JPH06136068A - Modified polyester - Google Patents

Abstract

PURPOSE:To provide a modified polyester having excellent compatibility with polypropylene resin and effective in improving the physical properties of polypropylene resin. CONSTITUTION:The modified polyester is produced by reacting 100 pts.wt. of a polyester polyol having a molecular weight of 500-10,000 with 5-100 pts.wt. of a compound containing unsaturated group and having >=2 methyl groups in the molecule.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a modified polyester having excellent compatibility, which is used as a modifier for polypropylene resin.

[0002]

2. Description of the Related Art Conventionally, problems with polypropylene resins (hereinafter abbreviated as PP) are poor impact resistance at low temperatures due to high embrittlement temperature and poor adhesion due to surface inactivity. As a method for solving these problems, a method of using a copolymer with ethylene or the like, and a method of adding polyisobutylene or diene rubber have been known.

[0003]

However, the conventional method using a copolymer is a method for improving the production of PP and cannot be said to be a simple method. Further, the method of adding a polymer such as polyisobutylene is not technically easy such as addition of a compatibilizer. Although the method using an additive having a molecular weight of about 10,000 or less is simple, there is no satisfactory compatibility with PP. An object of the present invention is to provide a useful additive having excellent compatibility with PP and improving the physical properties of PP.

[0004]

Means for Solving the Problems As a result of intensive studies to solve such conventional problems, the present inventors have found that a specific polyester modified product exhibits excellent additive performance, and the present invention It came to completion. That is, according to the present invention, 100 parts by weight of a polyester polyol having a molecular weight of 500 to 10000 is reacted with 5 to 100 parts by weight of an unsaturated group-containing compound having two or more methyl groups in the molecule and is excellent in compatibility. A modified polyester is provided.

In the blended product of modified polyester and PP obtained by the present invention, both components are uniformly dispersed, and as a result, the brittle temperature is low and the adhesiveness with other resins is excellent.
Further, it is expected that the adhesiveness with the urethane coating used as the surface coating is excellent. Examples of the polyester polyol of the present invention include polyesters having a molecular weight of 500 to 10,000, polyester amides, polyether esters, polycarbonates and the like which are usually used as reaction partners of polyisocyanates.

Examples of the polyesters and polyester amides include those obtained by a known method from polyhydric alcohols and polycarboxylic acids, optionally using diamines and amino alcohols in combination. Examples of polyhydric alcohols include ethylene glycol, diethylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol, 3-methylpentanediol, cyclohexanedimethanol, Examples include glycerin and trimethylolpropane. Examples of polyvalent carboxylic acids include succinic acid, adipic acid, sebacic acid, dimer acid, phthalic acid, phthalic acid alkyl esters, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid, and itaconic acid. Further, those obtained by ring-opening polymerization of cyclic esters such as butyrolactone, valerolactone and caprolactone are also included. Polyetheresters are the same as the above polyesters except that a part of the polyvalent alcohols used in the above polyesters is a polyetherpolyol.

As polycarbonates, esters of aliphatic diols or alicyclic diols such as 1,6-hexanediol and 1,4-cyclohexanedimethanol with cyclic carbonates such as dialkyl carbonates or diaryl carbonates or ethylene carbonates. Polycarbonate diol obtained by the exchange reaction can be mentioned.

The polyester polyol of the present invention preferably has a molecular weight of 500 to 10,000, more preferably 5
It is from 00 to 5000. When the molecular weight is less than 500, the characteristics as a polyester modified product, particularly the effect of lowering the embrittlement temperature of PP when added to PP, are not preferable. When the molecular weight exceeds 10,000, the viscosity of the polyester polyol increases and the reaction with the unsaturated group-containing compound becomes difficult, which is not preferable.

Examples of the unsaturated group-containing compound having two or more methyl groups in the molecule of the present invention include acrylic acid and isopropyl alcohol, isobutyl alcohol, neopentyl alcohol, 2-ethylhexanol. Esterification products such as methacrylic acid, itaconic acid, maleic acid and fumaric acid and methanol, ethanol, isopropyl alcohol, isobutyl alcohol, neopentyl alcohol, 2-ethylhexanol, etc. And so on. Unsaturated group-containing compounds having less than 2 methyl groups in the molecule are not preferred because the resulting modified polyester has poor compatibility with PP.

