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CN101103063B - Hydroxypivalyl hydroxypivalate ester plasticizer composition and method of preparing the same - Google Patents

Hydroxypivalyl hydroxypivalate ester plasticizer composition and method of preparing the same Download PDF

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CN101103063B
CN101103063B CN2006800021707A CN200680002170A CN101103063B CN 101103063 B CN101103063 B CN 101103063B CN 2006800021707 A CN2006800021707 A CN 2006800021707A CN 200680002170 A CN200680002170 A CN 200680002170A CN 101103063 B CN101103063 B CN 101103063B
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CN101103063A (en
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金显圭
李启锡
李揆一
田炳圭
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LG Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/44—Preparation of carboxylic acid esters by oxidation-reduction of aldehydes, e.g. Tishchenko reaction
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F214/02—Monomers containing chlorine
    • C08F214/04—Monomers containing two carbon atoms
    • C08F214/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/18—Plasticising macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0016—Plasticisers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters

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Abstract

Provided are a plasticizer composition including a hydroxypivalyl hydroxypivalate ester and a neopentylglycol ester, and a method of preparing the plasticizer composition. The plasticizer composition provides a polyvinyl chloride resin having excellent properties of heat loss, migration resistance and plasticization efficiency, and tensile strength, elongation, etc.

Description

The ester plasticizer composition and method of making the same of hydroxypivalyl hydroxypivalate
Technical field
The present invention relates to a kind of ester class (hydroxypivalylhydroxypivalate ester) plasticizer composition of hydroxypivalyl hydroxypivalate, and more specifically, relate to the ester plasticizer composition of hydroxypivalyl hydroxypivalate that a kind of usefulness acts on the softening agent of polyvinyl chloride (PVC) resin.
Background technology
Polyvinyl chloride (PVC) RESINS is the polymkeric substance of vinyl chloride monomer or contains 50% or the multipolymer of more vinylchlorid, and is the widely used resin of making by extrusion molding, injection-molded, calendering etc.Polyvinyl chloride (PVC) RESINS is used to widespread use, and as tubing, electric wire, electric and engineering goods, toy, film, plate, imitation leather, tarpaulin, adhesive tape, food product pack and medical product, it all can use the aforesaid method manufacturing.According to the additive as softening agent, stablizer, filler, pigment etc. that wherein adds with suitable proportion, polyvinyl chloride (PVC) RESINS can have multiple character.
The softening agent that adds in the polyvinyl chloride (PVC) RESINS is used for providing workability, elasticity, electrical insulating property, binding property etc. to polyvinyl chloride (PVC) RESINS.The example of this softening agent comprises phthalic ester, adipic acid ester and trimellitate.Particularly, usually use as the phthalic ester of di (2-ethylhexyl) phthalate (DEHP), dibutyl phthalate (DBP), Di Iso Decyl Phthalate (DIDP), butyl benzyl phthalate (BBP) and diisononyl phthalate (DINP) with as the adipic acid ester of di-2-ethylhexyl adipate (DEHA).
Yet in endocrine disrupter is listed phthalic ester and adipic acid ester by Environmental Protection Agency and Japanese state-run pharmaceuticals food sanitation institute.Therefore, need exploitation not contain the softening agent of O-phthalic ester and adipic acid ester.
The 2 ethyl hexanoic acid that makes by the reaction of triglycol and 2 ethyl hexanoic acid [2-{2-(2-ethyl hexanoyl oxygen base)-oxyethyl group } oxyethyl group]-ethyl ester is not for containing the softening agent of phthalic ester or adipic acid ester.This compound has excellent workability in the fluoropolymer resin manufacturing processed, but character such as the elongation of the fluoropolymer resin that makes, clinging power, transparency are relatively poor.
Romania's patent No. 62655 has been reported and will be a kind of be used as softening agent by neopentyl glycol and the ester cpds that makes as reactions such as the butyric acid of lipid acid, 2 ethyl hexanoic acids.Yet, the neighbour phthalic acid ester of the consistency of this ester cpds and polyvinyl chloride (PVC) RESINS low, and the polyvinyl chloride (PVC) RESINS that adds this ester cpds has low transparency, relatively poor elongation and relatively poor migration resistance.
Summary of the invention
Technical problem
The invention provides plasticizer composition a kind of and prepared the method for this plasticizer composition, this plasticizer composition does not comprise known endocrine disrupter phthalic ester and adipic acid ester, and have excellent consistency with fluoropolymer resin, and it can make fluoropolymer resin have excellent tensile strength, elongation, hardness and migration resistance.
