JP3449832B2 - Polyester plasticizer - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester plasticizer. [0002] Conventionally, phthalic acid has been used for the purpose of plasticizing a resin composed of a high molecular compound to improve moldability and to impart flexibility to a resin product composed of a high molecular compound. Plasticizers such as ester plasticizer, phosphate ester plasticizer, fatty acid ester plasticizer, epoxy plasticizer, polyhydric alcohol ester plasticizer, chlorinated paraffin, chlorinated biphenyl, and polyester plasticizer are used. ing. [0003] Among the above plasticizers, polyester plasticizers are superior in durability (age resistance, extraction resistance, migration resistance) to other plasticizers. But
It has been pointed out that low plasticizing efficiency and poor low-temperature flexibility, which are considered to be caused by the molecular weight, are problems, and it is desired to improve these. As a polyester plasticizer having excellent plasticization efficiency and low-temperature flexibility, a plasticizer comprising a polyester containing a branched diol as a diol component such as 2-methyl-1,3-propanediol or 2-methyl-1,8-octanediol. Have been proposed (see JP-A-61-78827 and JP-A-1-284520), and these can sufficiently solve the above problems. However, the dicarboxylic acid component, which is the other component of the polyester plasticizer, has not been sufficiently studied. Accordingly, an object of the present invention is to provide a polyester plasticizer having excellent plasticizing efficiency and low-temperature flexibility by focusing on the dicarboxylic acid component of the polyester plasticizer. Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of solving the above problems, and as a result, when a specific branched dicarboxylic acid is used as a dicarboxylic acid component in a polyester plasticizer, The inventors have found that a polyester plasticizer having improved plasticization efficiency and low-temperature flexibility can be obtained, and as a result of further investigation, the present invention has been completed. That is, the present invention relates to a polyester having a dicarboxylic acid unit represented by the following formula (1) —CO—CH ₂ —CH (CH ₃ ) —CO— (1) in the molecule, ie, a methyl succinic acid unit. Plasticizer. The polyester constituting the plasticizer in the present invention is preferably represented by the following formula (2) or (3). AM- (DM) n-A (2) T-D- (MD) n-T (3) In the above formula, M is a dicarboxylic acid unit represented by the formula (1) , D represents a diol unit, A represents a residue of a monoalcohol, and T represents a residue of a monocarboxylic acid. N represents the number of repetitions of (DM) or (MD). The dicarboxylic acid unit represented by the formula (1) is derived from an alkyl ester of methyl succinic acid or methyl succinic acid. The alkyl ester of methyl succinic acid can be obtained, for example, by subjecting a product obtained by hydroformylation of an alkyl methacrylate ester, which is mass-produced and easily available, to oxygen oxidation. Methyl succinic acid can be obtained, for example, by hydrolyzing an alkyl ester of methyl succinic acid. Thus, any of the compounds can be industrially manufactured at low cost. The polyester constituting the plasticizer in the present invention may contain a dicarboxylic acid unit other than the dicarboxylic acid unit represented by the formula (1) as long as the spirit of the present invention is not impaired. . As such a dicarboxylic acid unit,
The following formula (4) -CO-R-CO- (4) [In the above formula, R is a divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms (however, excluding a 1-methylethylene group), saturated Represents an alicyclic hydrocarbon group or an aromatic hydrocarbon group), for example, a saturated aliphatic dicarboxylic acid such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid Units, saturated alicyclic dicarboxylic acid units such as cyclohexanedicarboxylic acid, and aromatic dicarboxylic acid units such as phthalic acid, terephthalic acid, and isophthalic acid are used. It is desirable that the content of the dicarboxylic acid unit represented by the formula (4) is less than 50 mol% based on the total amount of the dicarboxylic acid units constituting the polyester. In addition, the dicarboxylic acid unit coexisted with the dicarboxylic acid unit represented by Formula (1) may be one type, or may be two or more types. In addition, D in the above formulas (2) and (3)
The diol unit represented by is not particularly limited. For example, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,3-
Butylene glycol, 1,4-butanediol, 1,5
-Pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 2-methyl-1,8-octanediol,
1,9-nonanediol, 1,10-decanediol,
Low molecular diol units such as neopentyl glycol are used. These diol units may be used alone or in combination of two or more. In the above formulas (2) and (3), the monoalcohol residue represented by A and the monocarboxylic acid residue represented by T are derived from monoalcohols or monocarboxylic acids which are polyester terminators. is there. As such a monoalcohol, a saturated aliphatic alcohol having 2 to 22 carbon atoms, preferably a saturated aliphatic alcohol having 6 to 18 carbon atoms is used, and examples thereof include isoheptanol, n-octanol, 2-ethylhexanol, isononanol, and isodecanol. , Stearyl alcohol and the like. Further, as the monocarboxylic acid, a saturated fatty acid having 2 to 22 carbon atoms, preferably a saturated fatty acid having 6 to 18 is used,
