenylmaleimide or cyclohexylmaleimide) as essential components and further (C) a polymerization component (preferably styrene, acrylonitrile, etc.) copolymerizable with the components (A) and/or (B). The polymerization composition ratio of the components (A) to (B) is preferably regulated so as to provide about 50mol% component (B) based on the total number of mol of the components (A) and (B).

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a novel indene-containing multi-component copolymer, and in particular to a multi-component copolymer whose melting temperature can be designed to a desired value by effectively utilizing the polymerization components in inexpensive naphtha oil. .

The multicomponent copolymer obtained by the present invention can be used as a resin modifier that imparts heat resistance to thermoplastic resins and the like, and as a polyamide resin modifier.

Furthermore, the multicomponent copolymer obtained according to the present invention can be used as a compatibilizer for polyamide alloy resins.

0004

[Prior art] ABS resin, which is a general-purpose plastic,
To improve the heat resistance of HIPS resin and PVC resin,
Various efforts have been made.

Plastics, vol. No. 9 (19
86), in order to improve the heat resistance of ABS resins and HIPS resins, by copolymerizing α-methylstyrene and p-methylstyrene in place of styrene in a styrene-acrylonitrile copolymer system, the heat distortion temperature can be improved. (HDT) is
It is said that it will improve, but the effect is not large.

[0006] JP-A-1-85207, US Patent No. 6
No. 2,257,952, No. 62,257,955, JP-A-62-100509, JP-A-62-10485
In Publication No. 9, acrylonitrile, α-methylstyrene,
The heat resistance of the copolymer (resin) obtained by copolymerizing indene with styrene, methyl methacrylate, etc. is improved by the addition of indene, and when this copolymer is blended into general-purpose plastics, the compounded It is disclosed that the heat resistance of (composition) is improved. However, the effect of indene on improving heat resistance is insufficient.

Conventionally, maleic anhydride and maleimide are known to be polymeric components that impart heat resistance to resins. JP-A-63-90557 and JP-A-63-128
No. 050, U.S. Patent No. 4,408,010,
It is disclosed that the heat resistance of general-purpose plastics is improved by forming a resin composition using a styrene-maleic anhydride copolymer (SMA) imide.

A copolymer of styrene and maleic anhydride has attracted attention as a polymer that imparts heat resistance to general-purpose plastics such as ABS resin, HIPS resin, PVC resin, and polystyrene resin. However, thermal decomposition of SMA itself begins at 200℃, while processes such as kneading with general-purpose plastics, extrusion molding, injection molding, etc.
Because of the above, SMA has the disadvantage that it can only be used under special conditions in this field. In order to solve this problem, partial imidization of SMA was considered. Tokuko Showa 5
According to Publication No. 6-39651, in a copolymer in which SMA is imidized with ammonia, when the imidization substitution rate increases by 1%, the glass transition temperature rises by about 3°C. It has been shown that in copolymers, when the imidization substitution rate increases by 1%, the glass transition temperature increases by about 2° C. or more.

[0009] Collection of Polymer Papers, vol. 39, P. 447
(1979) investigated the thermal decomposition characteristics of styrene-N-phenylmaleimide copolymer, and
The thermal decomposition initiation temperature of the N-phenylmaleimide copolymer is
It is reported that the temperature is 320°C, which is 120°C or more higher than that of SMA. However, imidized copolymers obtained only from styrene, maleic anhydride, and maleimide still had problems such as insufficient compatibility as resin modifiers that impart heat resistance to general-purpose plastics. .