Technical scheme
According to a technical scheme of the present invention, a kind of ester plasticizer composition of hydroxypivalyl hydroxypivalate is provided, it comprises: the neopentyl glycol ester cpds that contains at least a compound by Chemical formula 1～3 expression; The ester compound that contains the hydroxypivalyl hydroxypivalate of at least a compound by chemical formula 4～7 expression; And the ester compound that contains the hydroxypivalyl hydroxypivalate of at least a compound by chemical formula 8～10 expression:
R 1OCO-C(CH 3) 2-OCOR 1...(1)、
R 2OCO-C(CH 3) 2-OCOR 3...(2)、
R 4OCO-C(CH 3) 2-OCOR 4...(3)、
R 1OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 1...(4)、
R 3OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 2...(5)、
R 2OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 3...(6)、
R 4OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 4...(7)、
R 1OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2C(CH 3) 2-CH 2-OCOR 1...(8)、
R 2OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2C(CH 3) 2-CH 2-OCOR 3...(9)、
R 4OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2C(CH 3) 2-CH 2-OCOR 4...(10)，
Herein, R 1And R 2Be C3～C12 alkyl independently of one another, and R 3And R 4Be C6～C10 aryl.
The ester plasticizer composition of described hydroxypivalyl hydroxypivalate can comprise: the neopentyl glycol ester cpds that contains at least a compound by Chemical formula 1～3 expression of 1～50wt%; The ester compound of the hydroxypivalyl hydroxypivalate that contains at least a compound by chemical formula 4～7 expression of 40～90wt%; And the ester compound of the hydroxypivalyl hydroxypivalate that contains at least a compound by chemical formula 8～10 expression of 1～40wt%.
The ester plasticizer composition of described hydroxypivalyl hydroxypivalate can comprise:
2-ethyl-caproic acid 3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propyl ester,
Phenylformic acid 3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propyl ester,
Phenylformic acid 3-benzoyloxy-2,2-dimethyl-propyl ester,
2-ethyl-caproic acid 2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester,
Phenylformic acid 2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester,
Phenylformic acid 3-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester,
Phenylformic acid 3-[3-(benzoyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester,
2-ethyl-caproic acid 2-{2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propoxycarbonyl }-2-methyl-propyl ester,
Phenylformic acid 3-{3-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2,2-dimethyl-propyl ester and
Phenylformic acid 3-{3-[3-(benzoyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2,2-dimethyl-propyl ester.
According to another technical scheme of the present invention, a kind of ester plasticizer method for compositions for preparing hydroxypivalyl hydroxypivalate is provided, it comprises: the hydroxypivalyl hydroxypivalate or the hydroxypivalyl hydroxypivalate of 20～50wt% and the mixture of neopentyl glycol that make 20～50wt%, C3～C12 fatty acid response with 50～80wt%, or with the C6 of 50～80wt%～C10 aromatic acid reaction, or with C3～C12 lipid acid and the C6～C10 aromatic acid reaction of 50～80wt%.
Above-mentioned lipid acid can be 2 ethyl hexanoic acid, and above-mentioned aromatic acid can be a phenylformic acid.
The ester plasticizer composition of described hydroxypivalyl hydroxypivalate can make by reacting down at 100～300 ℃ in 4～14 hours.
Based on the reactant of 100 weight parts, can in above-mentioned reaction, further add the dimethylbenzene of 1～20 weight part and the titanium isopropylate of 0.0001～1 weight part.
According to another technical scheme of the present invention, provide a kind of polyvinyl chloride (PVC) RESINS that comprises the ester plasticizer composition of described hydroxypivalyl hydroxypivalate.
According to another technical scheme of the present invention, provide ester compound by the hydroxypivalyl hydroxypivalate of chemical formula 5,6,8,9 and 10 expressions.
The ester plasticizer composition of hydroxypivalyl hydroxypivalate of the present invention can be used as softening agent in the polyvinyl chloride manufacturing processed, have the polyvinyl chloride of the character of excellent tensile strength, elongation, hardness and migration resistance with preparation.
Now will describe the present invention in detail.
Ester plasticizer composition according to the hydroxypivalyl hydroxypivalate of an embodiment of the invention does not comprise phthalic ester and the adipic acid ester that is considered to endocrine disrupter, and be applicable to polyvinyl chloride, so that the character of excellent tensile strength, elongation, hardness and migration resistance to be provided.The ester plasticizer composition of this hydroxypivalyl hydroxypivalate comprises: the neopentyl glycol ester cpds that contains at least a compound by Chemical formula 1～3 expression; The ester compound that contains the hydroxypivalyl hydroxypivalate of at least a compound by chemical formula 4～7 expression; And the ester compound that contains the hydroxypivalyl hydroxypivalate of at least a compound by chemical formula 8～10 expression:
R 1OCO-C(CH 3) 2-OCOR 1...(1)、
R 2OCO-C(CH 3) 2-OCOR 3...(2)、
R 4OCO-C(CH 3) 2-OCOR 4...(3)、
R 1OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 1...(4)、
R 3OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 2...(5)、
R 2OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 3...(6)、
R 4OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-OCOR 4...(7)、
R 1OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2C(CH 3) 2-CH 2-OCOR 1...(8)、
R 2OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2C(CH 3) 2-CH 2-OCOR 3...(9)、
R 4OCO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2C(CH 3) 2-CH 2-OCOR 4...(10)，
Herein, R 1And R 2Be C3～C12 alkyl independently of one another, and R 3And R 4Be C6～C10 aryl independently of one another.
