CN101679708A - Composition of terephthalic acid esters for polymer resin and method of manufacturing the same - Google Patents
Composition of terephthalic acid esters for polymer resin and method of manufacturing the same Download PDFInfo
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- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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- C08L27/00—Compositions of homopolymers or 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
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- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
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Abstract
The present invention provides a terephthalic acid ester composition comprising at least three different terephthalic acid compounds. In this composition, at least one of those three different compounds has the terephthalic add with a different substituent and at least two of those compounds have the terephthalic acid with an identical substituent, the molar ratio of the compound having the terephthalic add with an identical substituent is 6-80 mol% for the total mol of the composition, and the molar ratio of the compound having the terephthalic add with a different substituent is 20-94 mol%.The composition of the present invention increases physical properties of polymer resin molded product including tensile strength, heating loss, elongation, age resistance and weatherability when it is added as a plastidzer during the processing of polyvinylchloride resin.
Description
Technical field
The present invention relates to a kind of terephthalate composition and method of making the same that can be used as softening agent, or rather, relate to a kind of terephthalate composition and method of making the same, said composition adds fashionable in the process of processable polymer resin (especially polyvinyl chloride (PVC) RESINS) as softening agent, the performance of fluoropolymer resin moulded product be can improve, tensile strength, weight loss on heating, elongation, ageing resistance and weathering resistance comprised.The invention still further relates to a kind of polymer resin composition that comprises this plasticizer composition and fluoropolymer resin.
Background technology
Fluoropolymer resin has been applied to every field and has come for life facilitates, and it is molded and shaped with multiple working method, and is used to produce multiple general merchandise or mechanicals thus.
Particularly, polyvinyl chloride (PVC) RESINS is modal resin, and it can be easy to by multiple working method molded and shaped, as compound extrusion moulding, injection molding, calendering and colloidal sol moulding etc.Polyvinyl chloride (PVC) RESINS can comprise tubing, interior wall or external wall of building material, electric wire, electronics or engineering goods, toy, film, sheet material, synthetic leather, band, food product pack and medical treatment product with the processing of one of aforesaid method to obtain multiple product as material.
Can give polyvinyl chloride (PVC) RESINS multiple processing characteristics as additives such as softening agent, extender plasticizer, stablizer, pigment, filler, whipping agent, lubricant, viscosity modifiers by adding.Softening agent is a kind of additive, and it plays the effect that improves workability by the frictional coefficient that reduces between fluoropolymer resin, and present known dissimilar softening agent and their different application and purposes.The most representative softening agent is phthalic ester, adipic acid ester, phosphoric acid ester and trimellitic acid ester plasticizer, and phthalic ester is modal softening agent among them.
Tetra hydro Phthalic anhydride (raw material of traditional phthalate plasticizers) has a unsettled ring structure, and except water and main raw, it is to very responsive with the reaction of impurity.And simultaneously, terephthalic acid has highly stable structure, so it can reduce the factor of the product purity that reduction causes because of side reaction.According to environmental regulations all over the world, therefore traditional phthalic acid softening agent must rethink the selection of raw material by progressively restriction use.
Some terephthalic acid ester compounds have been used as softening agent, but its performance as softening agent remains to be improved.
In order to overcome the problems referred to above, the inventor notices, unlike Tetra hydro Phthalic anhydride, as a small amount of terephthalic acid residual in p phthalic acid esterification's compound of softening agent quality of impact polymer rosin products not, and thus, because terephthalic acid can be at an easy rate and various pure combinations, so it can be the excellent matrix material standed for that multiple performance is transferred to softening agent.Therefore, the inventor attempts using terephthalic acid (raw material of PET resin) to replace generally being used for the Tetra hydro Phthalic anhydride of phthalate plasticizers, with by utilizing combining of terephthalic acid and suitable alcohol, the gratifying level that physicals is brought up to.
Summary of the invention
Technical problem
An object of the present invention is to provide a kind of terephthalic acid ester composition, it can comprise tensile strength, weight loss on heating, elongation, ageing resistance and weathering resistance by adding the performance that has improved the fluoropolymer resin moulded product in the fluoropolymer resin as softening agent.
Another object of the present invention provides a kind of terephthalate preparation of compositions method.
Another purpose of the present invention provides a kind of polymer resin composition that contains the terephthalic acid ester composition.
Technical scheme
Above-mentioned purpose of the present invention can be finished by following embodiment of the present invention.
Below will describe the present invention in detail.
The invention provides a kind of terephthalic acid ester composition, said composition comprises at least three kinds of different compounds that are selected from by in p phthalic acid esterification's compound of general formula 1 expression.
