JPH03296533A - Preparation of polypropylene-polyester graft copolymer - Google Patents

Abstract

PURPOSE:To prepare the title copolymer useful as a compatibilizer between a polycarbonate and a polyolefin by melt mixing a modified PP onto which a specific glycidyl compd. has been grafted with a polyester in a specified ratio. CONSTITUTION:90-10 pts.wt. modified PP onto which 0.01-20wt.% glycidyl compd. of formula I (wherein R is H or 1-6C alkyl; Ar is a 6-20C arom. hydrocarbon group having at least one glycidyloxy group; and n is 1-4) (e.g. a compd. of formula II) has been grafted is melt mixed with 10-90 pts.wt. polyester (e.g. a polyethylene terephthalate).

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention is directed to the production of a polypropylene-polyester graft copolymer that is effective as a compatibilizer for engineering plastics such as polycarbonate and polyolefin in resin compositions. More specifically, the present invention relates to a method for producing a graft copolymer with a high graft ratio from a polyester and a modified polyolefin.

[Conventional technology]

Aromatic polycarbonates have excellent impact resistance, heat resistance, rigidity, and dimensional stability, but have the drawbacks of poor solvent resistance and moldability. In order to obtain a composition that has well-balanced mechanical properties while covering these drawbacks,
Various studies have been made regarding blends with polyolefins. However, since the compatibility between polyolefin and polycarbonate is not very good, attempts have been made to add various third components to improve the compatibility.

For example, as a third component added to a composition of polycarbonate resin and polyolefin resin, JP-A-57-10
No. 8151 discloses butyl rubber, and JP-A-57-1
No. 08152 discloses ethylene-propylene copolymer and/or ethylene-propylene-diene copolymer, and JP-A-57-111351 discloses isoprene rubber and/or ethylene-propylene-diene copolymer.
or methylpentene polymers.

However, none of these third components is sufficient as a compatibilizer for polycarbonate resin and polyolefin,
If the amount of polyolefin increases, not only the impact resistance of the molded article will sharply decrease, but also the problem of surface peeling will occur.

Various compositions made by adding polyester and/or modified polyolefin to aromatic polycarbonate have also been disclosed (JP-A-61-225245, JP-A-61-2).
No. 35456, No. 61-238847). However, since none of these compositions contain polyolefin, they have a problem of poor solvent resistance.

JP-A No. 64-75547 discloses 95 to 5% by weight of aromatic polycarbonate, 5 to 95% by weight of polyolefin,
2 to 100 parts by weight of modified polyolefin based on 100 parts by weight of the aromatic polycarbonate and the polyolefin, and 2 to 100 parts of polybutylene terephthalate based on 100 parts by weight of the aromatic polycarbonate and the polyolefin. Discloses a thermoplastic resin composition containing the following.

In this composition, the modified polyolefin and polybutylene terephthalate form a graft copolymer, and this graft copolymer provides good compatibility between the aromatic polycarbonate and the polyolefin.

It has been found that in such a graft copolymer, the higher the grafting ratio, the more effectively it acts as a compatibilizer.

Therefore, the present inventors aimed at improving the grafting ratio of polyester to polyolefin, and developed a polyolefin with an intrinsic viscosity of 0.
．． 50-1.8 and the concentration of terminal carboxyl group is lO-L
10 to 90 parts by weight of polyether with an oom equivalent of 8 g, and 0
．． Modified polyolefin containing 2 to 5 mol% of epoxy groups and having a weight average molecular weight of 8,000 to 140,000 90 to 1
When reacting with parts by weight of O at 260 to 320°C,
A total of 10 of the polyester and the modified polyolefin
proposed a method characterized by adding 0.05 to 2.0 parts by weight of water to 0 parts by weight (Patent Application No. 1-324).
No. 268).

The present inventors also found that the intrinsic viscosity [η] was 0.50 to 1°8.
and the concentration of the terminal carboxyl group is lO ~ 100 m equivalent/k
10 to 90 parts by weight of polyester and 0.1 to 2.0 g of polyester
Contains % functional groups by weight and has a melt flow rate of 0°54
A method for producing a polypropylene-polyester graft copolymer, which comprises melt-kneading 90 to 10 parts by weight of a modified polyolefin at 240 to 300° C. at 240 to 300° C., wherein the polyolefin is a propylene random copolymer containing a non-conjugated diene. proposed a method characterized by using a material containing
No. 9).