The amount that contains the neopentyl glycol ester cpds of at least a compound by Chemical formula 1～3 expression can be at 1～50wt% of the ester plasticizer composition of hydroxypivalyl hydroxypivalate and more preferably in the scope of 10～40wt%.When the amount of this neopentyl glycol ester cpds was lower than 1wt%, meeting hindered plasticizing efficiency and other character of the polyvinyl chloride product that adds plasticizer composition owing to low tensile strength and high rigidity.On the other hand, when the amount of this neopentyl glycol ester cpds was higher than 60wt%, the cling film that comprises plasticizer composition can have too high binding property.
The amount of ester compound that contains the hydroxypivalyl hydroxypivalate of at least a compound by chemical formula 4～7 expression can be at 40～90wt% of the ester plasticizer composition of hydroxypivalyl hydroxypivalate and more preferably in the scope of 50～80wt%.When the amount of the ester compound of this hydroxypivalyl hydroxypivalate is lower than 40wt%, can reduce with the consistency of polyvinyl chloride (PVC) RESINS.When the content of the ester compound of this hydroxypivalyl hydroxypivalate was higher than 90wt%, the resin that makes can have character such as relatively poor tensile strength, elongation.
The amount of ester compound that contains the hydroxypivalyl hydroxypivalate of at least a compound by chemical formula 8～10 expression can be at 1～40wt% of the ester plasticizer composition of hydroxypivalyl hydroxypivalate and more preferably in the scope of 5～20wt%.When the ester compound of this hydroxypivalyl hydroxypivalate was lower than 1wt%, the cling film that comprises plasticizer composition can tangle in the cling film manufacturing processed owing to have too high binding property.On the other hand, when the amount of this hydroxypivalyl hydroxypivalate compound was higher than 40wt%, comprising the plasticizing efficiency of cling film of plasticizer composition and other character can reduce owing to low tensile strength and high rigidity.
In the compound of described chemical formulation, R 1And R 2Can be C6～C10 alkyl, more preferably 1-ethyl pentyl group independently of one another.R 3And R 4Can be C6～C8 aryl independently of one another, and phenyl more preferably.
Ester plasticizer composition according to the hydroxypivalyl hydroxypivalate of an embodiment of the invention can comprise:
2-ethyl-caproic acid 3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propyl ester (compound 1),
Phenylformic acid 3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propyl ester (compound 2),
Phenylformic acid 3-benzoyloxy-2,2-dimethyl-propyl ester (compound 3),
2-ethyl-caproic acid 2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester (compound 4),
Phenylformic acid 2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester (compound 5),
Phenylformic acid 3-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester (compound 6),
Phenylformic acid 3-[3-(benzoyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester (compound 7),
2-ethyl-caproic acid 2-{2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propoxycarbonyl }-2-methyl-propyl ester (compound 8),
Phenylformic acid 3-{3-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2,2-dimethyl-propyl ester (compound 9) and
Phenylformic acid 3-{3-[3-(benzoyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2,2-dimethyl-propyl ester (compound 10).
Figure S06802170720070716D000081
Compound (1),
Figure S06802170720070716D000082
Compound (2),
Compound (3),
Figure S06802170720070716D000084
Compound (4),
Figure S06802170720070716D000085
Compound (5),
Figure S06802170720070716D000086
Compound (6),
Figure S06802170720070716D000087
Compound (7),
Figure S06802170720070716D000088
Compound (8),
Figure S06802170720070716D000089
Compound (9),
Figure S06802170720070716D0000810
Compound (10).
Ester plasticizer composition according to the hydroxypivalyl hydroxypivalate of one embodiment of the present invention can be by a kind of method preparation, it comprises: the hydroxypivalyl hydroxypivalate or the hydroxypivalyl hydroxypivalate of 20～50wt% and the mixture of neopentyl glycol that make 20～50wt%, C3～C12 fatty acid response with 50～80wt%, or with the C6 of 50～80wt%～C10 aromatic acid reaction, or with C3～C12 lipid acid and the C6～C10 aromatic acid reaction of 50～80wt%.