[chemical formula 1]
Wherein, R and R ' are identical or different C3～C12 alkyl independently, are preferably C6～C10 alkyl.
In the present composition, at least a in described three kinds of different compounds contains the terephthalic acid with different substituents, and in the described compound at least two kinds contain and have identical substituent terephthalic acid.Total mole number with these compounds is a standard, and the mol ratio that contains the compound with identical substituent terephthalic acid is 6～80mol%, and the mol ratio that contains the compound of the terephthalic acid with different substituents is 20～94mol%.
Substituting group in preamble and hereinafter described terephthalic acid is not meant at the nuclear substituted substituting group of the benzene of terephthalic acid, and is meant the substituting group of the hydrogen on the terephthalic acid that has replaced the alcohol that is derived from the preparation method aspect.In this specification sheets, and the not mentioned nuclear substituted substituting group of benzene at terephthalic acid, if but have the characteristic that the substituent terephthalate on phenyl ring like this shows softening agent, it just can be included in the standard of the present invention or the component that is considered as the present composition maybe can become the component of the present composition.
Composition of the present invention comprises the p phthalic acid esterification's compound more than at least three kinds by general formula 2～4 expressions, or rather, its comprise 3～77mol% the p phthalic acid esterification's compound by general formula 2 expression, 20～94mol% by p phthalic acid esterification's compound of general formula 3 expressions and 3～77mol% p phthalic acid esterification's compound by general formula 4 expressions.
[chemical general formula 2]
[chemical general formula 3]
[chemical general formula 4]
Wherein, R1 is different C3～C12 alkyl with R2 independently, and is different C6～C10 alkyl independently preferably.
The compound with general formula 2～4 expressions that is used as the component of the present composition is preferably:
1) 1,4-phthalic acid two (2-ethylhexyl) ester;
C
8H
17OCOC
6H
4CO
2C
8H
17
2) 1,4-phthalic acid-1-(2-ethylhexyl)-4-(C8～C10 branched-chain alkyl) ester;
C
9H
19OCOC
6H
4CO
2C
8H
17
And
3) 1,4-phthalic acid two (C8～C10 branched-chain alkyl) ester;
C
9H
19OCOC
6H
4CO
2C
9H
19
At this, C8～C10 branched-chain alkyl is represented mainly to comprise the C9 alkyl, and is comprised a small amount of C8 and C10 alkyl, particularly C8.Alkyl herein is derived from isononyl alcohol.Described isononyl alcohol is not pure C9 alcohol, but the mixture of different C9 alcohol or be derived from the C9 alcohol cut of tunning, and comprise the pure and mild C10 alcohol of C8, particularly a spot of C8 alcohol.Therefore, isononyl alcohol of the present invention can be regarded as C9 alcohol cut, and the C9 alkyl in this specification sheets can be regarded as and is derived from isononyl alcohol.
Therefore, in the superincumbent general formula, R1 specifically is meant the C8 alkyl, and R2 is the C9 alkyl that contains a small amount of C8 and C10 alkyl.
Terephthalic acid ester composition of the present invention can be used as the softening agent of fluoropolymer resin, to significantly improve the performance of fluoropolymer resin (particularly polyvinyl chloride (PVC) RESINS) moulded product, comprises tensile strength, weight loss on heating, elongation, ageing resistance and weathering resistance.
Composition of the present invention comprises at least three kinds of different p phthalic acid esterification's compounds.For example, composition of the present invention is by having p phthalic acid esterification's compound of different substituents (substituting group is R1 and R2) on the terephthalic acid and having identical substituent p phthalic acid esterification's compound (substituting group all is R1 or all is R2) form on terephthalic acid.
These different compounds with different substituents can have different functions and not damage the plasticity-of fluoropolymer resin, show that these compounds have the effect of remarkable enhancing fluoropolymer resin moulded product performance (as tensile strength, weight loss on heating, elongation, ageing resistance and weathering resistance) and do not reduce workability.The enhancing or the improvement of this fluoropolymer resin plasticity-and workability can realize by the ratio of regulating composition component.
Each components contents that forms the present composition is preferably regulated in above-mentioned scope.If the content of the p phthalic acid esterification's compound with different substituents of general formula 3 expressions is too little, then composition will mainly be made up of the identical substituent p phthalic acid esterification's compound that has of general formula 2 or 4 expressions.Consider that the compounds by general formula 2 or 4 expressions are used as traditional softening agent, composition of the present invention may be as broad as long on the combination of component and performance with traditional softening agent, makes the advantage that can not fully represent the present composition.Otherwise, if the content of the p phthalic acid esterification's compound with different substituents of general formula 3 expressions is too high, the composition that then has described component ratio can not prepare by following simple preparation method of the present invention, and complicated production technique and unsatisfied productivity remain problem to be solved.