For example, caproic acid, caprylic acid, lauric acid, myristic acid, stearic acid, coconut oil fatty acid and the like can be mentioned. Incidentally, the polyester in the present invention, such A,
It is not necessary to have T. In the above formulas (2) and (3), n is 2 to
It is preferably in the range of 30 and more preferably in the range of 7 to 15. The method for producing the polyester constituting the plasticizer in the present invention is not particularly limited, and a known polyester condensation polymerization method can be applied. For example, methyl succinic acid or its alkyl ester or a dicarboxylic acid mixture containing the same and a low molecular weight diol are charged at a desired ratio, esterification or transesterification is performed, and the resulting reaction product is heated to a high temperature in the presence of a polycondensation catalyst. The polyester can be produced by further performing a polycondensation reaction under vacuum. In the above polyester production method, when obtaining a polyester having a predetermined n value, a reaction is carried out by adding a terminal terminator to a dicarboxylic acid mixture and a low molecular weight diol. At this time, the molar ratio of dicarboxylic acid / low molecular weight diol / terminal terminator is appropriately determined according to the type of dicarboxylic acid, low molecular weight diol and terminal terminator used. In the early stage of the reaction, only the dicarboxylic acid and the low molecular weight diol are reacted in the presence or absence of a solvent that can be azeotropic with water such as toluene and xylene but are incompatible with each other, and the desired acid is reacted. When a hydroxyl value or a hydroxyl value is obtained, a polyester having a predetermined n value can be produced by adding a terminal terminator. In the production of polyester, a wide variety of catalysts are used. Such catalysts include, for example,
Acid catalysts such as sulfuric acid, phosphoric acid, zinc chloride and p-toluenesulfonic acid, titanium compounds such as tetramethyl titanate, tetraethyl titanate, tetra-n-propyl titanate, tetraisopropyl titanate and tetrabutyl titanate, dibutyltin dilaurate and dibutyltin Oxides, tin compounds such as dibutyltin diacetate, and combinations of acetates such as magnesium, calcium, and zinc with antimony oxide or the above titanium compounds can be used. The production of the polyester is usually started by heating at atmospheric pressure to a temperature at which water can be distilled off, usually in the presence of these catalysts, when the distillation of water is complete or essentially complete. To remove excess low molecular weight diols and terminating agents. Usually, at the end of the reaction, the temperature is around 200 ° C. and the pressure is 1 to 10 torr.
r. The obtained polyester is used as a plasticizer as it is or by adding additives such as an anti-coloring agent, a whitening agent and a light-fast agent as needed. The plasticizer provided by the present invention has excellent plasticizing efficiency and low-temperature flexibility as compared with conventional polyester plasticizers, and has sufficient durability such as extraction resistance and migration resistance. , Synthetic resin, especially vinyl chloride resin,
It is used as a plasticizer for halogen-containing resins such as vinylidene chloride resins and chlorinated polyolefins. Further, the plasticizer of the present invention, for example, phthalic acid esters, phosphoric acid esters, aliphatic dicarboxylic acid esters, trimethyl litho acid esters, fatty acid esters, chlorinated fatty acid esters, epoxidized fatty acid esters, You may use together with other plasticizers, such as chlorinated paraffins. The polyester having a dicarboxylic acid unit represented by the formula (1) in the present invention is applicable not only to plasticizers but also to fields such as lubricants and lubricants. The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The “parts” in Examples and Comparative Examples
Represents parts by weight unless otherwise specified. In the following examples, the n value of the polyester was determined by the following method. That is, a 0.1% solution of polyester in tetrahydrofuran (THF) was prepared, and the number average molecular weight was measured using a GPC measuring device (manufactured by Tosoh Corporation) under the following measurement conditions, and the n value was calculated. Column: Showdex GPC KF-803,
Or Showdex GPC KF-802.5 (all manufactured by Showa Denko KK) Flow rate: THF, 1.0 ml / min Detector: RI detector Example 1 132 parts of methyl succinic acid, 1, 9- Nonanediol 15
Five parts were charged into a reaction vessel, and heated with stirring in a nitrogen gas stream, and the temperature was raised to 200 ° C. over 6 hours while continuously distilling off generated water outside the reaction system. Thereafter, 45 parts of 2-ethylhexanol and 50 parts of toluene were used as a terminal stopper.
Parts and tetraisopropyl titanate as catalyst.
