JPH036219A - Polyester resin and its preparation - Google Patents

Abstract

PURPOSE:To improve the bending strength and bending modulus by reacting a polyol component contg. a specific compd. with a polycarboxylic acid component. CONSTITUTION:A polycarboxylic acid component is reacted with a polyol component contg. a compd. of formula I [wherein Y is a group of formula II or III (wherein R is a 2-34C linear or branched alkyl or alkenyl group; R' is H, alkyl, or halogen); Z is a divalent residue of a hydroxyl compd.; A is a 2-3C alkylene group optionally substd. by phenyl; (m) is 1-100; and (n) is 0-100] in the presence of a zinc acetate catalyst at 140-230 deg.C for 2-15hr to give a polyester resin having mol.wt. of 300-80000 and repeating units of formula IV (wherein X is a polycarboxylic acid residue; and Q is a polyol residue and at least a part thereof is a residue of the compd. of formula I).

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to polyester resins and manufacturing methods.

[Prior Art] Conventionally, as a method for producing polyester resin, polyol components such as propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, and polyethylene glycol and polycarboxylic acid such as maleic anhydride, isophthalic acid, terephthalic acid, and adipic acid were used. A method of reacting acid components and the like is known.

[Problems to be Solved by the Invention] However, 1. When resins are molded using these polyol components, a product with very good hardness can be obtained, but there is a problem that the flexibility is insufficient. I'm here.

[Means for Solving the Problems] The present inventors have solved these problems and have arrived at the present invention as a result of intensive studies on a polyester resin that is easy to manufacture and a manufacturing method.

That is, the present invention provides a polyester resin having repeating units represented by the general formula (1) as essential units, [wherein, X is a polycarboxylic acid residue, Q is a polyol residue, and at least a portion thereof Represents the residue of the compound represented by formula (2).

Z-EObaYO:)(AO)-Hco (2)m
R is a linear or branched alkyl or alkenyl group having 2=34 carbon atoms, and R is a hydrogen atom or alkyl. ); and a method for producing a polyester resin, which comprises reacting a polyol component containing a compound represented by the general formula (2) according to claim 1 with a polycarboxylic acid component.

In general formula (2), the linear or branched alkyl group having 2 to 34 carbon atoms for R is a butyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a tocosyl group, 2-ethylhexyl group, 2-hexyldecyl group, 2-octylundecyl group, 2-decyltetradecyl group, 2-undecylhexadecyl group, etc.; straight chain or branched chain alkenyl group having 2 to 34 carbon atoms, Examples include decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, and octadecenyl group.

Among R, preferred is a straight chain or branched alkyl group having 8=24 carbon atoms. By using a hydrocarbon group having 2 or more carbon atoms as R, good water resistance can be obtained. Also, the number of carbon atoms is 34. If it exceeds , reactivity decreases.

Examples of the argyl group for R include argyl groups having 1 to 4 carbon atoms (such as methyl and ethyl groups), and examples of the halogen atom include chlorine and bromine atoms. Among R, preferred are a hydrogen atom and a methyl group.

In the general formula (2), the residue of the divalent hydroxyl group-containing compound of Z is the residue of the divalent hydroxyl group-containing compound.
It refers to a residue from which a valent hydroxyl group has been removed. The divalent hydroxyl group-containing compounds constituting this residue include alcohols, such as dihydric alcohols (ethylene glycol, propylene glycol, etc.), aliphatic diols having 3 to 10 carbon atoms (propane-1,3-diol, Butane-1
゜4-diol, pentane-1,5-diol, hexane-1,6-diol, etc.), alicyclic diols having 3 to 15 carbon atoms (cyclohexane-1,4-dimetatool, etc.), aromatic diols (Bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl)sulfone,.

2,2bis(4-hydroxy-3,5dibromophenyl)propane, etc.) and dihydric phenols (hydroquinone, etc.).

Among the hydroxyl group-containing compounds, dihydric alcohols are preferred, and ethylene glycol is particularly preferred.

In general formula (2), if A is an alkylene group, "C" is
Alkylene groups having 2 to 3 carbon atoms, such as 6.

Examples include tyrene, propylene U-butylene, etc.; substituted alkylene groups (styrene groups); and mixed groups thereof (for example, mixed groups of ethylene and propylene).