Substituting group as p phthalic acid esterification's compound of a component of the present composition is preferably the alkyl with suitable carbon number.If use the alkyl of too small carbon number, then anti-transport property will be very poor.Otherwise if use the alkyl of excessive carbon number, then the consistency with fluoropolymer resin will reduce.Therefore, in the present invention, substituting group is preferably C3～C12 alkyl, C6～C10 alkyl more preferably, and most preferably be C8～C9 alkyl.
' different substituting groups ' herein comprise that those carbon numbers are identical but substituting group that structure is different.Therefore, the 2-ethylhexyl must be interpreted as ' different substituting groups ' with n-octyl herein.
The present invention also provides by the single step esterification and has prepared described terephthalate method for compositions.That is to say, terephthalate preparation of compositions method of the present invention comprises the steps: to make the terephthalic acid alcohol reaction different with at least two kinds by esterification, particularly, in the presence of esterifying catalyst, make at least two kinds of different alcohol reactions of terephthalic acid with the 60～90mol% of 10～40mol% with C3～C12 alkyl; And, obtain described terephthalic acid ester composition.
In this method, when alcohol be two kinds different when pure, the mol ratio of first kind of alcohol and second kind of alcohol is 1: 9～9: 1.At this moment, at least two kinds of different alcohol are preferably 2-Ethylhexyl Alcohol and isononyl alcohol, and the mol ratio of 2-Ethylhexyl Alcohol and isononyl alcohol is 1: 9～9: 1.
Catalyzer herein is preferably metallic alkoxide compound or acid catalyst, and it particularly is selected from the metallic alkoxide compound in titanate ester that comprises metatitanic acid four isobutyl esters and titanium isopropylate and the tin class that comprises Dibutyltin oxide or is selected from the acid catalyst that comprises in tosic acid and the vitriolic acid.
In the presence of nitrogen, cause esterification, outside reaction system, flow into to stop air.In order to remove the water that in reaction process, generates, preferably in reaction soln, feed nitrogen and become bubble.Esterification preferably caused 4～24 hours down at 200～300 ℃.And esterification carries out in organic solvent, carries out in the organic solvent in being selected from dimethylbenzene, toluene, dimethyl formamide (DMF), normal hexane and benzene especially.
A unique distinction of the present invention is that the composition that will comprise at least three kinds of different p phthalic acid esterification's compounds is used in as softening agent in the processing of fluoropolymer resin (particularly polyvinyl chloride (PVC) RESINS), to improve the performance of fluoropolymer resin moulded product.Composition of the present invention comprises at least three kinds of different p phthalic acid esterification's compounds, and its alkyl substituent that will be derived from least two kinds of different alcohol by esterification is introduced in two substituting groups of terephthalic acid and prepared.
Therefore, terephthalate preparation of compositions method of the present invention is included under the existence of esterifying catalyst, and terephthalic acid is had C3～C12 alkyl with at least two kinds, the step of the different alcohol reaction of preferred C6～C10 alkyl.
The content of terephthalic acid in total reactant is preferably 10～40mol%.If terephthaldehyde's acid content is low excessively,, but must use excessive alkoxide component even purpose of the present invention still may reach, show and still wasted some unreacted alkoxide components, perhaps, need make extra work for reclaiming unreacted alkoxide component, this is unfavorable for economical efficiency and productivity.Otherwise, if terephthalic acid too high levels, will the unreacted terephthalic acid of excessive production and have a substituent compound (terephthalic acid mono alkyl ester) that is incorporated on the terephthalic acid, even remove excessive component fully by purification step, but this still is unfavorable for the performance of productivity and product.In theory, terephthalic acid has two esterification positions, and therefore the content of alcohol must be the twice of terephthalic acid mole number.But, in the ordinary course of things, can accept 1.5 times terephthalic acid alcohol and can not cause any the problems referred to above.Therefore, based on the reactant total mole number, the preferred content of terephthalic acid is 10～40mol%, and based on the reactant total mole number, the preferred content of alcohol is 60～90mol%.Yet, even the content that esterification adds has exceeded above-mentioned scope, owing to can reach the purpose of invention by extra step, so this content always is not limited to this.
Except reactant of the present invention comprises at least two kinds of different alcohol, and reaction product of the present invention comprises beyond three kinds of different p phthalic acid esterification's compounds at least, too not big different of preparation method of the present invention and conventional esterification.Therefore, method of the present invention can be carried out under conventional esterification condition.