Furthermore, the present inventors discovered that when melt-kneading and reacting 2 to 98 parts by weight of polyester and 98 to 2 parts by weight of a modified polyolefin containing a carboxyl group or an epoxy group at 260 to 320°C, an inert atmosphere was used. Inside,
A method was proposed in which heat treatment is carried out for 1 to 100 hours at a temperature 40 to 150° C. lower than the melting point of the polyester (Japanese Patent Application No. 1-218328).

In addition, the present inventors have found that 2 to 98 parts by weight of polyester,
When reacting with 98 to 2 parts by weight of a modified polyolefin containing a carboxyl group or an epoxy group, add 0.01 to 5 parts by weight of an acid catalyst based on a total of 100 parts by weight of the polyester and the modified polyolefin. proposed a method characterized by
issue).

[Problem to be solved by the invention]

However, it has been found that when polypropylene is selected as the polyolefin in the polyolefin-polyester graft copolymer described above, a sufficiently high graft ratio cannot necessarily be obtained.

It is also possible to use a random propylene copolymer copolymerized with a non-conjugated diene modified with maleic anhydride, etc., but in this case, a large amount of gel will be generated during grafting, and this will be removed using a compatibilizer. When used as
There is a problem that surface properties etc. deteriorate.

Therefore, an object of the present invention is to provide a method for producing a polypropylene-polyester graft copolymer from modified polypropylene and polyester, which can improve the graft ratio and reduce the occurrence of gel.

[Means to solve the problem]

As a result of intensive research in view of the above objectives, the present inventors have found that after melt-kneading polypropylene modified with a specific glycidyl compound having an acrylamide group and an epoxy group and a polyester, the resulting product The inventors have found that the rate is high and the generation of gel is low, and the present invention has been devised.

That is, the method for producing a polypropylene-polyester graft copolymer of the present invention is as follows: (a) The following general formula: In the present invention, the skeleton of (a) modified polypropylene is not limited to a homopolymer of propylene, but also a combination of propylene and ethylene. Including block copolymers or random copolymers. For copolymers, the ethylene content is 10
% by weight or less. Such polypropylene resin usually has a melt flow rate (
MFR, JISK7210, load 2.16kg, 23
0°C).

In the present invention, the skeleton of polypropylene is expressed by the following general formula (1) (wherein R is H or an alkyl group having 1 to 6 carbon atoms,
^r is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n is an integer of 1 to 4).
0% by weight graft polymerized modified polypropylene 90-1
0 parts by weight and 10 to 90 parts by weight of (b) polyester are melt-kneaded.

The present invention will be explained in detail below.

(However, R9-R1 is H or an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 20.) Using a random copolymer of a non-conjugated diene comonomer and propylene represented by Can be done.

Examples of such non-conjugated dienes include 2-methyl-
1,4-pentadiene, 1,4-hexadiene, 4-methylidene-1-hexeno, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1.4-
hebutadiene, 4-ethyl=1.4-hexadiene, 4
．． 5-dimethyl-1,4-hexadiene, 4-methyl-
1,4-hebutadiene, 4-ethyl-1,4-heptadiene, 5-methyl-14-hebutadiene, 5-methyl-
1,4-octadiene, 1.5-heptadiene, 1.5
-octadiene, 5-methyl-1,5-heptadiene,
6-methyl-1,5-hebutadiene, 2-methyl-1,
5-hexadiene, 1.6 octadiene, 6-methyl-
Examples include 1,6-octadiene, 7methyl-1,6-octadiene, 2-methyl-1,6-hebutadiene, 1,9-decadiene, and 1,13-tetradecadiene. Among these, 1゜4-hexadiene, 2-methyl-1,5-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene, 1,13-tetradecadiene, etc. are particularly useful. preferable. Two or more of these non-conjugated diene comonomers can also be used in combination.

To carry out the trirandom copolymerization of propylene and a non-conjugated diene comonomer, an ordinary copolymerization method using a Ziegler-Natsuta catalyst may be applied. In this case, it is desirable that the proportion of the non-conjugated diene is 0.05 to 10 mol%. When the content of non-conjugated diene is less than 0.05 mol%, a high grafting rate cannot be obtained in the subsequent grafting reaction. Moreover, if it exceeds 10 mol%, the crystallinity of the copolymer will be significantly reduced. A more preferable content of non-conjugated diene is 0.11 to 3 mol%.

