CN101654546B - Hydrolysis resistant polyester resin composition and preparation method thereof - Google Patents
Hydrolysis resistant polyester resin composition and preparation method thereof Download PDFInfo
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- CN101654546B CN101654546B CN 200810124530 CN200810124530A CN101654546B CN 101654546 B CN101654546 B CN 101654546B CN 200810124530 CN200810124530 CN 200810124530 CN 200810124530 A CN200810124530 A CN 200810124530A CN 101654546 B CN101654546 B CN 101654546B
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Abstract
The invention discloses a hydrolysis resistant polyester resin composition. The composition is prepared from thermoplastic polyester and an end group blocking agent, wherein the mass of the end group blocking agent is 0.1 to 5 percent of that of the thermoplastic polyester resin. The invention also discloses a preparation method for the composition. The method comprises the following steps of: premixing the thermoplastic polyester and the end group blocking agent, and then melting and blending to prepare the composition. Compared with the matrix polyester resin, the hydrolysis resistant polyester resin blend has better hydrolysis resistance.
Description
Technical field
The invention belongs to polymeric material field, be specifically related to a kind of polymer blend with anti-hydrolytic performance with and preparation method thereof.
Background technology
Polyester resin is owing to characteristics such as its excellent chemical stability, solvent resistance, wear resistance, glossiness, barrier properties for gases and electrical insulating property are widely used in monofilament, fiber, film, moulded product and container etc.Yet, most polyester material under hot and humid condition during long-time the exposure because the hydrolytic deterioration of polymer chain and can not keep the physicals of material fully.The hydrolytic resistance of improving polymer blend seems extremely important and necessary with the application that adapts to polyester material and more and more widely reach under the severe condition.
People know that the hydrolytic deterioration of vibrin is owing to the ester bond in the water molecules attack polyester molecule causes the polymer chain break, and the end carboxyl on the polyester molecule chain can quicken the hydrolytic cleavage of ester bond again.Therefore, through the content of carboxyl end group of control vibrin, can improve the stability to hydrolysis of polyester material.More effective means are in polyester material, to add the carbodiimide compounds at present.
Chinese invention patent 02124938.5 discloses a kind of fastener product of synthetic resins manufacturing of hydrolysis.It is in vibrin, to add aromatic polycarbodiimide (Stabaxol that German Rhein-Chemie company produces) and realize.It is said that the fastener product of manufacturing has the excellent damp and hot weather resistance of resisting, and can keep stable bonding state, and do not produce such as defectives such as intensity reduction and variable colors.
It is the anti-method for hydrolysis of main body plastics that Japanese Patent JP9296097 discloses a kind of polyester (such as urethane, PET, POLYACTIC ACID or the like).It is to add the stablizer of special carbodiimide as hydrolysis in the plastics of main body at polyester.Have good consistency between filler and main body, make filler well be dispersed in the resin, the matrix material that finally obtains has outstanding resistance to hydrolysis ability.
One Chinese patent application 200480001526.6 discloses the good based resin molded goods of aromatic polyester segmented copolymer of a kind of hydrolytic resistance, thermotolerance and yellowing resistance.It is that oxidation inhibitor and sulphur are that oxidation inhibitor is realized through in ester block copolymer, adding polycarbodiimide compound, epoxy compounds, phenol.USP discloses the method for manufacture of the improved oriented polyester article of a kind of stability to hydrolysis for No. 5763538.It is that the polyoxyethylene glycol of vibrin and methoxy-terminated and polycarbodiimide compound are carried out blend, adds the thermosetting melt, is shaped to orientation products then.
Yet, in all disclosed technology of improving the vibrin anti-hydrolytic performance, use the carbodiimide compounds to have following shortcoming at these: cost an arm and a leg, poor heat stability, the course of processing produces the deleterious smell of HUMAN HEALTH.
In order to solve the problem that exists in the prior art, must use a kind of effective additives, it can significantly improve the hydrolysis characteristic of vibrin, is easy to processing simultaneously again, in the course of processing, can not produce the deleterious smell of HUMAN HEALTH.
Summary of the invention
The objective of the invention is to keep the shortcoming of material property, a kind of hydrolysis resistant polyester resin composition is provided in order to solve the polyester material facile hydrolysis.
Another object of the present invention provides a kind of preparation method of above-mentioned hydrolysis resistant polyester resin composition.
The object of the invention can reach through following measure:
A kind of hydrolysis resistant polyester resin composition, said composition is made up of thermoplastic polyester and terminal group end-capping reagent, and wherein the quality of terminal group end-capping reagent is 0.1～5% of a thermoplastic polyester.
Wherein thermoplastic polyester is the thermoplastic polyester that is made up of aromatic series and/or aliphatic dibasic acid and aromatic series and/or aliphatic dihydroxy alcohol unit; Comprise variously can being used as monofilament, fiber, film, the thermoplastic polyester of moulded product and container wherein is preferably polyethylene terephthalate (PET).
Wherein the terminal group end-capping reagent is a bisphenol A type epoxy resin, and its molecular formula can be expressed as:
Wherein n is 4～20.
The number-average molecular weight of this bisphenol A type epoxy resin is 1000～5000.Preferred 1200～4000.