In the present invention, esterifying catalyst is preferably metallic alkoxide compound or acid catalyst.The example of metallic alkoxide compound is as four titan-alkoxides of metatitanic acid four isobutyl esters and titanium isopropylate [Ti (OR)
4] and as the dialkoxy tin [Sn (OR) of Dibutyltin oxide
2].The example of acid catalyst is tosic acid and sulfuric acid.With respect to the reaction mixture of 100 weight parts, the content of described catalyzer is preferably 0.001～1 weight part.If catalyst levels is very few, then reaction efficiency will reduce.Otherwise,, then may cause the product variable color if catalyst levels is too high.
Esterification of the present invention can carry out in organic solvent, and the example of described organic solvent is dimethylbenzene, toluene, dimethyl formamide (DMF), normal hexane and benzene.Esterification preferably carried out 4～24 hours (entering outside reaction system to stop air and steam) in the presence of nitrogen under 200～300 ℃.In order to remove water, preferably in reaction soln, feed nitrogen and become bubble by the condensation reaction generation of esterification.If necessary, reaction can be carried out under vacuum or decompression, to reach other purposes.
After esterification was finished, method of the present invention can comprise a purification step, removing residual terephthalic acid (though being a small amount of), and unreacted alcohol excess component.Particularly, solvent and unreacted alcohol excess can be removed by underpressure distillation.These compositions also can be by with in the alkaline solution and terephthalic acid or terephthalic acid mono alkyl ester and clean and remove.The example of alkaline solution herein is 2～25% yellow soda ash, 2～25% metabisulfite solutions, 2～25% potassium hydroxide solutions and 2～25% sodium hydroxide solutions.After removing unreacted composition or byproduct, use the absorption agent dehydration.Then, obtain the present composition by removing by filter absorption agent.
The inventive method is characterised in that, makes the terephthalic acid alcohol generation esterification different with at least two kinds, comprises the composition of at least three kinds of different p phthalic acid esterification's compounds with preparation.Compare with the method that has earlier that wherein prepares composition by at least three kinds of different p phthalic acid esterification's compounds that prepare separately of mixing, the advantage of the inventive method is to produce, exactly, present method has realized the simplification of production line, help productivity and economical efficiency, and kind by conditioned reaction condition and concentration of reactants or mol ratio, reactant and quantity etc., a kind of plasticizer composition is provided, and this plasticizer composition has and is used for the required multiple physicals of multiple polymers resin.
In a preferred embodiment of the present invention, use terephthalic acid (to call " HOOC-TP-COOH " in the following text) to carry out esterification with two kinds of different alcohol (following branch another name " R1OH " and " R2OH ").In this example, product is the mixture of three kinds of different p phthalic acid esterification's compounds (R1-OOC-TP-COO-R1, R1-OOC-TP-COO-R2 and R2-OOC-TP-COO-R2).At this moment, the esterification of each terephthalic acid that carries out at each response location is independently (to this means that each reaction result does not influence each other), and the content of terephthalic acid is that the content of 1 mole and R1OH and R2OH is respectively 1 mole, finish if react completely and R1OH and R2OH the speed of reaction of esterification is identical separately, then product will be R1-OOC-TP-COO-R1: R1-OOC-TP-COO-R2: the R2-OOC-TP-COO-R2 ratio is 1: 2: 1 a mixture.
If the content of R1OH and R2OH is different, for example 0.5mol and 1.5mol, then the product quantity that product quantity reduces and R2 replaces that replaces of R1 increases, and will generate the product of a small amount of R1 and R2 replacement.This result can estimate by regulating the alkoxide component ratio.Even, also can estimate consistent result when the add-on of alcohol therein during greater than terephthalic acid.For example, when R1OH added 2mol and R2OH adding 3mol, the ratio of product will be according to the ratio adjustment of alkoxide component.
The speed of response of R1OH is different with R2OH.Therefore, in real reaction, the speed of response of alkoxide component must be the important factor that influences the component ratio of reaction product.That is to say, even the add-on of each alkoxide component is identical, if the content of alkoxide component is bigger than terephthalic acid, for example the R1OH of 2mol and the R2OH of 2mol are joined in the 1mol terephthalic acid, the alkoxide component with fast response speed replaces manyly than the alkoxide component with long response time speed.
In actual esterification, still might take place two differential responses positions of terephthalic acid and not exclusively independent or reaction can not be finished fully or the influence of other reaction conditionss with expect different.However, still reasonably, supporting reactions thing mol ratio and speed of response are the viewpoints that influences the principal element of product component ratio to above-mentioned hypothesis.Therefore, having the composition of different components ratio can be by regulating these factors preparations among the present invention.