The hydroxypivalyl hydroxypivalate of said mixture and neopentyl glycol can 5:5～9.5:0.5 weight ratio mix.Above-mentioned lipid acid can have 6～10 carbon atoms, and is preferably 2 ethyl hexanoic acid, and above-mentioned aromatic acid can have 6～8 carbon atoms, and is preferably phenylformic acid.
The ester plasticizer composition of the hydroxypivalyl hydroxypivalate of one embodiment of the present invention can be by preparing reactant reaction with above-mentioned weight ratio.
In other words, when hydroxypivalyl hydroxypivalate and fatty acid response, make the ester based composition that contains by the hydroxypivalyl hydroxypivalate of Chemical formula 1,4 and 8 compounds of representing.When hydroxypivalyl hydroxypivalate and aromatic acid reaction, make the hydroxypivalyl hydroxypivalate that contains by the compound of chemical formula 3,7 and 10 expressions.When hydroxypivalyl hydroxypivalate and lipid acid and aromatic acid reaction, make the hydroxypivalyl hydroxypivalate that contains by the compound of Chemical formula 1～10 expressions.For making other composition, can use method well-known in the art from contain compound compositions, to separate required compound by Chemical formula 1～10 expressions, wherein separation method is without limits.
For example, can use column chromatography to come separating compound.Sorbent material as stationary phase can be Al 2O 3, SiO 2, charcoal, MgSiO 2Deng, it all is well-known in the art.Especially, sorbent material can be a silica gel.Yet sorbent material is not limited to these materials.Moving phase can be the organic solvent as normal hexane, ethyl acetate, chloroform or toluene well known in the art.For example, moving phase can be normal hexane or ethyl acetate.Yet moving phase is not limited to above-mentioned these materials.Though the type of required solvent needs to change along with the polarity of the polarity of separated mixture and required stationary phase, but, usually use by having high polar solvent and having low polar solvent and mix the suitable polar solvent that has that makes in the proper ratio.
In compound by described chemical formulation, R 1And R 2Can be the 1-ethyl pentyl group, and R 3And R 4Can be phenyl, but be not limited thereto.
In esterification reaction process, owing to transesterify takes place and be produced as Chemical formula 1～3 and the by product of the compound of 8～10 expressions, so can make various types of ester cpds.Transesterify occurs in by lipid acid and aromatic acid reconstruction and is contained in the process of the ester bond in the hydroxypivalyl hydroxypivalate.
When hydroxypivalyl hydroxypivalate and lipid acid and aromatic acid reaction, the weight ratio of lipid acid and aromatic acid can be 1:99～99:1.
Reactor can be batch reactor, mixed-flow reactor or tubular reactor, but reactor is not limited thereto.
Esterification can be carried out under 100～300 ℃ 4～14 hours.When temperature of reaction was lower than 100 ℃, reaction was carried out very slow, thus preparation feedback product effectively.On the other hand, when temperature of reaction is higher than 300 ℃, reaction product decomposes and variable color.When the reaction times is less than 4 hours, the reacting weight deficiency, so transformation efficiency and productive rate are lower.On the other hand, when the reaction times surpassed 10 hours, reaction almost reached equilibrium conversion, and therefore further reaction stops basically.
Described method may further include entrainment agent.Based on the reactant of 100 weight parts, can in reaction, comprise the liquid entrainment agent of 1～20 weight part, perhaps in reactant, add the gas entrainment agent with the flow velocity of 0.1～10 times of reactor volume per hour.Entrainment agent is to help as the by product of esterification and the H that produces 2O discharges the material outside the reaction.According to the Le Xiatelie principle, remove the H of generation 2O helps the change of molecular balance, thereby owing to the reversed reaction of esterification reduces the preparation that helps required product.Therefore, use entrainment agent that the productive rate of required product is improved.Entrainment agent can be as the organic solvent of normal hexane, toluene, dimethylbenzene or as the rare gas element of nitrogen.Preferably, entrainment agent can be normal hexane, toluene, dimethylbenzene, nitrogen etc.Yet entrainment agent is not limited to these above-mentioned materials.
Described method may further include catalyzer.Based on the reactant of 100 weight parts, the amount of catalyzer can be 0.0001～1 weight part.Catalyzer can promote esterification.The example of catalyzer comprises an acidic catalyst as sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, tosic acid, methylsulfonic acid, alkylsurfuric acid etc.; Metal-salt as Tai-Ace S 150, lithium fluoride, Repone K, cesium chloride, calcium chloride, iron(ic) chloride, aluminum phosphate etc.; Metal oxide as heteropolyacid etc.; Natural/synthetic zeolite; Positively charged ion or anionite-exchange resin; And as the organo-metallic of tetralkyl titanate, its polymkeric substance etc.For example, catalyzer can be tosic acid or titanium isopropylate.Yet catalyzer is not limited thereto.