Note that the random copolymer may be copolymerized with 5 mol% or less of other unsaturated monomers such as ethylene and butene-1. The molecular weight of this copolymer is usually 100,000 to 100
It is appropriate to set it at 10,000.

Further, the monomer for modifying the polypropylene skeleton as described above has the following general formula (2): (wherein, R is H or an alkyl group having 1 to 6 carbon atoms,
^r is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n is 1 to 4
It is a glycidyl compound represented by (representing an integer of ).

Preferred glycidyl compounds have the following general formula (
3].

(In the formula, R is H or an alkyl group having 1 to 6 carbon atoms,
(n represents an integer of 1 to 4) Such glycidyl compounds are disclosed in, for example, JP-A-60-1
It can be produced by the following method shown in No. 30580.

First, an aromatic hydrocarbon having at least one phenolic hydroxyl group and an alkyl ether derivative of N-methylol acrylamide, N-methylol methacrylamide, or N-methylol methacrylamide.
By condensing these (hereinafter referred to as N-methylolacrylamides) with an acid catalyst, the following general formula (4
) (wherein R is H or an alkyl group having 1 to 6 carbon atoms,
^r゛ has at least one hydroxyl group and has 6 or more carbon atoms
20 aromatic hydrocarbon groups, and n represents an integer of 1 to 4. ) is produced.

The aromatic hydrocarbon having at least one phenolic hydroxyl group is not particularly limited, but examples include phenol, 0-cresol, m-cresol, p-cresol, 2.6-xylenol, 2.4-xylenol,
- Phenolic compounds such as chlorophenol, m-chlorophenol, 0-phenylphenol, p-chlorophenol, 2゜6-diphenylphenol, polyphenolic compounds such as hydroquinone, catechol, phloroglucinol, 1-naph)-ol , 2-naphthol, 9
Examples include polycyclic hydroxy compounds such as -hydroxyanthracene, bisphenols such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol-^), and bis(4-hydroxyphenyl)methane.

Next, by glycidylating the hydroxyl group of the compound represented by the above general formula (4), a glycidyl compound represented by the general formula (2) can be obtained.

This glycidylation is preferably carried out by carrying out an addition reaction between the compound represented by the general formula (4) and shrimp helohydrin, followed by dehydrohalogenation with a caustic alkali.

The addition reaction with shrimp herohydrin is carried out using a phase transfer catalyst.

As the shrimp herohydrin, epichlorohydrin, epibromohydrin, shrimp iodohydrin, etc. can be used.

Examples of phase transfer catalysts include quaternary ammonium salts such as tetrabutylammonium bromide, trioctylmethylammonium chloride, and benzyltriethylammonium chloride; quaternary phosphonium salts such as tetraphenylphosphonium chloride and triphenylmethylphosphonium chloride; Quaternary arsonium salts and the like can be used.

The amount of the phase transfer catalyst used is 0.01 to 100 mol%, based on 100 mol% of the compound represented by general formula (4).
It is preferable to use it within the range of . A particularly preferred amount of phase transfer catalyst used is 0.05 to 10 mol%.

In addition, the reaction time and reaction temperature are 50 to 120℃ for 5 minutes to 2
The time is preferably 10 to 30 minutes at 80 to 110°C.

Subsequently, dehydrohalogenation is performed using caustic alkali.

As the caustic alkali, caustic soda, caustic potash, lithium hydroxide, etc. can be used. These can be used as solids or as aqueous solutions. Further, as a catalyst for dehydrohalogenation, the same one as the above-mentioned phase transfer catalyst can be used. Catalysts other than the above-mentioned phase transfer catalysts include crown ethers, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, and the like.

The amount of the caustic alkali to be used is preferably equimolar to the compound represented by the general formula (4). More preferably, 1.1 to 1.5 times the mole is used. In addition, the reaction time and reaction temperature are 20 to 90°C for 10 minutes to 3 hours.
More preferably, the temperature is 40 to 70°C for 30 minutes to 2 hours.