On the other hand, resins made from maleic anhydride or maleimide have acid anhydride groups and carbonyl groups in the resin. These functional groups react with the amide groups and amino groups of polyamide (PA) resins such as nylon, and by utilizing this property, they can be used with PA resins such as nylon, which are difficult to finely disperse by mechanical manipulation alone. It is used as a compatibilizer for PC resins, modified PPO resins, etc. For this purpose, Japanese Patent Application Laid-Open No. 63-90557 and Japan Rubber Association Journal Vol.
61, No. 8, P. 542 (1988) proposed a copolymer of styrene and maleic anhydride or its imidized product, but the thermal decomposition initiation temperature of these imidized products is different from that of the fully imidized copolymer of styrene and N-phenyl. Let's use imidized products as compatibilizers between polyamide resins, polycarbonate resins, polyphenylene oxide resins, etc., or as modifiers for polyamide resins, at a temperature lower than 320°C, which is the thermal decomposition initiation temperature of copolymers with maleimide. However, since the kneading and molding temperature of these resins is around 300°C, the imidide decomposes during the kneading and molding process with the resin, so it is difficult to use conventional imidide as a resin modifier. has many problems.

As mentioned above, a number of technologies have been developed for resin compositions (hereinafter referred to as heat-resistant resin modifiers) that impart heat resistance to general-purpose plastics such as ABS resin, HIPS resin, and PVC resin. However, there are the following problems.

(1) The effect as a heat-resistant resin modifier is insufficient, and the heat distortion temperature (HD
There are problems with the degree of improvement in T) and glass transition temperature (Tg).

(2) When the temperature is from 200°C to 250°C in the process of mechanical kneading, extrusion molding, and injection molding for blending and molding general-purpose plastic and heat-resistant resin modifier, conventional heat-resistant resin Since the thermal decomposition temperature of the modifier is near this temperature range, there is a problem that the resin modifier itself is thermally decomposed during the kneading and molding steps.

(3) When a general-purpose plastic and a heat-resistant resin modifier are mechanically blended or molded at a certain temperature, blending is difficult unless the melt viscosities of both are close. The melt viscosity of conventional heat-resistant resin modifiers is problematic because it differs from the melt viscosity of general-purpose plastics.

In addition, polyamide alloy resins such as polyamide (PA)-polycarbonate (PC) resins and polyamide (PA)-modified polyphenylene oxide (PPO) resins have good mechanical properties and chemical resistance. Therefore, it is attracting attention. However, originally PA-PC resin, P
Since A-modified PPO resins and the like are not compatible, a compatibilizer is required to finely disperse the two types of resins, but conventional compatibilizers have the following problems.

(4) Conventional compatibilizers include PA-PC type,
The ability to finely disperse PA-modified PPO resins and the like is weak, and the mechanical properties of polyamide alloy resins obtained using these compatibilizers are insufficient.

(5) PA-PC resin, PA-modified PP
The temperature range for mechanically kneading and molding O-based resin etc. is usually 3.
The temperature is around 00°C, and the compatibilizer itself is thermally unstable in this temperature range.

For fully imidized copolymers obtained only from indene and maleimide, see Polymer Jou.
rnal, Vol. 20, NO. 11, pp 979
-985 (1988) and Japanese Patent Publication No. 49-26949. However, these contents only consider kinetic studies and production methods using radiation polymerization methods, and do not touch on the use of heat-resistant resin modifiers or compatibilizers for polyamide alloy resins. Also, the molecular weight of the multi-component copolymer has not been disclosed.

Furthermore, JP-A-60-86152 discloses a flame-resistant ABS resin using a resin composition containing indene and maleimide, but the application is different from that of the present invention, and there are The optimum indene content and maleimide content are not stated, or it is unclear whether indene and maleimide are essential, and there are no examples containing indene and maleimide.

[0020] Furthermore, the present applicant previously disclosed a copolymer using a polymerization component in naphtha oil as follows.

[0021] Coal-based or petroleum-based naphtha has a boiling point range of 80 to 220°C and is mainly composed of aromatic hydrocarbons having 8 to 11 carbon atoms. This naphtha oil contains a component (polymerization component) having a reactive double bond with indene as the main polymerization component. Indene has a bicyclic structure and is more rigid than styrene. Therefore, resins containing indene as a polymerization component can be expected to have improved heat resistance.