Required aftertreatment without limits after esterification was finished.For example, remove unreacted reactive material, use as NaOH, KOH and Na then by vacuum distilling 2CO 3The basic solution of the aqueous solution carries out neutralization reaction.Then make to wash neutralized reaction product with water, and optionally dehydration under reduced pressure, then to wherein adding sorbent material and filtering.
Now will describe the ester plasticizer method for compositions of the hydroxypivalyl hydroxypivalate of preparation one embodiment of the present invention in detail.
In flask, add the 2 ethyl hexanoic acid of mixture, 1～80wt% of the hydroxypivalyl hydroxypivalate of the hydroxypivalyl hydroxypivalate of 20～50wt% or 20～50wt% and neopentyl glycol and benzoic mixture with agitator and condenser, based on 1～20 weight part of the reactant of 100 weight parts as the dimethylbenzene of entrainment agent, based on 0.0001～1 weight part of the reactant of 100 weight parts titanium isopropylate as catalyzer, temperature rises to 220 ℃, makes this mixture reaction 4～14 hours then.After the esterification, use the vacuum pump decompression, then,, use the NaOH aqueous solution of 5～50 weight parts to carry out neutralization reaction based on the reactant of 100 weight parts to remove unreacted acid.Washing, dehydration are also filtered neutralized reaction product.As a result, make the ester plasticizer composition of hydroxypivalyl hydroxypivalate.
Can use the polyvinyl chloride (PVC) RESINS for preparing character according to the ester plasticizer composition of the hydroxypivalyl hydroxypivalate of one embodiment of the present invention with excellent tensile strength, elongation, hardness and migration resistance.Except the ester plasticizer composition of hydroxypivalyl hydroxypivalate, can use the material that is generally used for resins to prepare polyvinyl chloride (PVC) RESINS by the method that is generally used for resins.
In addition, can be used for any resin according to the ester plasticizer composition of the hydroxypivalyl hydroxypivalate of one embodiment of the present invention, to improve tensile strength, elongation, migration resistance and hardness except polyvinyl chloride (PVC) RESINS.Especially, the ester plasticizer composition of this hydroxypivalyl hydroxypivalate is applicable to the polyvinyl chloride (PVC) RESINS of cling film used in the food product pack, but also can be used for the polyethylene foams plate.
Beneficial effect
The ester plasticizer composition of hydroxypivalyl hydroxypivalate of the present invention can be used as softening agent in the polyvinyl chloride manufacturing processed, have the polyvinyl chloride of the character of excellent heat rejection, migration resistance and plasticizing efficiency with preparation.In addition, tensile strength, elongation etc. have been improved.
Embodiment
With reference to the following examples the present invention will be described in more detail.These embodiment only are used for the illustrative purpose, and are not in order to limit the scope of the invention.
Embodiment
Measure tensile strength, elongation, hardness, migration resistance and the heat rejection of the polyvinyl chloride resin samples that makes in embodiment and the comparative example by the following method.The results are shown in table 2.
Tensile strength
Based on ASTM D638, use U.T.M to measure tensile strength.Setting pinblock speed is 200mm/min, the breakpoint of working sample (breaking point).Tensile strength uses following formula to calculate: tensile strength (kgf/mm 2)=bear a heavy burden (kgf)/{ thickness (mm) * width (mm) }.
Elongation
Based on ASTM D638, use U.T.M to measure elongation.Setting pinblock speed is 200mm/min, the breakpoint of working sample.Elongation uses following formula to calculate: elongation (%)={ elongation/original length } * 100.
Hardness
Measure hardness so that plasticizing efficiency meets the requirements.Based on ASTM D2240,, read hardness value after 5 minutes with the syringe needle of sclerometer (A type) and a bit contacting fully of sample.Five points of each sample determination, and get its mean value respectively.Measuring immediately after the specimen preparation and its hardness is measured in specimen preparation after one day.
Above-mentioned test result is shown in table 2.
Measure heat rejection and migration resistance by following method.
Heat rejection
Use roller mill under 165 ℃ with compositions-treated 3 minutes with the thick thin slice of preparation 0.8mm.Then, use roller mill thin slice that 60g0.8mm is thick under 185 ℃ to handle 10 minutes with the thick sample of preparation 0.4mm.After 24 hours, the weight of working sample, and heat rejection uses following formula to measure: heat rejection (wt%)={ 1-(example weight after handling 10 minutes under 185 ℃)/60g} * 100.