If (R1OH, R2OH and R3OH) is used for esterification with three kinds of different alcohol, then generate 6 kinds of different p phthalic acid esterification's compounds, R1-OOC-TP-COO-R1, R1-OOC-TP-COO-R2, R1-OOC-TP-COO-R3, R2-OOC-TP-COO-R2, R2-OOC-TP-COO-R3 and R3-OOC-TP-COO-R3.As mentioned above, the ratio of these products is influenced by the amount and the speed of reaction thereof of the reactant that added.If three kinds of different alcohol add with identical amount, and the total mole number of alcohol is the twice of terephthalic acid total mole number, and reaction carries out fully, and this ratio will be 1: 2: 2: 1: 2: 1.That is to say, total ratio with identical substituent p phthalic acid esterification's compound and total p phthalic acid esterification's compound with different substituents will be 1: 2, show the p phthalic acid esterification's compound with different substituents total amount will than react with two kinds of different alcohol obtain greatly.Can consider that these features select the type of alcohol, and determine its content.
In this invention, the ratio of product can be by using the quantity regulating based on the alkoxide component of above-mentioned hypothesis and condition, if but too many reactant in a reaction, occurs, then the possibility of result principal element of not only being expected changes, also can be changed, illustrate to be not easy to control this reaction by other secondary causes.Therefore, the reaction product that can generate by the esterifications of two kinds of different alcohol with suitable mixed and by the reaction product of other esterifications generations of two or three different alcohol to make plasticizer composition of the present invention with improved physicals.Compare with the ordinary method that makes composition with wherein preparing each component separately and the component of preparation mixed, this method has many-sided advantage.
The present invention further provides a kind of polymer resin composition that comprises described ester plasticizer composition.In the present invention, based on the polymer resin composition of 100 weight parts, the content of described plasticizer composition in polymer resin composition is preferably 5～250 weight parts.If content is less than 5 weight parts, then the workability of fluoropolymer resin will descend.If instead content surpasses 250 weight parts, then owing to the increase of the migration from fluoropolymer resin, the physicals of composition will reduce.
According to the application target of fluoropolymer resin, can add multiple additives, to reach needed resin property.For example, can add extender plasticizer, stablizer, pigment, filler, whipping agent, lubricant, viscosity modifier etc.
Plasticizer composition of the present invention can be used for fluoropolymer resin, and the example of described fluoropolymer resin is polyvinyl chloride (PVC) RESINS, acrylic resin, ABS resin, urethane resin, olefin resin, engineering plastic resin and vibrin, but is not limited thereto.
Polymer resin composition of the present invention can be used for producing mixture, electric wire mixture, waterproof cloth, flexible pipe, section bar, wallpaper, film, food product pack, medical treatment product, synthetic leather, sheet material, band, auto parts machinery, toy, electrical equipment or mechanical component etc.
Embodiment
Practice of the present invention and at present preferred embodiment will be by following embodiment illustration.
Yet, should be understood that according to present disclosure, those skilled in the art can make adjustment and improve within the spirit and scope of the present invention.
Embodiment
Embodiment 1
In 2 liter of 4 neck round-bottomed flask that agitator and condenser are housed, add the reaction mixture that the titanium isopropylate catalyzer of the isononyl alcohol of 2-Ethylhexyl Alcohol by mixing 1.806mol terephthalic acid, 3.611mol and 3.611mol and 0.0042mol makes, stir then.Be warming up to 220 ℃, under nitrogen, reacted 9 hours then.After reaction was finished, unreacted matters was removed in decompression under 150～220 ℃.Then with reaction mixture with the neutralization of 10% sodium hydroxide, and with 10% sodium sulfate cleaning.Reaction mixture is under reduced pressure dewatered and filter to obtain the ester plasticizer composition.The component ratio of composition is as follows: 1 of 9.8mol%, 1 of 4-phthalic acid two (2-ethylhexyl) ester, 54.2mol%, 1 of 4-phthalic acid-1-(2-ethylhexyl)-4-(different nonyl) ester, 36mol%, 4-phthalic acid dinonyl.
Embodiment 2
In 2 liter of 4 neck round-bottomed flask that agitator and condenser are housed, add by mixing 1.806mol terephthalic acid, the 2-Ethylhexyl Alcohol of 3.609mol and the isononyl alcohol of 3.611mol, and to carry out following experiment with embodiment 1 described identical mode.The component ratio of composition is as follows: 1 of 19.1mol%, 1 of 4-phthalic acid two (2-ethylhexyl) ester, 50.9mol%, 1 of 4-phthalic acid-1-(2-ethylhexyl)-4-(different nonyl) ester, 30mol%, 4-phthalic acid dinonyl.
