JP3449833B2 - 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 dicarboxylic acid unit represented by the following formula (1) —CO—CH ₂ —CH (CH ₃ ) —CH ₂ —CO— (1) in the molecule, ie, 3-methylpentane It is a plasticizer composed of a polyester having diacid units. 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 3
Derived from alkyl esters of -methylpentanedioic acid or 3-methylpentanedioic acid. 3-methylpentanedioic acid is, for example, mass-produced and easily available 3-methylpentanedioic acid
Methyl-1,5-pentanediol, β-methyl-δ-
It can be industrially produced from valerolactone, 2-hydroxy-4-methyltetrahydropyran or the like by an oxygen oxidation method. The polyester 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. Examples of the dicarboxylic acid unit include the following formula (4) -CO-R-CO- (4) [wherein, R is a divalent saturated aliphatic hydrocarbon group having 2 to 20 carbon atoms (provided that 1- Excluding methyl propylene group),
Represents a saturated alicyclic hydrocarbon group or an aromatic hydrocarbon group]
Preferred are dicarboxylic acid units represented by, for example, adipic acid, pimelic acid, suberic acid, azelaic acid, saturated aliphatic dicarboxylic acid units such as sebacic acid, saturated alicyclic dicarboxylic acid units such as cyclohexanedicarboxylic acid, phthalic acid, Aromatic dicarboxylic acid units such as 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, 3-methylpentanedioic acid or an alkyl ester thereof or a dicarboxylic acid mixture containing the same and a low molecular weight diol are charged at a desired ratio, and an esterification or transesterification reaction is performed.
A polyester can be produced by further subjecting the resulting reaction product to a polycondensation reaction in the presence of a polycondensation catalyst at high temperature and 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. In Examples and Comparative Examples, “parts” means “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 1 146 parts of 3-methylpentanedioic acid 142 parts of 1,8-octanediol are charged into a reaction vessel, and the mixture is heated under stirring in a stream of nitrogen gas to raise the temperature to 190 to 200 ° C. over 6 hours while continuously distilling out generated water outside the reaction system. Warmed. Thereafter, 45 parts of 2-ethylhexanol as the terminating agent, and 0.5 parts tetraisopropyl titanate was added as a beauty catalysts Oyo 50 parts of toluene, the acid value is below 1.0KOHmg / g with a reflux condenser Up to 180-1
The heating was continued at 90 ° C., and the generated water was azeotropically removed with toluene, and was continuously removed from the reaction system. Next is 1 torr
Then, toluene, excess alcohol components and low boiling components were removed to obtain polyester A (n = 11.7). 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 A reaction vessel was charged with 314 parts of 3-methylpentanedioic acid, 310 parts of 1,9-nonanediol and 0.4 part of dibutyltin oxide as a catalyst, and heated under stirring in a stream of nitrogen gas. The temperature was raised to 200 ° C. over 6 hours while continuously distilling out the generated water out of the reaction system. Then 10t
The pressure was reduced to orr and heating was continued to drive the reaction to sufficiently lower the acid value. Thereafter, the pressure was returned to normal pressure, and 2 g
-Add 90 parts of ethylhexanol and 80 parts of toluene,
Hereinafter, polyester B (n
= 10.4). Using this polyester B, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1, and a tensile test and a low-temperature flexibility test were performed. The results are shown in Table 1. Example 3 219 parts of 3-methylpentanedioic acid, 146 of azelaic acid
Parts, 3-methyl-1,5-pentanediol 51 parts,
276 parts of 1,9-nonanediol, n-octanol 2
20 parts, 60 parts of toluene and 0.8 parts of tetraisopropyl titanate as a catalyst are charged into a reaction vessel equipped with a reflux condenser, and heated to 200 ° C. while refluxing toluene while stirring in a nitrogen gas stream to produce. Water was continuously distilled out of the reaction system. Then, the reaction was further performed at 200 ° C. under a reduced pressure of 1 to 3 torr to lower the acid value and distill off toluene and the like to obtain polyester C (n = 10.
3) was obtained. Using this polyester C, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1, and a tensile test and a low-temperature flexibility test were performed. The results are shown in Table 1. Comparative Example 1 Polyester D (n = 11.8) was obtained in the same manner as in Example 1, except that 146 parts of adipic acid was used instead of 3-methylpentanedioic acid. Using this polyester D, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1, and a tensile test and a low-temperature flexibility test were performed. The results are shown in Table 1. Comparative Example 2 Polyester E (n = 10.5) was obtained in the same manner as in Example 2, except that 314 parts of adipic acid was used instead of 3-pentanedioic acid. Using this polyester E, a sheet having a thickness of 1 mm was prepared in the same manner as in Example 1, and a tensile test and a low-temperature flexibility test were performed. The results are shown in Table 1. [Table 1] As is apparent from Table 1, when polyesters A to C containing 3-methylpentanedioic acid units are used as plasticizers, polyesters D and E containing no 3-methylpentanedioic acid units are used as plasticizers. 100% modulus (M10
The value of 0) is small, which indicates that polyesters A to C have excellent plasticizing 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, there is provided a polyester plasticizer having excellent plasticizing efficiency and low-temperature flexibility. The polyester plasticizer of the present invention has sufficient durability such as extraction resistance and migration resistance, and is useful for plasticizing halogen-containing resins such as synthetic resins, especially vinyl chloride resins, vinylidene chloride resins, and chlorinated polyolefins. Useful as an agent.

Claims (1)

(57) The Claims 1. A formula in the molecule _{(1) -CO-CH 2 -CH} (CH 3) a dicarboxylic acid unit represented by -CH ₂ -CO- (1) A plasticizer comprising a polyester.