Therefore, the present inventors investigated the production of a copolymer of maleic anhydride and a polymerization component in naphtha oil containing indene as the main polymerization component, and found that Macromol. , Chem. , 62,120
(1963), it is possible to industrially produce copolymers of polymeric components in naphtha oil and maleic anhydride in high yields and with various molecular weight distributions depending on the combination of reaction conditions, etc. It was shown that Furthermore, the obtained copolymers, including alkali hydrolysates, esters, sulfonated alkali hydrolysates, and unmodified products, can be used in various dispersants, paint compositions, adhesives, and heat-resistant resins for general-purpose plastics. We have discovered and proposed that it is effective as a modifier and compatibilizer for polyamide resins. (Patent Application No. 1-326299, EPC Publication No. 0348
975)

However, when used as a heat-resistant resin modifier for general-purpose plastics, the compounding conditions with general-purpose plastics are restricted, or when used as a compatibilizer for polyamide resins, the resulting alloying There were problems such as there was room for improvement in the mechanical properties of the resin.

[0024]

OBJECTS OF THE INVENTION An object of the present invention is to solve the problems in the prior art, and to be able to be used as a resin modifier that imparts heat resistance to thermoplastic resins and as a polyamide resin modifier. The present invention aims to provide a multi-component copolymer that can be used as a compatibilizer for polyamide-based alloyed resins, and whose melting temperature etc. are well-balanced with the resin with which it is blended.

[0025]

[Means for Solving the Problems] The present inventors have developed a copolymer of a naphtha oil polymerization component containing indene as the main polymerization component and maleic anhydride as a heat-resistant resin modifier for thermoplastic resins and as a polyamide resin. We conducted extensive research to improve the use as a compatibilizer for alloyed resins. As a result, an imidized product in which part or all of the acid anhydride groups of a copolymer of a naphtha oil polymerization component whose main polymerization component is indene and maleic anhydride is imidized can be used as a heat-resistant resin modifier or It was found to be useful as a compatibilizer for polyamide alloyed resins, leading to the present invention.

[0026] Furthermore, when attempting to mechanically knead and blend these copolymers with various plastics, a problem arises in that the melting temperature of the copolymer is significantly different from the melting temperature of the plastic with which it is blended. In this case, if copolymerizable components such as styrene, acrylonitrile, methyl methacrylate, and butadiene are added to the polymerization composition and copolymerization is carried out, a better balance can be achieved in terms of heat distortion temperature and melting temperature. It was found that it can be used as a heat-resistant resin modifier for plastics, leading to the present invention.

That is, the present invention provides a multicomponent copolymer which contains a polymeric component in indene or naphtha oil and maleimide and/or maleic anhydride as essential components, and further comprises a polymeric component copolymerizable with at least one of these essential components. Provides coalescence.

The maleimide is preferably N-phenylmaleimide or cyclohexylmaleimide.

Copolymerizable polymer components include the following (a) and (
At least one or all of b), (C) and (d) are preferable. (a) Styrenes such as styrene, α-methylstyrene, methylstyrene, and chlorostyrene (b) Vinyl cyanides such as acrylonitrile and methacrylonitrile (c) Acrylic acid esters such as alkyl acrylates or alkyl methacrylates or methacrylic acid esters (d) dienes such as isoprene or butadiene. These multicomponent copolymers are useful as main components of resin modifiers for thermoplastic resins, modifiers for polyamide resins, and compatibilizers for polyamide alloy resins.

The configuration of the present invention will be explained in detail below. Coal- or petroleum-based naphtha oil has a boiling point range of 80℃ to 220℃
The main component is an aromatic hydrocarbon having 8 to 11 carbon atoms. This naphtha oil contains a polymerization component whose main component is indene.

[0031] To give an example, as shown below, the main component is indene, and the polymerization component in the naphtha oil component is 5 wt% or more, and the polymerization component is the following component (A),
It is composed of the weight percentages of (B) and (C),
(A), (B), and (C) are specifically shown. (A) Indene 60-99wt% (B) Styrene 0.5-29.5wt% (C) α-
At least one or two of methylstyrene, methylstyrene, methylindene, dimethylstyrene, trimethylstyrene, coumaron, and dicyclopentadiene
The total of the above is 0.5 to 29.5 wt%

Here, the sum of (A), (B), and (C) is substantially (
A)+(B)+(C)=100wt%.