Embodiment 3
Except using reaction mixture, to experimentize with embodiment 1 described identical mode by the isononyl alcohol preparation of the 2-ethylhexyl of the terephthalic acid that mixes 1.806mol, 5.023mol and 2.162mol.The component ratio of composition is as follows: 1 of 37.6mol%, 1 of 4-phthalic acid two (2-ethylhexyl) ester, 47.9mol%, 1 of 4-phthalic acid-1-(2-ethylhexyl)-4-(different nonyl) ester, 14.5mol%, 4-phthalic acid dinonyl.
Embodiment 4
Except using reaction mixture, to experimentize with embodiment 1 described identical mode by the isononyl alcohol preparation of the 2-ethylhexyl of the terephthalic acid that mixes 1.806mol, 5.744mol and 1.44mol.The component ratio of composition is as follows: 1 of 56.3mol%, 1 of 4-phthalic acid two (2-ethylhexyl) ester, 38.4mol%, 1 of 4-phthalic acid-1-(2-ethylhexyl)-4-(different nonyl) ester, 6.3mol%, 4-phthalic acid dinonyl.
Embodiment 5
Except using reaction mixture, to experimentize with embodiment 1 described identical mode by the isononyl alcohol preparation of the 2-ethylhexyl of the terephthalic acid that mixes 1.806mol, 6.501mol and 0.722mol.The component ratio of composition is as follows: 1 of 64.4mol%, 1 of 4-phthalic acid two (2-ethylhexyl) ester, 25.3mol%, 1 of 4-phthalic acid-1-(2-ethylhexyl)-4-(different nonyl) ester, 10.3mol%, 4-phthalic acid dinonyl.
The terephthalic acid ester composition of embodiment 1～5 preparation is used for the processing of polyvinyl chloride resin samples as softening agent.The physicals of using method hereinafter described to test this sample, its result is as shown in table 1.Based on the fluoropolymer resin of 100 weight parts, the content of described plasticizer composition is 42 weight parts, and does not use other additives.
The comparative example 1
By using conventional softening agent (di-2-ethylhexyl phthalate) preparation sample, use and test its physicals, and the result is as shown in table 1 with method identical described in the embodiment.
The comparative example 2
By using conventional softening agent (dioctyl terephthalate) preparation sample, use and test its physicals, and the result is as shown in table 1 with method identical described in the embodiment.
Table 1
It is real to implement the real contrast of contrast
Example 1 example 2 examples 3 examples 4 examples 5 are executed example 1 and are executed example 2
Tensile strength (kgf/mm
2) 2.38 2,40 2.43 2.27 2.28 2.09 2.24
Elongation (%) 225 226 227 227 226 212 227
Weight loss on heating (mg/cm
2) 1.24 1.26 1.25 1.25 1.24 5.76 2.5
Heating back draft intensity (%) 99.0 99.5 100.8 101.3 101.8 97.1 95.1
Heating back elongation (%) 93.8 94.1 94.3 95.5 95.8 68.2 88.2
(performance evaluation)
The ester plasticizer composition of preparation in embodiment and comparative example 1 and 2 is tested physicals by the following method.
Be used for the preparation of the sample of weight loss on heating and measurement
Composition was made the thin slice of 0.8 mm thick in 3 minutes 165 ℃ of following rollings by roller mill.Adopt pressing machine to press the sample that was transformed into 0.4 mm thick in 10 minutes the thin slice of 200g at 185 ℃.After 24 hours, with this samples weighing.Weight loss on heating calculates with following formula.Weight loss on heating (wt%)=1-(weight of 185 ℃ of reactions after 10 minutes)/200g * 100.
Measure the preparation of the sample of physicals
Poly (vinyl chloride) resin composition of the present invention was made the thin slice of 0.5 mm thick in 3 minutes 180 ℃ of following rollings by roller mill.With the thin slice of 200g adopt pressing machine 180 ℃, 15MPa pressed down 15 minutes and 10Mpa presses down the sample of making 1 mm thick in 2 minutes.
Tensile strength
Tensile strength is measured with ASTM D638.Particularly, use test instrument U.T.M is the stretching sample in the pinblock speed of 200mm/min.Measure breaking point also with following formula tensile strength calculated.Tensile strength (kgf/mm
2)=load value (kgf)/{ thickness (mm) * (mm) }.