Modification (graft polymerization) of polypropylene with a glycidyl compound as described above can be carried out by either a solution method or a melt-kneading method. In the case of the melt-kneading method, polypropylene, the above-mentioned glycidyl compound for modification, and a catalyst if necessary are put into an extruder or twin-screw kneader, etc., and 1
0.1~ while melting by heating to a temperature of 80~300℃
Knead for 20 minutes.

In the case of a solution method, the starting material is dissolved in an organic solvent such as xylene, and the solution is stirred at a temperature of 90 to 200° C. for 0.1 to 100 hours. In either case, ordinary radical polymerization catalysts can be used as catalysts, such as benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, acetyl peroxide, tert-butyl peroxybenzoic acid, dicumyl peroxide, Peroxides such as peroxybenzoic acid, peroxyacetic acid, tert-butyl peroxybivalate, 2,5-dimethyl-2,5-ditertiary-butyl peroxyhexine, diazo compounds such as azobisisobutyronitrile, etc. is preferred. The amount of the catalyst added is about 0.1 to 10 parts by weight per 100 parts by weight of the modified glycidyl compound. In the present invention, a phenolic antioxidant can be added during the graft reaction. However, if a radical polymerization catalyst is not added, it is preferable not to add it.

The grafting ratio of the glycidyl compound to polypropylene is 0.01 to 20% by weight, preferably 01 to 10% by weight.
It is. Grafting rate of glycidyl compound is 0, old weight%
If it is less than 20% by weight, it will be difficult to achieve a high grafting rate of the polyester, and if it exceeds 20% by weight, the molecular weight of the modified polypropylene obtained will decrease.

The polyester (b) used in the present invention is generally a thermoplastic resin consisting of a saturated dicarboxylic acid and a saturated dihydric alcohol, such as polyethylene terephthalate, polypropylene terephthalate, polytetramethylene terephthalate (polybutylene terephthalate), polyhexamethylene terephthalate, etc. -To, polycyclo cow sun-1.4
- Dimethylol terephthalate, polyneopentyl terephthalate and the like. Among these, polyethylene terephthalate and polybutylene terephthalate are particularly preferred.

Preferably, the polyester has an intrinsic viscosity [η] of 0.30 to 1.8 and a terminal carboxyl group concentration of 10 to 200 m equivalent/kg. Here, the intrinsic viscosity [η] (dl/g
) is calculated from the solution viscosity measured at 25°C in O-chlorophenol solvent.

When the intrinsic viscosity [η] of polyester is less than 0.30,
The effect of improving compatibility is insufficient, and if it exceeds 1.80, the melt viscosity of the reactant becomes high and processing becomes difficult, which is not preferable. On the other hand, if the concentration of the terminal carboxylic group is less than 10 m equivalent/kg, the reactivity with the modified polyolefin will be low;
If it exceeds this amount, the reactivity with the modified polyolefin becomes too high and gel is likely to be formed, which is not preferable.

Especially in the case of polyethylene terephthalate, the intrinsic viscosity [η
] is 0.30 to 1.2, and the terminal carboxyl group concentration is 1.
0 to 200 m equivalents of 8 g are preferred.

If the intrinsic viscosity [η] exceeds 1.2, the melt viscosity of the graft copolymer will increase and gel will easily form, which is not preferable. The terephthalic acid component in polyethylene terephthalate may be substituted with an alkyl group, a halogen group, etc., and the glycol component may contain up to about 50% by weight of other glycols, such as 1.
It may contain 4-butylene glycol, propylene glycol, hexamethylene glycol, etc.

In addition, in the case of polybutylene terephthalate, the intrinsic viscosity [
η] is preferably 0.30 to 1.8, and the terminal carboxyl group concentration is preferably 10 to 200 m equivalent/kg.

In this case as well, the terephthalic acid component may be substituted with an alkyl group, a halogen group, etc., and the glycol component may contain up to about 50% by weight of other glycols, such as ethylene gelcol, in addition to 1,4-butylene glycol. It may contain propylene glycol, hexamethylene gelcol, etc.