Migration resistance
4 of the original weights (Wi) of measuring each sample to the radix point back, and be between the ABS resin plate that in 70 ℃ the baking oven sample thin slice of 3cm * 3cm is placed in temperature.Place 1kg to bear a heavy burden following 72 hours in the gained sample, in water-bath, preserve to surpass 4 hours, the weight of working sample (Wo) then so that with following formula calculating migration resistance: ooze the amount of moving (wt%)=(Wi-Wo)/Wi} * 100.
Embodiment 1
(1) the ester plasticizer preparation of compositions of hydroxypivalyl hydroxypivalate
2mol hydroxypivalyl hydroxypivalate, 1.6mol2-thylhexoic acid, 3.6mol phenylformic acid, 60g are had in the 2L4 neck round flask of agitator and condenser as the titanium isopropylate adding of catalyzer as dimethylbenzene, the 1.5g of entrainment agent, temperature rises to 220 ℃, makes this mixture reaction 8 hours then.
After the esterification, the pressure of flask is decompressed to 5mmHg,, uses the NaOH aqueous solution of 10wt% to carry out neutralization reaction then to remove unreacted acid at 220 ℃ of following use vacuum pumps.Make to wash neutralized reaction product and dehydration with water, to wherein adding sorbent material and filtering.As a result, make the ester plasticizer composition of hydroxypivalyl hydroxypivalate.Analyze the ester compound of prepared hydroxypivalyl hydroxypivalate, discovery consists of: 2-ethyl-caproic acid 3-(2-ethyl-hexylyloxy)-2 of 0.4wt%, 2-dimethyl-propyl ester, the phenylformic acid 3-of 2.5wt% (2-ethyl-hexylyloxy)-2,2-dimethyl-propyl ester, the phenylformic acid 3-benzoyloxy-2 of 4.3wt%, 2-dimethyl-propyl ester, 2-ethyl-caproic acid 2-[3-(2-ethyl-hexylyloxy)-2 of 6.2wt%, 2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester, the phenylformic acid 2-[3-of 16.9wt% (2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester, the phenylformic acid 3-[3-of 14.6wt% (2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester, the phenylformic acid 3-[3-(benzoyloxy)-2 of 44.9wt%, 2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester, 2-ethyl-caproic acid 2-{2-[3-(2-ethyl-hexylyloxy)-2 of 0.6wt%, 2-dimethyl-propoxycarbonyl]-2-methyl-propoxycarbonyl }-2-methyl-propyl ester, the phenylformic acid 3-{3-[3-of 2.7wt% (2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2, the phenylformic acid 3-{3-[3-(benzoyloxy)-2 of 2-dimethyl-propyl ester and 4.0wt%, 2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2,2-dimethyl-propyl ester.
Mentioned component and amount use gas chromatography mass spectrograph (GC-MS) to identify.
(2) the ester plasticizer preparation of compositions polyvinyl chloride (PVC) RESINS of use hydroxypivalyl hydroxypivalate.
Polyvinyl chloride (LG chemical company preparation with 100 weight parts, ProductName: LS100S) mix with the KP-630P as the Korea S Daehyup company limited preparation of Ca-Zn stablizer of 60 weight parts as the ester plasticizer composition of the hydroxypivalyl hydroxypivalate of the preparation of softening agent and 3 weight parts, then, use roller mill under 175 ℃ with mixture process 3 minutes, to form the thick thin slice of 5mm.Then, use reduction unit with the thin slice that makes 185 ℃ of following preheatings 3 minutes, heat 3 minutes, cooled off again 3 minutes, thereby the thick thin slice of formation 1mm.Then, with the thick web preparation C type dumbbell shaped sample of 1mm, and test.
Embodiment 2
Except according to the amount that changes employed reactive material shown in the table 1, prepare the ester plasticizer composition of hydroxypivalyl hydroxypivalate with the method identical with embodiment 1.The ester based composition of the hydroxypivalyl hydroxypivalate that analysis makes, and find to consist of: compound 1～10 is respectively 1.4wt%, 3.5wt%, 2.2wt%, 20.5wt%, 19.8wt%, 21.3wt%, 20.0wt%, 2.4wt%, 5.1wt% and 2.5wt%.
Then, the sample for preparing the ester plasticizer composition of the above-mentioned hydroxypivalyl hydroxypivalate that makes with the method identical with embodiment 1.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Embodiment 3
Except according to the amount that changes employed reactive material shown in the table 1, prepare the ester plasticizer composition of hydroxypivalyl hydroxypivalate with the method identical with embodiment 1.The ester based composition of the hydroxypivalyl hydroxypivalate that analysis makes, and find to consist of: compound 1～10 is respectively 2.2wt%, 3.4wt%, 1.4wt%, 32.0wt%, 19.5wt%, 17.3wt%, 10.6wt%, 4.0wt%, 5.1wt% and 1.6wt%.