Elongation
Elongation is measured with ASTM D638.Particularly, use test instrument U.T.M stretches sample at the pinblock velocity pull-down of 200mm/min.Measure breaking point and calculate elongation with following formula.Elongation (%)={ elongation/initial length } * 100.
Heating back draft intensity
Sample was heated 168 hours in 100 ℃ heat-resistant experiment usefulness baking oven, test its tensile strength with ASTMD638 then.Particularly, use test instrument U.T.M stretches sample at the pinblock velocity pull-down of 200mm/min.Measure breaking point also with following formula tensile strength calculated.Tensile strength (kgf/mm
2)=load value (kgf)/{ thickness (mm) * (mm) }.The result that the result who at room temperature obtains with ASTM D638 obtains after divided by heating, it is represented by percentage ratio.
Heating back elongation
Sample was heated 168 hours in 100 ℃ heat-resistant experiment usefulness baking oven, test its elongation with ASTMD638 then.Particularly, use test instrument U.T.M stretches sample at the pinblock velocity pull-down of 200mm/min.Measure breaking point and calculate elongation with following formula.Elongation (%)={ elongation/initial length } * 100.The result that the result who at room temperature obtains with ASTM D638 obtains after divided by heating, it is represented by percentage ratio.
Compare with 2 conventional softening agent with comparative example 1, confirm to have better physicals by the ester plasticizer that uses terephthalic acid, 2-Ethylhexyl Alcohol and isononyl alcohol preparation in an embodiment, comprise tensile strength and elongation, particularly You Yi weight loss on heating, heating back draft intensity and heating back elongation.Therefore, unlike other conventional softening agent, when composition of the present invention adds as softening agent, can improve the ageing resistance and the weathering resistance of fluoropolymer resin moulded product.
Industrial applicibility
Ester plasticizer composition of the present invention has played the effect that improves as the physicals of weight loss on heating, weathering resistance and ageing resistance, these performances are non-constants when using conventional softening agent, and it does not damage other physicalies as elongation and tensile strength of fluoropolymer resin when playing excellent softening agent effect.
It will be appreciated by those skilled in the art that disclosed notion can be easily as revising or design the basis of realization with other embodiments of the identical purpose of the present invention with embodiment in the above-mentioned specification sheets.Those skilled in the art it is also understood that these embodiments of equal value do not depart from the spirit and scope of the invention of illustrating in the appended claims.
Claims (18)
1, a kind of terephthalic acid ester composition, wherein, said composition comprises at least three kinds of different compounds that are selected from by in p phthalic acid esterification's compound of general formula 1 expression, at least a terephthalic acid that contains in described three kinds of different compounds with different substituents, and at least two kinds in the described compound contain and have identical substituent terephthalic acid, total mole number with respect to composition, the mol ratio that contains the compound with identical substituent terephthalic acid is 6～80mol%, and the mol ratio that contains the compound of the terephthalic acid with different substituents is 20～94mol%
[chemical formula 1]
Wherein, R and R ' are identical or different C3～C12 alkyl independently.
2, terephthalic acid ester composition according to claim 1, wherein, described composition comprises at least three kinds of p phthalic acid esterification's compounds by general formula 2～4 expressions, and total mole number with respect to the compound of representing by general formula 2～4, said composition comprise 3～77mol% the p phthalic acid esterification's compound by general formula 2 expression, 20～94mol% by p phthalic acid esterification's compound of general formula 3 expressions and p phthalic acid esterification's compound of 3～77mol% by general formula 4 expressions
[chemical general formula 2]
[chemical general formula 3]
[chemical general formula 4]
Wherein, R1 is different C3～C12 alkyl with R2 independently.
3, terephthalic acid ester composition according to claim 2, wherein, described compound by general formula 2～4 expressions is respectively:
1) 1,4-phthalic acid two (2-ethylhexyl) ester;
C
8H
17OCOC
6H
4CO
2C
8H
17
2) 1,4-phthalic acid-1-(2-ethylhexyl)-4-(C8～C10 branched-chain alkyl) ester;
C
9H
19OCOC
6H
4CO
2C
8H
17
And
3) 1,4-phthalic acid two (C8～C10 branched-chain alkyl) ester
C
9H
19OCOC
6H
4CO
2C
9H
19
4, terephthalic acid ester composition according to claim 2, wherein, described R1 is that C8 alkyl and described R2 are the C9 alkyl.
5, according to each the described terephthalic acid ester composition in claim 1～claim 4, wherein, described ester composition is with acting on the softening agent of producing fluoropolymer resin.