In order to graft-polymerize the above-mentioned modified polyolefin (a) and the polyester manufactured by the company, they are first tri-blended and then melt-kneaded. The crosstalk temperature is 240~
320°C is preferred, particularly 260 to 300 t. Further, the kneading time is preferably 0.5 to 30 minutes. . Preference is given to carrying out in an extruder, especially a twin-screw extruder. If the reaction temperature is less than 240 t', grafting will not be sufficient, and if it exceeds 320°C, overreaction will occur and the extruder will be clogged due to gel formation, which is not preferable. At the same time, the resin tends to deteriorate.

The blending amount of the polyester and modified polyolefin is 10 to 90 parts by weight, preferably 20 to 80 parts by weight for the former, and 90 to 10 parts by weight, preferably 80 parts by weight for the latter.
~20 parts by weight. If the amount of polyester is less than 10 parts by weight or more than 90 parts by weight, the amount of graft copolymer produced will be small.

In addition, in the present invention, an acid catalyst can be further added to the polyester and modified polyolefin for the purpose of improving the grafting rate.

In the present invention, the acid catalyst refers to an acid that acts as a catalyst, and examples include sulfuric acid, phosphoric acid, hydrogen fluoride, and organic sulfonic acids. Among these, organic sulfonic acids are preferred, and P-)luenesulfonic acid is particularly preferred.

Further, the amount of the acid catalyst added is preferably from 0.01 to 5 parts by weight, particularly preferably from 0.1 to 3 parts by weight, based on a total of 100 parts by weight of the modified polypropylene and polyester. If the amount of the acid catalyst is less than 0.01 parts by weight, the effect of improving the grafting rate will not be sufficient, and if it exceeds 5 parts by weight, gel will be generated due to excessive reaction, which is not preferable.

In addition, in the present invention, in order to further prevent gel formation when the polyester and the modified polyolefin are melt-kneaded and reacted, 0% per 100 parts by weight of the modified polypropylene and the polyester in total is
．． 0.5 to 2.0 parts by weight of water may be added. If the amount of water added is less than 0.05 parts by weight, gel formation cannot be sufficiently prevented, and if it exceeds 2.0 parts by weight, the molecular weight of the graft copolymer will be too low and the compatibility will not be improved. becomes insufficient, which is not desirable. When an extruder is used for melt-kneading, water is continuously supplied into the extruder by a pump. In particular, it is preferable to add water after the kneading zone of the extruder.

In the present invention, the thus obtained kneaded product of modified polypropylene and polyester is heat treated in an inert atmosphere at a temperature 50 to 150°C lower than the melting point of the polyester for 1 to 100 hours to increase the grafting rate. further improvement can be achieved.

If the heat treatment temperature is higher than the melting point of polyester -50°C, the polymer will decompose and the pellets will be melted, while if it is lower than the melting point of polyester -150°C, the effect of improving the grafting rate will not be sufficient, which is not preferable. When polyethylene terephthalate is used as the polyester, the preferred heat treatment temperature is 120 to 230°C.

In addition, the heat treatment time depends on the heat treatment temperature, but generally 1
If the time is less than 1 hour, the effect of improving the grafting rate will not be sufficient, and 1
Even if it exceeds 00 hours, no further improvement in the grafting rate can be obtained, which is not preferable. More preferable heat treatment time is 5 to 50
It's time.

The inert atmosphere in which the heat treatment is performed is an atmosphere that does not substantially cause deterioration of the kneaded material, and includes an inert gas such as argon, a non-reactive gas such as nitrogen and hydrogen, or a vacuum. In particular, from a practical standpoint, it is preferable to perform the heat treatment in a nitrogen stream.

In addition, in order to perform the heat treatment efficiently, it is preferable that the kneaded material be in the form of pellets.

The polypropylene-polyester graft copolymer thus obtained has a high grafting rate and is good as a compatibilizer for engineering plastics such as polycarbonate resin and polyolefin, and generally has a content of 1 to 30% per 100 parts by weight of both. Add in parts by weight.

[For production]

After melt-kneading polypropylene modified with a specific glycidyl compound having an acrylamide group and an epoxy group and a polyester, the resulting product has a high grafting rate and little gel formation.

The reason why such an effect is obtained is not necessarily clear, but the reason is that the epoxy group of the glycidyl compound in the modified polypropylene and the -OH group or -C at the terminal of the polyester
This is thought to be due to its good reactivity with O-leaf groups.

〔Example〕

The present invention will be explained in further detail by the following examples.

In each of the Examples and Comparative Examples, the following were used as the raw material polypropylene, modifying resin, polyester, and additives.