5 parts were added and a reflux condenser was attached.
Heating was continued at 180 to 190 ° C. until the concentration became not more than mg / g, and the generated water was azeotropically distilled with toluene and continuously removed from the reaction system. Then, the pressure was reduced to a maximum of 1 torr to remove toluene, excess alcohol components and low boiling components,
Polyester A (n = 11.9) was obtained. Such polyester A was used as a plasticizer as it was. Using a kneader, 50 parts of the polyester A obtained above, 100 parts of polyvinyl chloride, 1 part of cadmium stearate and 1 part of barium stearate are mixed using a kneader.
The mixture was kneaded at 10 ° C for 10 minutes to prepare a compound. Then
This compound was press-molded at 160 ° C. for 5 minutes to obtain a sheet having a thickness of 1 mm. The following physical properties were measured for the obtained sheet. Table 1 shows the results. (1) Tensile test: A tensile test was performed according to JIS-K6723, and the tensile strength at 100% elongation (M100: 100% modulus) was measured. M10
The smaller the value of 0, the better the plasticization efficiency. (2) Low temperature flexibility test: ASTM-D-1043-51
The softening temperature was measured according to the method described in the above. The lower the softening temperature,
Excellent low temperature flexibility. Example 2 284 parts of methylsuccinic acid, 1,10-decanediol 3
37 parts and 0.4 parts of dibutyltin oxide as a catalyst were charged into a reaction vessel, and heated under stirring in a nitrogen gas stream, and 190 ° C. over 6 hours while continuously distilling out generated water outside the reaction system. Temperature. Then, the pressure was reduced to 10 torr and heating was continued to drive the reaction to lower the acid value sufficiently. Thereafter, the pressure was returned to normal pressure, and 90 parts of 2-ethylhexanol and 80 parts of toluene were added as a terminal stopper.
By the same operation as in Example 1, polyester B (n = 1
0.1) was obtained. Using this polyester B, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1.
A tensile test and a low temperature flexibility test were performed. The results are shown in Table 1. Example 3 231 parts of methylsuccinic acid, 141 parts of azelaic acid, 3-
63 parts of methyl-1,5-pentanediol, 258 parts of 1,9-nonanediol, 220 parts of n-octanol, 60 parts of toluene and 0.8 part of tetraisopropyl titanate as a catalyst are charged into a reaction vessel equipped with a reflux condenser. Then, heating was continued to 200 ° C. while refluxing toluene under stirring in a nitrogen gas stream, and water produced was continuously distilled out of the reaction system. Then, under reduced pressure of 1-3 torr, 20
The reaction was further carried out at 0 ° C. to drive the reaction to lower the acid value, and at the same time, distilling off toluene and the like to obtain polyester C (n = 1).
0.1) was obtained. Using this polyester C, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1.
A tensile test and a low temperature flexibility test were performed. The results are shown in Table 1. Comparative Example 1 Polyester D (n = 11.9) was obtained in the same manner as in Example 1, except that 146 parts of adipic acid was used instead of methylsuccinic acid. Using this polyester D, a thickness of 1 mm was obtained in the same manner as in Example 1.
Were prepared and subjected to a tensile test and a low-temperature flexibility test. The results are shown in Table 1. Comparative Example 2 Polyester E (n = 10.0) was obtained in the same manner as in Example 2, except that 314 parts of adipic acid was used instead of methylsuccinic acid. Using this polyester E, a thickness of 1 mm was obtained in the same manner as in Example 1.
Were prepared and subjected to a tensile test and a low-temperature flexibility test. The results are shown in Table 1. [Table 1] As apparent from Table 1, when polyesters A to C containing methyl succinic acid units are used as plasticizers, polyesters D containing no methyl succinic acid units are used.
In comparison with the case where E and E were used as plasticizers, the value of the 100% modulus (M100) of the obtained sheet was small, and it can be seen that polyesters A to C have excellent plasticization efficiency. Further, the sheet obtained when polyesters A to C are used as a plasticizer has a low flexibility temperature in a low-temperature flexibility test, and is excellent in low-temperature flexibility. According to the present invention, a polyester plasticizer having excellent plasticizing efficiency and low-temperature flexibility is provided. The polyester plasticizer of the present invention has sufficient durability such as extraction resistance and migration resistance, and is a synthetic resin, especially a plasticizer of a halogen-containing resin such as a vinyl chloride resin, a vinylidene chloride resin, and a chlorinated polyolefin. Useful as

Claims (1)

(57) From Claims 1] following formula in the molecule _{(1) -CO-CH 2 -CH} (CH 3) -CO- polyesters having dicarboxylic acid units represented by (1) Plasticizer.