6, a kind of preparation terephthalate method for compositions, this method comprise the steps: to make terephthalic acid and at least two kinds of different alcohol reactions with C3～C12 alkyl by esterification in the presence of esterifying catalyst; And obtain the terephthalic acid ester composition, said composition comprises at least three kinds of different compounds that are selected from by in p phthalic acid esterification's compound of general formula 1 expression, wherein, at least a terephthalic acid that contains in described three kinds of different compounds with different substituents, and at least two kinds in the described compound contain and have identical substituent terephthalic acid, total mole number with respect to composition, the mol ratio that contains the compound with identical substituent terephthalic acid is 6～80mol%, and the mol ratio that contains the compound of the terephthalic acid with different substituents is 20～94mol%
Chemical formula 1
Wherein, R and R ' are identical or different C3～C12 alkyl independently.
7, preparation terephthalate method for compositions according to claim 6, wherein, with respect to the total mole number of reactant, the content of described terephthalic acid is that the content of 10～40mol% and described alcohol is 60～90mol%.
8, preparation terephthalate method for compositions according to claim 6, wherein, described two kinds of different alcohol are 2-Ethylhexyl Alcohol and isononyl alcohol, and the ratio of 2-Ethylhexyl Alcohol and isononyl alcohol is 1: 9～9: 1.
9, preparation terephthalate method for compositions according to claim 6, wherein, described catalyzer is metallic alkoxide compound or acid catalyst.
10, preparation terephthalate method for compositions according to claim 6, wherein, described catalyzer is the metallic alkoxide compound that is selected from metatitanic acid four isobutyl esters, titanium isopropylate and the Dibutyltin oxide, perhaps for being selected from the acid catalyst in tosic acid and the sulfuric acid.
11, preparation terephthalate method for compositions according to claim 6, wherein, described esterification carries out in the presence of nitrogen with the air admission outside the prevention reaction system, and feeds nitrogen one-tenth bubble to remove the water that produces in the reaction process in reaction soln.
12, preparation terephthalate method for compositions according to claim 6, wherein, described esterification carries out under 200～300 ℃.
13, preparation terephthalate method for compositions according to claim 12, wherein, described esterification carried out 4～24 hours.
14, preparation terephthalate method for compositions according to claim 6 wherein, is carried out in the organic solvent of described esterification in being selected from dimethylbenzene, toluene, dimethyl formamide (DMF), normal hexane and benzene.
15, a kind of polymer resin composition, said composition comprise the fluoropolymer resin of 100 weight parts and a kind of as in the described terephthalic acid ester composition of claim 1～5 of 20～150 weight parts of softening agent.
16, polymer resin composition according to claim 15, wherein, described fluoropolymer resin is selected from polyvinyl chloride (PVC) RESINS, acrylic resin, ABS resin, urethane resin, olefin resin, engineering plastic resin and the vibrin.
17, polymer resin composition according to claim 15, wherein, described polymer resin composition comprises one or more additives that are selected from extender plasticizer, stablizer, pigment, filler, whipping agent, lubricant and the viscosity modifier in addition.
18, polymer resin composition according to claim 15, wherein, described polymer resin composition is used to produce mixture, electric wire mixture, waterproof cloth, flexible pipe, section bar, wallpaper, film, food product pack, medical treatment product, synthetic leather, sheet material, band, auto parts machinery, toy and electrical equipment or mechanical component.
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| KR1020070046087A KR100868194B1 (en) | 2007-05-11 | 2007-05-11 | Composition of terephthalic acid esters for polymer resin and method for manufacturing the same |
| KR1020070046087 | 2007-05-11 | ||
| KR10-2007-0046087 | 2007-05-11 | ||
| PCT/KR2008/000992 WO2008140177A1 (en) | 2007-05-11 | 2008-02-20 | Composition of terephthalic acid esters for polymer resin and method of manufacturing the same |
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| CN102807491A (en) * | 2012-08-22 | 2012-12-05 | 中国林业科学研究院林产化学工业研究所 | Method for preparing terephthalic acid ester plasticizer with pressurization method |
| US9085670B2 (en) | 2012-10-10 | 2015-07-21 | Lg Chem, Ltd. | Plasticizer, plasticizer composition, heat-resistant resin composition and method for preparing the same |
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| US4654390A (en) * | 1984-08-10 | 1987-03-31 | The Dow Chemical Company | Monomeric plasticizers for halogen-containing resins |
| DE102006001795A1 (en) * | 2006-01-12 | 2007-07-19 | Oxeno Olefinchemie Gmbh | Terephthalic acid dialkyl esters and their use |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN101679708B (en) | 2012-06-20 |
| KR100868194B1 (en) | 2008-11-10 |
| WO2008140177A1 (en) | 2008-11-20 |
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