[1] Polypropylene HPP: Bropyrepromo polymer [Melt flow rate (MFR230℃ 2.16kg load) 1.5g
/10 minutes, 9g/10 minutes] ■RPP: Propylene-ethylene random copolymer [ethylene content 2% by weight, melt flow rate 1.0g/10 minutes] ■PP-00
: Propylene bow, 9-decadiene (DO) random copolymer [ethylene content 0°4% by weight, melt flow rate 5g 710 minutes] ■PP-MUD : Propylene/7-methyl-1,6-
Octadiene (MUD) random copolymer [ethylene content 1.0% by weight, melt flow rate 2g/10 min] [2] Modifier AXE: Glycidyl compound represented by the following general formula [
Manufactured by Kanebuchi Chemical Industry (6)] ・MAH: Maleic anhydride [3] polyester ・PET: Polyethylene terephthalate (TR450
0, manufactured by Teijin ■, weight average molecular weight 104゜000, intrinsic viscosity [η] 0゜7, concentration of terminal carboxyl group 35m equivalent/kg) PBT: polybutylene ethylene terephthalate)
(TRB-K.

Manufactured by Teijin Mari, weight average molecular weight 38.000° Intrinsic viscosity [η
]0.73, concentration of terminal carboxyl group 60m equivalent 8g
to [4-acid catalyst/P-TSA: Bala-toluenesulfonic acid (Tokyo Kasei ■
[Manufactured by NOF ■] [51 radical generator/pox: Perhexin 2-5B]
Examples 1 to 8 and Comparative Examples 1 to 5 Various polypropylenes (PP) shown in Table 1 and
A modifying comonomer of the type and amount shown in the table, and a first
Tri-blend the amount of radical generator shown in the table using a Henschel mixer, then use Labo Plastomill.
200 t: The mixture was melt-kneaded at 80 rpm for 5 minutes to carry out graft polymerization to obtain modified polypropylene.

The modified polypropylene obtained in this way, polyethylene terephthalate (PET) or polybutylene terephthalate (PBT) as a polyester, and an acid catalyst as required are blended in the proportions shown in Table 1, and in a lab blast mill, Graft polymerization was carried out by melt-kneading at 280° C. and 80 rpm for 5 minutes.

The graft ratio of polyester in the obtained polypropylene-polyester graft copolymer was measured.

The results are shown in Table 1 together with the grafting rate of the modifying monomer in the modified polypropylene.

(1) MFR: Value measured according to JIS K7210.

(2) Grafting rate of modifying monomer: ■For AX: After dissolving modified polypropylene in boiling xylene and removing insoluble components, the dissolved components were precipitated with methanol, and this was pressed to a thickness of about 50 mm. , I
The R spectrum was measured, and the peak of the expansion and contraction of the C-〇 bond of AXE (1648 cm"") and the isotaph f 4-/
It was calculated from the ratio of PP to one of the peaks (840 cm-') characteristic of PP.

■For MAR: Press modified polypropylene to a thickness of about 50 cm, measure the IR spectrum, and measure the expansion and contraction peak of the C=0 bond of maleic anhydride (1780 cm -'
) and one of the peaks specific to Aitsu Tactical PP (
840 cm-').

(3) Grafting ratio of polyester: modified polypropylene-polybutylene terephthalate graft copolymer and modified polypropylene-polyethylene terephthalate graft copolymer with a particle size of 0.246 mm.
It was pulverized and extracted with metacresol at 120°C to remove unreacted polybutylene terephthalate. After that, the remaining sample was press-molded to a thickness of 50 to 10 mm.
A film of 0.0 cm was prepared, the IR spectrum was measured, and the peaks (700, 1504, 1580 cm
-'), the content was calculated using the following formula.

As is clear from Table 1, the polypropylene-polyester graft copolymer produced by the production method of the present invention had a high polyester grafting rate.

On the other hand, a polypropylene-polyester graft copolymer made of modified polypropylene using maleic anhydride as a modifying polymer had a low polyester grafting rate.

The polypropylene-polyester graft copolymers obtained in Examples 2 and 6 were heat-treated at 170°C under a N2 stream for 24 hours, and the subsequent grafting rates were determined as in Example 1.
It was measured in the same manner.