The alkylene group A forms an oxyalkylene group (AO) with zero oxygen atoms. The plurality of oxyalkylene groups (AO) may be the same or different, and the addition form may be a block addition type, a random addition type, or a mixture of both.

m is preferably 1-20.

n is preferably 0 to 50, particularly preferably 0 to 20,
be.

Two m's and two n's may be the same or different.

In general formula (2), m (YO) and n (AO)
may be combined in any order, or may be combined randomly or in blocks.

As the polyol component represented by general formula (2), table-
I can give you one thing.

Table-1 EO PO EO: Ethylene group: - Oxyethylene group Nioxypropylene group Nioxystyrene group The compound represented by the general formula (2) is added to a hydroxyl group-containing compound with an olefin oxide and, if necessary, an alkylene oxide. obtained by

Polyols other than the compound represented by general formula (2) forming the polyol residue of Q in general formula (1) include (1) propylene glycol, ethylene glycol, dipropylene glycol, diethylene glycol, 1 ,3
-butanediol, 1,4-butanediol, 2,3-
Butanediol, 1,5-bentanediol, 1,6-
Aliphatic glycols such as hexanediol and neopentyl glycol and their alkylene oxides [
(2) Hydroquinone, catechol, resorcinol, pyrogallol, bisphenols (bisphenol A1 bisphenol AD, bisphenol F1 bisphenol sulfone, etc.) and hydrogenated bisphenols Phenolic glycols with alkylene oxide added to; (3) Glycerin, trimethylolpropane, trimethylolethane, hexanetriol, pentaerythritol, jigata serine, α-methyl glucoside, sorbitol, xylit, mannitol, glucose, fructose , tri- to octavalent alcohols such as sucrose, and their alkylene oxide adducts; (4) Alkanolamines (triethanolamine, tripropaturamine, etc.), alkylene diamines (carbon number 2-6) [ethylene diamine, hexa Polyalkylene such as methylenediamine (alkylene has 2 to 2 carbon atoms)
6) Polyamines [diethylenetriamine, triethylenetriamine, etc., aromatic amines (aniline, phenylenediamine, diaminotoluene, xylylenediamine,
methylene dianiline, diethyltolylene diamine, diphenyl ether diamine, etc.), alicyclic amines (isophorone diamine, cyclohexylmethane diamine, cyclohegysylene diamine, etc.), heterocyclic amines (piperazine, aminethyl biverazine, etc.) 21
Examples include amino group-containing polyhydric alcohols obtained by adding alkylene oxide to such as those described in Japanese Patent Publication No. 044; and mixtures of two or more of these.

The polycarboxylic acids forming the polycarboxylic acid residue of (2) Dibasic acids such as glutaconic acid, adipic acid, malonic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, nadic acid, methylnadic acid, octylsuccinic acid, dodecenylsuccinic acid; Acid, 1,2,4-cyclohexanedicarboxylic acid, 2,5,7-naphthalene!・Dicarboxylic acid, 1.2.4-butanetricarboxylic acid, 1,2.5-
hexanetricarboxylic acid, 1,3-dicarboxyl-2
-, Methyl-2-methylene-carboxylic acid, pyromellitic acid, benzophore-7-carboxylic acid 4, cyclopentadiene-tetracarboxylic acid, tetra(methylene-carboxylic)methane, 1,2,7.8-octane tetracarboxylic acid Polycarboxylic acids having a valence of 3 or more, such as acids; can be used.

(3) Polymerized fatty acids such as dimers and trimers of ruic acid; and functional derivatives of these acids (anhydrides, lower alkyl esters, etc.).

These can be used alone or in a mixture of 52 or more.

Specific examples of polyester resins having repeating units represented by the general formula (1) of the present invention as essential units are shown in the table in Examples.
Shown in 2.

In the production of polyester resin, the amount of polyol is
The amount is usually 0.01 parts mol to 5 parts mol, preferably 0.1 parts mol to 1.2 parts mol, based on the polycarboxylic acid. If it exceeds this range, the physical properties of the resin will be extremely degraded.

When using the compound of general formula (2) in combination with other polyols, the amount of the compound of general formula (2) to be used is usually 5 to 50% by weight.
It is 100%.