The unsaturated group-containing compound of the present invention is preferably reacted in an amount of 5 to 100 parts by weight based on 100 parts by weight of polyester polyol. If less than 5 parts by weight, PP
It is not preferable because the compatibility with is poor. If it exceeds 100 parts by weight, the viscosity of the modified polyester becomes high and the workability is deteriorated, which is not preferable.

The modified polyester of the present invention can be obtained by reacting a polyester polyol with an unsaturated group-containing compound. This reaction method is not particularly limited, and an ordinary polymerization method of an ethylenic monomer using a radical initiator or the like as a reaction catalyst can be used. In this reaction, a solvent can be used if necessary. Examples of the solvent include butyl acetate, dioctyl phthalate, dimethylformamide, cyclohexane and the like.

[0012]

The polyester modified product obtained by the present invention can be easily dispersed in PP by blending with PP, and the physical properties of PP can be improved. As a blending method, for example, a method of performing dry blending followed by melt mixing with a twin-screw extruder can be used.

[0013]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples,
All "parts" mean "parts by weight" and all "%" mean "% by weight".

Example 1 Poly (butylene adipate) polyol having a molecular weight of 2000 (hydroxyl value 56) 2 in a 500 ml separable flask.
Charge 10 parts and heat to 100 ° C. while flowing nitrogen gas. 90 parts of 2-ethylhexyl methacrylate in which 1.8 parts of benzoyl peroxide was dissolved was added dropwise from the dropping funnel. After completion of the dropping, the reaction was carried out for 1 hour, and the mixture was heated at 120 ° C. for 1 hour to obtain a modified polyester.

PP (manufactured by Mitsubishi Yuka, general-purpose grade MA for injection molding) in a kneader type Labo Plastmill (manufactured by Toyo Seiki)
3) 35 parts were charged and kneaded at 190 ° C for 3 minutes, and 15 parts of the polyester modified product obtained in this example was charged and kneaded at 190 ° C for 12 minutes. As a result of taking out the mixed resin and observing the dispersed state with a microscope (magnification: 400), it was found that the modified polyester was uniformly dispersed in a size of several microns.

Comparative Example 1 In the same manner as in Example 1, poly (butylene adipate) polyol 1 having 35 parts PP and a molecular weight of 2000 was prepared using Laboplast mill.
5 parts were kneaded. As a result of microscopic observation of the mixed resin,
The poly (butylene adipate) polyol was not dispersed in PP.

Example 2 A 500 ml separable flask was charged with 240 parts of poly (ethylene butylene adipate) polyol (hydroxyl value 110) having a molecular weight of 1000, and 100 was charged while flowing nitrogen gas.
Heat to ℃. 60 parts of isopropyl methacrylate in which 1.2 parts of benzoyl peroxide was dissolved was added dropwise from the dropping funnel. After completion of the dropping, the reaction was carried out for 1 hour, and the mixture was heated at 120 ° C. for 1 hour to obtain a modified polyester.

In the same manner as in Example 1, 35 parts of PP was charged into a kneader type Labo Plastomill and kneaded at 190 ° C. for 3 minutes, and 15 parts of the polyester modified product obtained in this Example was charged and the mixture was heated at 190 ° C. for 1 minute.
Kneaded for 2 minutes. Take out the mixed resin with a microscope (magnification 40
As a result of observing the dispersed state in 0), the modified polyester was uniformly dispersed in a size of several microns to 10 microns.

Comparative Example 2 In the same manner as in Example 1, 35 parts of PP and 15 parts of poly (ethylenebutylene adipate) polyol having a molecular weight of 1000 were kneaded with a Labo Plastomill. As a result of microscopic observation of the mixed resin, poly (ethylenebutylene adipate) polyol
The le was not dispersed in the PP.

Example 3 Poly (caprolactone) polyol having a molecular weight of 2000 (hydroxyl value 56) 210 was put in a 500 ml separable flask.
Part is charged and heated to 100 ° C. while flowing nitrogen gas.
90 parts of neopentyl acrylate in which 1.8 parts of benzoyl peroxide was dissolved was added dropwise from the dropping funnel. After dropping 1
After reacting for an hour, it was heated at 120 ° C. for 1 hour to obtain a modified polyester.

In the same manner as in Example 1, 35 parts of PP was charged into a kneader type Labo Plastomill and kneaded at 190 ° C. for 3 minutes, and 15 parts of the polyester modified product obtained in this Example was charged and the mixture was heated at 190 ° C. for 1 minute.
Kneaded for 2 minutes. Take out the mixed resin with a microscope (magnification 40
As a result of observing the dispersed state in (0), the modified polyester was uniformly dispersed in a size of several microns.