Then, the sample for preparing the ester plasticizer composition of the above-mentioned hydroxypivalyl hydroxypivalate that makes with the method identical with embodiment 1.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Embodiment 4
Except according to the amount that changes employed reactive material shown in the table 1, prepare the ester plasticizer composition of hydroxypivalyl hydroxypivalate with the method identical with embodiment 1.The ester based composition of the hydroxypivalyl hydroxypivalate that analysis makes, and find to consist of: compound 1～10 is respectively 4.2wt%, 9.5wt%, 5.1wt%, 18.1wt%, 20.9wt%, 16.7wt%, 18.8wt%, 1.2wt%, 2.7wt%, 1.3wt%.
Then, the sample for preparing the ester plasticizer composition of the above-mentioned hydroxypivalyl hydroxypivalate that makes with the method identical with embodiment 1.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Embodiment 5
Except according to the amount that changes employed reactive material shown in the table 1, prepare the ester plasticizer composition of hydroxypivalyl hydroxypivalate with the method identical with embodiment 1.The ester based composition of the hydroxypivalyl hydroxypivalate that analysis makes is found to consist of: the compound 8 of the compound 1 of 5.3wt%, the compound 4 of 77.3wt%, 10.7wt% and other compound of 6.7wt%.Here, other compound is not an impurity, but intermediate.
Then, the sample for preparing the ester plasticizer composition of the above-mentioned hydroxypivalyl hydroxypivalate that makes with the method identical with embodiment 1.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Embodiment 6
Except according to the amount that changes employed reactive material shown in the table 1, prepare the ester plasticizer composition of hydroxypivalyl hydroxypivalate with the method identical with embodiment 1.The ester based composition of the hydroxypivalyl hydroxypivalate that analysis makes is found to consist of: the compound 10 of the compound 3 of 5.4wt%, the compound 7 of 87.1wt%, 5.1wt% and other compound of 2.4wt%.Here, other compound is not an impurity, but intermediate.
Then, the sample for preparing the ester plasticizer composition of the above-mentioned hydroxypivalyl hydroxypivalate that makes with the method identical with embodiment 1.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Comparative example 1
Except using plasticizer phthalic acid two-2-ethylhexyl of normal use (the LG chemistry company limited preparation of 60 weight parts, ProductName: DOP) as softening agent, and the KP-630P of Korea S Daehyup company limited preparation that uses 3 weight parts is as outside the Ca-Zn stablizer, prepares sample with the method identical with embodiment 1.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Comparative example 2
Except using normally used softening agent di-2-ethylhexyl adipate (preparation of LG chemistry company limited, ProductName:, prepare sample with the method identical with embodiment 1 DOA) as outside the softening agent.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Comparative example 3
Except using normally used plasticizer phthalic acid dinonyl (preparation of LG chemistry company limited, ProductName:, prepare sample with the method identical with embodiment 1 DINP) as outside the softening agent.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Comparative example 4
Except using normally used softening agent diisononyl adipate (preparation of LG chemistry company limited, ProductName:, prepare sample with the method identical with embodiment 1 DINA) as outside the softening agent.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Comparative example 5
Except using the acetyl tributyl citrate (ATBC) that usually in medical product, is used as non-softening agent based on phthalic ester, prepare sample with the method identical with embodiment 1 as the softening agent.Sample to preparation carries out the test identical with embodiment 1.The results are shown in table 2.
Table 1
Figure S06802170720070716D000191
Table 2
Tensile strength (kg/cm 2) Elongation (%) Heat rejection (wt%) Migration resistance (wt%) Hardness
Embodiment 1 2.13 408 2.45 0.27 74.9
Embodiment 2 2.11 412 2.51 0.31 74.8
Embodiment 3 1.74 415 2.52 0.38 74.6
Embodiment 4 2.12 416 1.74 0.63 74.4
Embodiment 5 1.72 420 3.05 0.88 73.5
Embodiment 6 2.02 409 2.82 0.72 75.6
Comparative example 1 1.75 397 2.14 0.26 74.5
Comparative example 2 1.71 392 3.62 0.72 73.9
Comparative example 3 1.83 419 2.01 0.41 75.2
Comparative example 4 1.91 410 2.86 0.64 74.6
Comparative example 5 2.08 422 4.15 0.60 74.0
As shown in table 2, to compare with those plasticizer compositions of comparative example, the plasticizer composition of the embodiment 1～6 that makes according to one embodiment of the present invention has the character of more excellent tensile strength, elongation, heat rejection and migration resistance.The hardness of embodiment 1～6 is similar to comparative example.
Though specify and described the present invention with reference to its illustrative embodiments, but will be understood by those skilled in the art that, do not depart under the spirit and scope of the present invention that limit as following claims and can carry out various changes in form and details.