Naphtha oil also contains xylene, ethylbenzene, propylbenzene, tetramethylbenzene, ethyltoluene, indane, trimethylbenzene, tetramethylbenzene, naphthalene, etc. as non-polymerized components.

When only indene is used as a raw material, it can be obtained by precision distillation of naphtha oil, but this is not advantageous in terms of cost. 90 of the polymerized components
When naphtha oil containing at least % by weight of indene is used as a raw material, the properties of the obtained multi-component copolymer are no different from those of multi-component copolymers produced using indene.

Maleic anhydride used in the present invention is usually used in a solid state, but it may be used after being dissolved in an aromatic hydrocarbon or a solvent such as methyl ethyl ketone or methyl isobutyl ketone.

When maleic anhydride is used as a raw material for the multi-component copolymer, it becomes possible to introduce a reactive acid anhydride group into the copolymer, and the copolymer can be further esterified,
It can be used in graft polymerization reactions.

[0037] A multi-component copolymer containing indene and maleic anhydride as essential components and a polymeric component copolymerizable with these components has indene as its main component, so when used as a resin modifier, the heat resistance of the other resin increases. Increase sex.

The method for producing an imidized multi-component copolymer of the present invention involves using maleic anhydride as a raw material and modifying the acid anhydride group introduced into the resin with ammonia or a primary amine. , a method for producing a multicomponent copolymer,
There is a method of making a multicomponent copolymer using maleimide as part of the raw material. In terms of cost, it is more advantageous to produce a multicomponent copolymer using maleimide as a raw material. The maleimide to be used has the structure shown below, and R may be any alkyl group such as methyl, ethyl, propyl, or cyclohexyl, an aryl group such as phenyl or tolyl, or hydrogen, but in particular R may be cyclohexyl or phenyl. Multi-component copolymers obtained from the maleimide group are particularly good as heat-resistant resin modifiers and compatibilizers.

[0039]

[Chemical formula 1]

[0040] In the present invention, a multicomponent copolymer containing a polymeric component (or indene) in naphtha oil and maleimide and/or maleic anhydride as essential components has a copolymerizable component copolymerizable with at least one of these essential components. Add other polymerization ingredients. An example of such a polymeric component is listed below. (a) Styrenes such as styrene, α-methylstyrene, methylstyrene, chlorostyrene, etc. (b) Vinyl cyanides such as acrylonitrile, methacrylonitrile, etc. (c) Acrylic acid esters such as alkyl acrylates or alkyl methacrylates, Or methacrylic acid esters (d) dienes such as isoprene or butadiene.

4 of the above (a), (b), (c), and (d)
There may be at least one group, or two or more groups.

[0042] When such other polymerization components are copolymerized,
The melting temperature of the resulting multi-component copolymer can be appropriately lowered, and when used as a resin modifier or resin compatibilizer, it can be designed to have a well-balanced melting temperature with the other resin.

Regarding the polymerization composition ratio between the polymerization component (or indene) of naphtha oil and maleimide, the amount of maleimide is 25 mol % or more to 75 mol % based on the total number of moles of the polymerization component (or indene) of naphtha oil and maleimide.
% or less, and 40 to 60 mol %, more preferably around 50 mol %, is industrially advantageous since it is possible to produce an imidized multi-component copolymer with a high yield.

The blending ratio of maleic anhydride is 25 mol % to 75 mol % in the multi-component copolymer based on the total amount with maleimide.
It may be within 1%.

The composition ratio of the polymeric component (or indene) of naphtha oil and the polymeric component copolymerizable with maleimide is as follows:
The effect is recognized if the total amount of naphtha oil polymerization component (or indene) and maleimide is 10 mol % or more with respect to the entire polymerization component.