Comparative Example 3 In the same manner as in Example 1, 35 parts of PP and 15 parts of poly (caprolactone) polyol having a molecular weight of 2000 were kneaded with a Labo Plastomill. As a result of microscopic observation of the mixed resin, poly (caprolactone) polyol was not dispersed in PP.

Example 4 Poly (ethylene adipate) polyol having a molecular weight of 1000
200 parts of maleic acid and 10 parts of maleic anhydride were heated at 160 ° C. for 5 hours to obtain poly (ethylene adipate maleate) pol
(Hydroxyl value 55). 120 parts of this polyester and 66.6 parts of butyl acetate are charged into a 500 ml separable flask and heated to 100 ° C. while flowing nitrogen gas.
80 parts of 2-ethylhexyl methacrylate in which 1.6 parts of benzoyl peroxide was dissolved was added dropwise from the dropping funnel. After reacting for 1 hour after the dropwise addition and heating at 120 ° C. for 1 hour,
The pressure was gradually reduced to distill off butyl acetate to obtain a modified polyester.

In the same manner as in Example 1, 35 parts of PP was charged into a kneader type Labo Plastomill and kneaded at 190 ° C. for 3 minutes, and 15 parts of the polyester modified product obtained in this Example was charged at 190 ° C. for 1 minute.
Kneaded for 2 minutes. Take out the mixed resin with a microscope (magnification 40
As a result of observing the dispersed state in (0), the modified polyester was uniformly dispersed in a size of several microns.

Comparative Example 4 In the same manner as in Example 1, 35 parts of PP and 15 parts of poly (ethylene adipate maleate) polyol having a molecular weight of 2000 were kneaded with a Labo Plastomill. As a result of microscopic observation of the mixed resin, this polyol was not dispersed in PP.

Example 5 Poly (butylene adipate) polyol having a molecular weight of 1000
200 parts of fumaric acid and 12 parts of fumaric acid were heated at 180 ° C. for 6 hours to obtain poly (butylene adipate fumarate) polyol (hydroxyl value 54). 140 parts of this polyester and 50 parts of butyl acetate are placed in a 500 ml separable flask and heated to 100 ° C. while flowing nitrogen gas. 60 parts of isopropylmethacrylate in which 1.2 parts of benzoyl peroxide was dissolved was added dropwise from the dropping funnel. After completion of dropping, the reaction was carried out for 1 hour, heating at 120 ° C. for 1 hour, and then gradually depressurizing to distill off butyl acetate to obtain a modified polyester.

In the same manner as in Example 1, 35 parts of PP was charged into a kneader type Labo Plastomill and kneaded at 190 ° C. for 3 minutes, and 15 parts of the polyester modified product obtained in this Example was charged and the mixture was heated at 190 ° C. for 1 minute.
Kneaded for 2 minutes. Take out the mixed resin with a microscope (magnification 40
As a result of observing the dispersed state in (0), the modified polyester was uniformly dispersed in a size of several microns.

Using a 30 mm diameter twin-screw extruder, PP7
A mixture obtained by dry blending 0 part and 30 parts of polyester modified product was melt-kneaded at a rotation speed of 60 rpm and a temperature of 190 ° C. to be pelletized. Cylinder-Temperature 1
A sheet sample was prepared by applying an injection molding machine at 90 ° C and a mold temperature of 70 ° C. As a result of an Izod impact test (notched) at 25 ° C and -30 ° C, the results were 20.0 at 25 ° C and 9.0 at -30 ° C. (Unit is Kg.cm
/ cm) PP alone sample was also tested in the same way, 25 ℃
And 4.0 at -30 ° C.

Comparative Example 5 In the same manner as in Example 1, 35 parts of PP and 15 parts of poly (butylene adipate fumarate) polyol having a molecular weight of 2000 were kneaded with Laboplast mill. As a result of microscopic observation of the mixed resin, this polyol was not dispersed in PP.

Claims (1)

[Claims] 1. A polyester having an excellent compatibility obtained by reacting 100 parts by weight of a polyester polyol having a molecular weight of 500 to 10000 with 5 to 100 parts by weight of an unsaturated group-containing compound having two or more methyl groups in the molecule. Modified body.