In addition, the molecular weight of polyester resin is usually 300 to s o
o o o, preferably 1000 to 60000.

If the groove is not 300, the physical properties of the resin are not sufficient, and the 80,000
The production of polyester resins that exceed 100% is time consuming and does not have the benefit of improving the physical properties of the resin.

Any method can be used to produce the polyester resin. [For example, there is a method described in Sakae Takiyama - "Plastic Materials Course Polyester Resin" (1970).

] Specifically, for example, polyol, polycarboxylic acid, and zinc acetate as a catalyst are charged. Gradually increase the temperature to 140-23
React at 0°C for 2-15 hours. Furthermore, the reaction may be carried out under reduced pressure if necessary.

When the polyester resin is an unsaturated polyester resin, it is possible to produce a cured resin by crosslinking with a crosslinking agent such as styrene, p-methylstyrene, chlorostyrene, α-methylstyrene, vinyl acetate, methacrylate, diallyl phthalate, etc. Ru.

If necessary, a reinforcing filler can be added to the polyester resin of the present invention to further improve its physical properties. Suitable reinforcing fillers include glass fibers, mineral fibers, talc, mica, kaolin, and the like.

Further, if necessary, a flame retardant can be added to the polyester resin ζ of the present invention to impart flame retardancy.

Suitable flame retardants C include halogenated diphenyl ether compounds, halogenated polycarbonate compounds, halogenated polyphenylene oxide compounds, halogenated bisphenol resins, halogen-containing S-triazine compounds, halogenated polystyrene compounds, Examples include red phosphorus flame retardants, and if necessary, flame retardant aids such as antimony trioxide and zinc oxalate may be added to these to develop a synergistic effect.

Additionally, other additives such as thermal antioxidants, light stabilizers, pigments, dyes, nucleating agents, plasticizers, lubricants, crystallization promoters, and other thermoplastics (e.g. polyesters, polyolefins, polyamides, polycarbonates) can be added. , polyphenylene oxide, etc.) may be added to the extent that the physical properties are not impaired.

With respect to the weight of the polyester resin composition, the amount of reinforcing filler added is 0 to 70%, the amount of flame retardant added is 0 to 20%,
The amount of flame retardant aid added is preferably 0 to 15%.

[Examples] Hereinafter, the present invention will be briefly described with reference to Examples, but the present invention is not limited thereto.

Examples 1-6. Comparative Examples 1 and 2 A polyester resin was produced using a polyol component and a polycarboxylic acid component as shown in Table 2.

Table-2 No, f to No. 8: Compound P of the corresponding No. in Table-1
G: Brobylene glycol EG: Ethylene glycol 8AEO2: E02 mole adduct DE to bisphenol
C Nidiethylene glycol MA: Maleic anhydride TP: Terephthalic acid IP = Isophthalic acid AP: Adibic acid Wood Nigel The molecular weight of the polyester resin was measured using permeation chromatography.

Examples 7 to 12, Comparative Example 3.4 40 parts of glass fiber was sufficiently dispersed in 100 parts of each of the polyester resins obtained in Examples 1 to 6 and Comparative Example 1.2 using a twin-screw extrusion kneader to form a pellet. A polyester resin was obtained. After thoroughly drying this pellet, a test piece was molded using an injection molding machine. Table 3 shows the physical properties of the molded product obtained.

Table 3 [Effects of the Invention] The polyester resin obtained by the production method of the present invention has 1. , which solves the drawback of conventional products such as lack of flexibility, has excellent mechanical strength, especially bending strength and bending modulus.

Claims (1)

[Claims] 1. A polyester resin having repeating units represented by general formula (1) as essential units. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) [In the formula, It is a residue. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) (In the formula, Y is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R is a linear or branched alkyl or alkenyl group with 2 to 34 carbon atoms, R' is a hydrogen atom, an alkyl group or a halogen atom, Z is a residue of a divalent hydroxyl group-containing compound, and A has 2 to 2 carbon atoms, which may be substituted with a phenyl group.
In the alkylene group of 3, m is an integer of 1 to 100, and n is 0 or an integer of 1 to 100. )] 2. A method for producing a polyester resin, which comprises reacting a polyol component containing a compound represented by the general formula (2) according to claim 1 with a polycarboxylic acid component.