The molecular weight of the multi-component copolymer thus obtained can be determined by gel permeation chromatography (Gel permeation chromatography).
2,000 to 100,00 as the molecular weight (number average molecular weight (Mn)) determined using the polystyrene standard using the PC) method.
It is in the range of 0.

Further, among the multi-component copolymers of the present invention, the imidized multi-component copolymer may be a fully imidized copolymer or a partially imidized multi-component copolymer, as explained below.

(1) Fully imidized multi-component copolymer A fully imidized multi-component copolymer is an imidized copolymer in which the entire amount of acid anhydride groups in the copolymer has been exchanged with imide groups, Alternatively, since maleic anhydride is not used during resin synthesis, it refers to an imidized multi-component copolymer that does not have an acid anhydride group.

The fully imidized multicomponent copolymer has particularly good thermal stability. For example, naphtha oil containing 90 wt% or more of indene or a copolymer of indene and N-phenylmaleimide has a thermal decomposition onset temperature of 360°C, compared to 320°C for a copolymer of styrene and N-phenylmaleimide. , excellent thermal stability. However, the melting temperature is 33
Because the temperature is as high as 0°C, mechanical kneading with other resins may be difficult. In such cases, in order to reduce the melting temperature, an imidized multi-component copolymer is produced by adding other polymeric components that can be copolymerized with the essential components shown in groups (a) to (d) above. do.

(2) Partially imidized copolymer The partially imidized copolymer refers to an imidized copolymer containing an acid anhydride group in the copolymer. The partially imidized multicomponent copolymer of the present invention also has good thermal stability because of the rigid and thermally stable indane ring and imide group resulting from the polymerization component (or indene) of naphtha oil. In addition, the acid anhydride group of the partially imidized multi-component copolymer reacts with the terminal amino group of the polyamide resin to form a graft, so it can be used as a compatibilizer for polyamide alloy resin or as a modifier for polyamide resin. It is useful as

The proportion of acid anhydride groups introduced into the copolymer is:
It is determined by the proportions of polymeric components (or indene), maleimide, and maleic anhydride in naphtha oil. An appropriate range of the acid anhydride group is 1 mol % or more based on the total mol of the polymerization component (or indene), maleimide, and maleic anhydride in the naphtha oil, so that the characteristics of the acid anhydride group are exhibited.

[0052] The acid anhydride group content is determined by the polymerization component (
Alternatively, instead of adding maleimide to the acid anhydride group of a copolymer of (indene) and maleic anhydride, a partially imidized multicomponent copolymer may be prepared by treating it with a primary amine. The partially imidized multi-component copolymer thus obtained also
It has high heat resistance because it contains rigid and heat-stable indane rings, acid anhydride groups, and imide groups in the copolymer. In particular, the indane ring makes a large contribution to thermal stability.

[0053]Although this partially imidized copolymer has high thermal stability, it also has a high melting temperature. Since the processing temperature for general-purpose plastics, such as kneading and molding, is usually around 250°C, the melting temperature of the partially imidized multi-component copolymer is too high. For this reason, in order to reduce the melting temperature, the polymeric components (
or indene), maleic anhydride, or other polymeric components copolymerizable with maleimide are added and copolymerized to produce a partially imidized multi-component copolymer.

The multi-component copolymer of the present invention may be produced by any method such as bulk polymerization, solution polymerization, or suspension polymerization in an aqueous system, but when maleic anhydride is contained in the copolymer composition, Synthesis by suspension polymerization is not advantageous because maleic anhydride is hydrolyzed by water and migrates toward the aqueous layer. This synthesis reaction proceeds in the presence of a radical polymerization initiator, and the radical polymerization initiator that can be used may be either a peroxide type or a diazo type, but the effective temperature range is 30°C to 180°C. It is necessary to use a radical polymerization initiator. The radical polymerization initiator may be added in its entirety into the reaction vessel together with the polymerization components, but if the decomposition rate of the initiator is rapid, it is better to gradually introduce it into the reaction vessel.