Claims (12)

1. ester compound that is selected from by the hydroxypivalyl hydroxypivalate of the group of chemical formula 5～10 expression:
R 3C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 2...(5)
R 2C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 3...(6)
R 4C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 4...(7)
R 1C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 1(8)
R 2C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 3(9)
R 4C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 4(10)
Wherein, R 1And R 2Be C3～C12 alkyl independently of one another, and R 3And R 4Be C6～C10 aryl independently of one another.
2. the ester compound of hydroxypivalyl hydroxypivalate as claimed in claim 1, wherein R 1And R 2Be the 1-ethyl pentyl group, and R 3And R 4Be phenyl.
3. the ester plasticizer composition of a hydroxypivalyl hydroxypivalate, it comprises:
1～50wt% by in the neopentyl glycol ester cpds of Chemical formula 1～3 expression one or more;
40～90wt% by in the ester compound of the hydroxypivalyl hydroxypivalate of chemical formula 4～7 expression one or more; And
1～40wt% by in the ester compound of the hydroxypivalyl hydroxypivalate of chemical formula 8～10 expression one or more:
R 1C(＝O)-O-CH 2-C(CH 3) 2-CH 2-O-COR 1...(1)
R 2C(＝O)-O-CH 2-C(CH 3) 2-CH 2-O-COR 3...(2)
R 4C(＝O)-O-CH 2-C(CH 3) 2-CH 2-O-COR 4...(3)
R 1C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 1...(4)
R 3C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 2...(5)
R 2C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 3...(6)
R 4C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 4...(7)
R 1C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 1(8)
R 2C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 3(9)
R 4C(＝O)-O-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-COO-CH 2C(CH 3) 2-CH 2-O-COR 4(10)
Wherein, R 1And R 2Be C3～C12 alkyl independently of one another, and R 3And R 4Be C6～C10 aryl independently of one another.
4. the ester plasticizer composition of hydroxypivalyl hydroxypivalate as claimed in claim 3, it comprises:
2-ethyl-caproic acid 3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propyl ester,
Phenylformic acid 3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propyl ester,
Phenylformic acid 3-benzoyloxy-2,2-dimethyl-propyl ester,
2-ethyl-caproic acid 2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester,
Phenylformic acid 2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propyl ester,
Phenylformic acid 3-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester,
Phenylformic acid 3-[3-(benzoyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propyl ester,
2-ethyl-caproic acid 2-{2-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propoxycarbonyl]-2-methyl-propoxycarbonyl }-2-methyl-propyl ester,
Phenylformic acid 3-{3-[3-(2-ethyl-hexylyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2,2-dimethyl-propyl ester and
Phenylformic acid 3-{3-[3-(benzoyloxy)-2,2-dimethyl-propionyloxy]-2,2-dimethyl-propionyloxy }-2,2-dimethyl-propyl ester.
5. ester plasticizer method for compositions for preparing hydroxypivalyl hydroxypivalate as claimed in claim 3, it comprises: the hydroxypivalyl hydroxypivalate or the hydroxypivalyl hydroxypivalate of 20～50wt% and the mixture of neopentyl glycol that make 20～50wt%, C3～C12 fatty acid response with 50～80wt%, or with the C6 of 50～80wt%～C10 aromatic acid reaction, or with C3～C12 lipid acid of 50～80wt% and C6～C10 aromatic acid reaction
Wherein, the hydroxypivalyl hydroxypivalate in the described mixture is mixed with 5: 5～9.5: 0.5 weight ratio with neopentyl glycol.
6. method as claimed in claim 5, wherein, described lipid acid is 2 ethyl hexanoic acid, and described aromatic acid is a phenylformic acid.
7. method as claimed in claim 5, wherein, described being reflected at carried out under 100～300 ℃ 4～14 hours.
8. method as claimed in claim 5 wherein, based on the reactant of 100 weight parts, further comprises the liquid entrainment agent of 1～20 weight part in the described reaction, perhaps add the gas entrainment agent with the flow velocity of 0.1～10 times of reactor volume per hour in reactant.
9. method as claimed in claim 8, wherein, described entrainment agent is selected from the group that comprises normal hexane, toluene, dimethylbenzene, nitrogen and helium.
10. method as claimed in claim 5 wherein, based on the reactant of 100 weight parts, further adds the catalyzer of 0.0001～1 weight part in described reaction.
11. method as claimed in claim 10, wherein, described catalyzer is tosic acid or titanium isopropylate.
12. a polyvinyl chloride (PVC) RESINS, it comprises the ester plasticizer composition as claim 3 or 4 described hydroxypivalyl hydroxypivalate.
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