The grafting rate was 22.3% by weight for the copolymer of Example 9 (heat-treated copolymer of Example 2), and 22.3% by weight for the copolymer of Example 10 (heat-treated copolymer of Example 6). ) and 3
It was 0.7% by weight, which was better than each of the corresponding examples.

〔Effect of the invention〕

As detailed above, in the method of the present invention, polypropylene modified with a specific glycidyl compound having an acrylamide group and an epoxy group and a polyester are melt-kneaded to form a graft copolymer. is high, and there is little gel formation.

The polypropylene-polyester graft copolymer thus obtained is extremely effective as a compatibilizer for engineering plastics such as polycarbonate resins and polyolefins.

Procedural amendment (spontaneous) June 7, 1991 1990 Patent Application No. 100647 2 Name of the invention Process for producing polypropylene-polyester graft copolymer 3 Relationship with the case of the person making the amendment Name of patent applicant Name Tonen Corporation 4 Agent address: 1-8-10-5 Iidabashi, Chiyoda-ku, Tokyo
Date of amendment order Heisei Month, Day (starting port) 6 Specification subject to amendment (1) [Polyolefin J] on page 3, line 17 of the specification
"Polypropylene", corrected.

(2) On page 7, line 1 of the specification, [Polyolefin J is corrected to be "polypropylene."

(3) "Polyolefin" on page 7, line 4 of the specification is corrected to "polypropylene."

(4) "It is an alkyl group, and n represents an integer from 1 to 4" on page 13, lines 3 and 4 of the specification is corrected to "it is an alkyl group."

(5) On page 16, line 19 of the specification, "equimolar amount" is corrected to "equimolar amount or more."

(6) "Polyolefin" on page 19, line 16 of the specification is corrected to "polypropylene."

(7) "Polyolefin" on page 19, lines 17 to 18 of the specification is corrected to "polypropylene j."

(8) "Polyolefin" in the first line of page 21 of the specification is replaced with "
"Polypropylene", corrected.

(9) [Preferable] on page 21, lines 5 and 6 of the specification.

. ] is corrected to "preferable."

GO) "Polyolefin" on page 21, line 12 of the specification is corrected to "polypropylene."

"Polyolefin" on page 21, line 19 of the αυ specification is replaced with "
"Polypropylene", corrected.

Q22 “Polyolefin” in line 22, line 14 of the specification is “
"Polypropylene", corrected.

rl on page 25, line 17 of the 03 specification, 5 g/10 minutes,
Correct "9g/10 minutes" to "rl, 5 g/10 minutes".

"Ethylene content" on page 26, line 2 of the Q41 specification is r
DD content”.

A99 Specification No. 26, lines 6 to 7, "ethylene content" is corrected to "rMOD content".

that's all

Claims (5)

[Claims] (1) (a) The following general formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is H or an alkyl group having 1 to 6 carbon atoms,
Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms and having at least one glycidyloxy group, and n is an integer of 1 to 4.
0% by weight graft-polymerized modified polypropylene 90-1
0 parts by weight of polyester (b) and 10 to 90 parts by weight of polyester (b). (2) In the method according to claim 1, the polypropylene skeleton of the modified polypropylene has the following general formula: ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R_1 to R_4 are H or an alkyl group having 1 to 6 carbon atoms. , n represents an integer of 1 to 20.) A method for producing a polypropylene-polyester graft copolymer, comprising a copolymer of a non-conjugated diene comonomer represented by the following formula and propylene. (3) The method according to claim 1 or 2, characterized in that, following the melt-kneading, heat treatment is performed in an inert atmosphere at a temperature 50 to 150°C lower than the melting point of the polyester for 1 to 100 hours. A method for producing a polypropylene-polyester graft copolymer. (4) In the method according to any one of claims 1 to 3, 0.01 to 5 parts by weight of an acid catalyst based on a total of 100 parts by weight of the (a) modified polypropylene and the (b) polyester. 1. A method for producing a polypropylene-polyester graft copolymer, which comprises adding. (5) In the method according to any one of claims 1 to 4, the polyester has an intrinsic viscosity [η] of 0.3 to 1.8.
and the concentration of terminal carboxyl group is 10 to 200 m equivalent/k
A method for producing a polypropylene-polyester graft copolymer, characterized in that g.