[0055] The reaction may or may not use a solvent. When a solvent is used, aromatic hydrocarbons, halogenated hydrocarbons such as dichloroethane, ketones such as methyl ethyl ketone and methyl isobutyl ketone are used, and benzene, toluene, and cumene are preferred.

The multi-component copolymer thus produced is acrylonitrile-butadiene-styrene (ABS).
When used as a resin modifier for thermoplastic resins such as resin and polyvinyl chloride resin (PVC), it improves the heat resistance, compatibility,
Improving mechanical strength etc. can be achieved by grafting.

When the multi-component copolymer of the present invention is used as a modifier for polyamide resins, the heat resistance, compatibility, and mechanical strength due to grafting are improved.

Furthermore, when the multi-component copolymer of the present invention is used as a compatibilizer for a polyamide alloy resin, it is possible to obtain an alloy resin with good mechanical properties.

[0059]

[Examples] The present invention will be explained below with reference to specific examples, but the present invention is not limited thereto.

The methods for measuring number average molecular weight, thermal decomposition start temperature (weight loss start temperature), melting temperature, heat distortion temperature (HDT), and tensile strength at break in Examples are as follows. (Number average molecular weight) Determined using gel permeation chromatography (GPC) based on polystyrene standards. (Thermal decomposition starting temperature) Using a thermobalance, the temperature at which the weight of the resin starts to decrease was determined under a nitrogen atmosphere (temperature at which the temperature starts to increase from room temperature at 3° C./min during weight reduction). It is an indicator of the thermal stability of the resin. (Melting temperature) Flow tester CFT manufactured by Shimadzu Corporation
-500 was used to determine the temperature at which the resin viscosity was 5000 poise. (Heat distortion temperature) Based on ASTM D648, (HD
T) The test was conducted under a load of 18.6 kg/cm2. (Tensile strength at break) Measured according to ASTM D638 at a humidity of 50% RH and a temperature of 23±1°C. (Izod impact strength) Measured in accordance with ASTM D256. With notch. (Softening temperature) Measured according to JIS K-6745.

(Example 1) The reaction was carried out so that the total amount of polymerization components was 1 mole. 2 in a 4-necked flask with an internal volume of 1L (with stirring blade, cooling tube, dropping funnel, and nitrogen gas introduction tube)
00 mL of MEK (methyl ethyl ketone) was charged and maintained at 80° C. with a small amount of nitrogen gas flowing through it. Naphtha oil (polymerization content 50wt% (including 90w indene)
t%, styrene 3wt%, other polymeric components 7wt%)
Contains) 92.8g (0.4 mol as polymerization component), 10.4 g (0.1 mol) of styrene, 87 g of phenylmaleimide
(0.5 mol) and 1.64 g of azoisobutyronitrile (AIBN) as an initiator were diluted with 300 mL of MEK, charged into a dropping funnel, and gradually dropped into the flask.

After the dropwise addition was completed, the reaction was carried out at a reaction temperature of 80° C. for 5 hours. After the reaction was completed, the reaction solution was poured into a large amount of methanol, and the copolymer was recovered as a white powder. Thereafter, it was dried under reduced pressure at 150° C. until it reached a constant weight. The resin yield was determined from the weight of the resin after drying relative to the total weight of raw polymerization components.

(Examples 2 to 7), (Comparative Example 1) Example 1
A multicomponent copolymer was synthesized in a similar manner. The results of Example 1 are also shown for the ratio of polymerized components, yield, number average molecular weight, Tg (glass transition temperature), and thermal decomposition initiation temperature.

[0064]

[Table 1]

FIG. 1 shows the relationship between the amount of styrene added and the melting temperature of the copolymers of Examples 1 to 7 and Comparative Example 1. Figure 1
It can be seen that the melting temperature of the copolymer decreases with the addition of styrene.

In FIG. 1, the a-line shows the styrene of the polymerization component (NAPH) in the naphtha oil of Examples 1 to 3 and Comparative Example 1, a copolymer of styrene (sty) and maleic anhydride (MA). It is a graph showing the relationship between fraction and melting temperature.

The b line shows the styrene fraction and melting temperature of the polymerization component (NAPH) in the naphtha oil of Examples 4 to 7, and the copolymer of styrene (sty) and N-phenylmaleimide (PMI). It is a graph showing the relationship between.

Therefore, the a-line shows the relationship between the styrene fraction and the melting temperature of a copolymer with an imidization rate of 0, and the b-line shows the relationship between
The relationship between the styrene fraction and the melting temperature of a copolymer with an imidization rate of approximately 100% is shown.

The melting temperature of the partially imidized multi-component copolymer is:
It is between the a line and the b line.

(Examples 8 to 48) Copolymers were synthesized in the same manner as in Example 1, except that acrylonitrile, methyl methacrylate, and butadiene were further added as polymerization components. Table 2 shows the polymerization composition, yield, and some results of measurement of number average molecular weight, glass transition temperature (Tg), and melting temperature by GPC method. Moreover, the relationship between the amount of styrene added and the melting temperature is shown in FIG. 2 for Examples 8, 10, 12, and Examples 40 to 42.

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

(Examples 49 to 57), (Comparative Example 2) The multi-component copolymer of the present invention was added to ABS resin (MV GRATE) manufactured by Sumitomo Naugatuck Co., Ltd., and the treatment temperature was 250° C. using a single screw extruder. It was molded into pellets. This sample was used to produce test pieces for evaluation of thermal properties and mechanical properties using an injection molding machine. The measurement results are shown in Table 3.

[0075]

(Examples 58, 59) and (Comparative Example 3,
4) A copolymer having the composition shown in Table 4 was synthesized in the same manner as in Example 1.

[0077] Note) CMI: cyclohexylmaleimide

[0078](
Examples 60, 61) and (Comparative Examples 5, 6) Example 60
, 61 and the copolymers obtained in Comparative Examples 4 and 5, and a polyvinyl chloride resin (Sumilit SX-11F, Sumitomo Chemical Co., Ltd., degree of polymerization 1050), a resin composition was prepared having the composition shown in Table 5. did.

Each of the obtained resin compositions was heated to a surface temperature of 1
5 minutes with an 8 inch diameter hot roll heated to 90℃.
The mixture was kneaded to obtain a sheet-like resin composition. This was press-molded for 10 minutes under a pressure of 100 kg/cm2 using a flat press to prepare a test piece, and the Izod impact strength and softening temperature were measured.

Table 5 shows that when the multi-component copolymer of the present invention is blended with polyvinyl chloride resin, the Izod impact strength and softening temperature are improved compared to conventional resin modifiers.

Note) M101A: Dithioctyltin dimaleate stabilizer (
(manufactured by Tokyo Fine Chemical Co., Ltd.) E-101: Dithioctyltin dilaurate stabilizer (manufactured by Tokyo Fine Chemical Co., Ltd.) Kalen A-88: Higher alcohol-based lubricant (manufactured by Tokyo Fine Chemical Co., Ltd.)

(Examples 62-67) AIB as an initiator
A multi-component copolymer was synthesized using the charging composition shown in Table 6 in the same manner as in Example 1 except that N was halved to 820 mg. Table 6 shows the resin yield, number average molecular weight, and glass transition temperature.

[0083]

[Table 5]

(Examples 68 to 76) and (Comparative Example 6,
7) A predetermined amount of nylon 6 resin (manufactured by Unitika Co., Ltd., A1
030JR), the multi-component copolymer, and other copolymers using a screw-type twin-screw extruder (L/D=28, rotation speed 50r).
pm, cylinder temperature: 260° C.) and pelletized. The obtained pellets were heated at 40°C for 10 hours.
After drying under a reduced pressure of 4 mmHg, a resin test piece was obtained using an injection molding machine. The composition and evaluation results are shown in Table 7.

[0085]

[Table 6]

(Examples 77 to 81) and (Comparative Examples 8 to 81)
12) Takayuki Otsu, Masakotsu Kinoshita; Experimental methods for polymer synthesis,
PPO (polyphenylene oxide) was synthesized according to Kagaku Dojin (1972), p. 293, and a polymer alloy with nylon 6 (A1030JR, manufactured by Unitika) was produced. The number average molecular weight of the synthesized PPO is 16,000.

[0087] Using a twin-screw extruder, the cylinder temperature was 30
Pelletization was performed at 0° C. and a screw rotation speed of 200 rpm. The obtained pellets were molded into test pieces using an injection molding machine under conditions of a cylinder temperature of 280°C and a mold temperature of 80°C. Evaluation was conducted using this. The composition and evaluation results are shown in Table 8.

[0088]

[Table 7]

[0089]

[Effects of the Invention] The novel multi-component copolymer of the present invention has a polymeric component in indene or naphtha oil and maleimide and/or maleic anhydride as essential components, and further contains a polymeric component that can be copolymerized with these essential components. Copolymerize.

Therefore, when the multi-component copolymer of the present invention is used as a resin modifier for thermoplastic resins, a modifier for polyamide resins, or a compatibilizer for polyamide alloy resins, the heat resistance of the other resin can be improved. properties and mechanical properties. Furthermore, by selecting the type and amount of polymerizable components that can be copolymerized, it is possible to set the melting temperature, etc. of the multi-component copolymer to a desired value. A compatibilizing agent and a compatibilizing agent are obtained.

[Brief explanation of the drawing]

FIG. 1 is a graph showing the relationship between the styrene fraction and melting temperature in the multi-component copolymers of Examples 8, 10, and 12.

FIG. 2 is a graph showing the relationship between the styrene fraction and melting temperature in the multi-component copolymers of Examples 40 to 42.

Claims (11)

[Claims] Claim 1: An aromatic hydrocarbon having 8 to 11 carbon atoms, which contains indene as a main component, and which contains a polymeric component in naphtha oil and maleimide as essential components, and further comprises a polymeric component in naphtha oil and/or maleimide. A multicomponent copolymer consisting of a polymeric component that can be copolymerized with maleimide. 2. An aromatic hydrocarbon having 8 to 11 carbon atoms, which contains indene as a main component, and which contains a polymeric component in naphtha oil and maleic anhydride as essential components, and further comprises a polymeric component in naphtha oil and maleic anhydride. /or A multi-component copolymer consisting of a polymeric component copolymerizable with maleic anhydride. 3. An aromatic hydrocarbon having 8 to 11 carbon atoms, containing indene as a main component, a polymerization component in naphtha oil, maleimide and maleic anhydride as essential components, and at least at least of these essential components. A multicomponent copolymer consisting of a polymer component that can be copolymerized with one component. 4. A multicomponent copolymer comprising indene and maleimide as essential components and further comprising a polymeric component copolymerizable with indene and/or maleimide. 5. A multicomponent copolymer comprising indene and maleic anhydride as essential components and further comprising a polymeric component copolymerizable with indene and/or maleic anhydride. 6. A multicomponent copolymer comprising indene, maleimide, and maleic anhydride as essential components, and further comprising a polymeric component copolymerizable with at least one of these essential components. 7. The copolymerizable polymer component is the following (
The multi-component copolymer according to any one of claims 1 to 6, comprising at least one selected from the group consisting of a), (b), (c) and (d), or all of them. (a) Styrenes (b) Vinyl cyanides (c) Acrylic esters or methacrylic esters (d) Dienes 8. The multicomponent copolymer according to claim 1, wherein the maleimide is N-phenylmaleimide and/or cyclohexylmaleimide. 9. A resin modifier for thermoplastic resins comprising the multicomponent copolymer according to any one of claims 1 to 8 as a main component. 10. A modifier for polyamide resins comprising the multi-component copolymer according to any one of claims 1 to 8 as a main component. 11. A compatibilizing agent for a polyamide alloy resin, the main component being the multi-component copolymer according to any one of claims 1 to 8.