A kind of preparation method of hydrolysis-resistant polyester composition; Thermoplastic polyester and terminal group end-capping reagent melt blending are prepared hydrolysis-resistant polyester composition, and being about to behind terminal group end-capping reagent and the thermoplastic polyester premix of thermoplastic polyester quality 0.1～5% again, melt blending prepares hydrolysis-resistant polyester composition; Or add the terminal group end-capping reagent again at the back segment of the polyreaction of thermoplastic polyester and carry out blend and prepare hydrolysis-resistant polyester composition.
Wherein the temperature during blend is 210～300 ℃.Melt blending behind the premix can utilize forcing machine to carry out.
Hydrolysis resistant polyester resin blend among the present invention is compared with the polyester as matrix resin, has excellent hydrolytic resistance, and this advantage seldom is confirmed by the increase degree of middle-end carboxyl concentration behind the moulding article pyrohydrolysis.
For further specifying above and other objects of the present invention, characteristic and advantage, will illustrate through embodiment below.
Embodiment
Sample hydrolysis and evaluation test method
The hydrolysis experiment of vibrin is to be 150 ℃ in temperature, is full of to carry out in the autoclave of moist steam, and hydrolysis time was respectively 6 hours and 21 hours.After hydrolysis finishes, place 80 ℃ of vacuum drying ovens dry on sample.
End carboxyl concentration adopts the optics titration measuring.Polyester is dissolved in the mixed solution (weight ratio 70:30) of neighbour-cresols and chloroform, adds bromthymol blue indicator, carry out titration in the ethanolic soln with the Pottasium Hydroxide of 0.05N then
Embodiment 1
With polyethylene terephthalate (PET; F20S, toray company) 150 ℃ of vacuum-drying after 6 hours, with EPON1001 (the epoxy chloropropane bisphenol A-type solid epoxy of PET quality 0.5%; Mn1200) do to mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 1.
Embodiment 2
With polyethylene terephthalate (PET; F20S, toray company) 150 ℃ of vacuum-drying after 6 hours, with EPON1001 (the epoxy chloropropane bisphenol A-type solid epoxy of PET quality 1%; Mn1200) do to mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 1.
Embodiment 3
With polyethylene terephthalate (PET; F20S, toray company) 150 ℃ of vacuum-drying after 6 hours, with EPON1001 (the epoxy chloropropane bisphenol A-type solid epoxy of PET quality 3%; Mn1200) do to mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 1.
The resin hydrolyzing test-results of table 1 embodiment 1-3
Embodiment 4
With polyethylene terephthalate (PET; F20S, toray company) 150 ℃ of vacuum-drying after 6 hours, with EPON1009 (the epoxy chloropropane bisphenol A-type solid epoxy of PET quality 0.5%; Mn4000) do to mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 2.
Embodiment 5
With polyethylene terephthalate (PET; F20S, toray company) 150 ℃ of vacuum-drying after 6 hours, with EPON1009 (the epoxy chloropropane bisphenol A-type solid epoxy of PET quality 1%; Mn4000) do to mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 2.
Embodiment 6
With polyethylene terephthalate (PET; F20S, toray company) 150 ℃ of vacuum-drying after 6 hours, with EPON1009 (the epoxy chloropropane bisphenol A-type solid epoxy of PET quality 3%; Mn4000) do to mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 2.
The resin hydrolyzing test-results of table 2 embodiment 4-6
Embodiment 7
Under 250 ℃ temperature; Make 166 parts of (weight) terephthalic acids and 75 parts of (weight) terepthaloyl moietie carry out the direct esterification reaction; The gained reaction product is placed the polymerization flask of being furnished with rectifying tower, and progressively add the catalyzer antimony compounds, under atmospheric pressure be decompressed to about 300Pa then through one hour; Temperature was warming up to 290 ℃ through one and a half hours; Under nitrogen protection, add 1.2 parts of (weight) EPON1001 (epoxy chloropropane bisphenol A-type solid epoxy, epoxy group content are Mn1200) while stirring and react then.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 3.
Embodiment 8
Under 250 ℃ temperature; Make 166 parts of (weight) terephthalic acids and 75 parts of (weight) terepthaloyl moietie carry out the direct esterification reaction; The gained reaction product is placed the polymerization flask of being furnished with rectifying tower, and progressively add the catalyzer antimony compounds, under atmospheric pressure be decompressed to about 300Pa then through one hour; Temperature was warming up to 290 ℃ through one and a half hours; Under nitrogen protection, (epoxy chloropropane bisphenol A-type solid epoxy Mn1200) reacts to add 2.4 parts of (weight) EPON1001 while stirring then.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 3.
Embodiment 9
Under 250 ℃ temperature; Make 166 parts of (weight) terephthalic acids and 75 parts of (weight) terepthaloyl moietie carry out the direct esterification reaction; The gained reaction product is placed the polymerization flask of being furnished with rectifying tower, and progressively add the catalyzer antimony compounds, under atmospheric pressure be decompressed to about 300Pa then through one hour; Temperature was warming up to 290 ℃ through one and a half hours; Under nitrogen protection, (epoxy chloropropane bisphenol A-type solid epoxy Mn1200) reacts to add 7.2 parts of (weight) EPON1001 while stirring then.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 3.
The resin hydrolyzing test-results of table 3 embodiment 7-9
Comparative Examples 1
Polyethylene terephthalate (PET, F20S, toray company) 150 ℃ of vacuum-dryings after 6 hours, is extruded through twin screw extruder and to be obtained blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 4.
Comparative Examples 2
With polyethylene terephthalate (PET, F20S, toray company) 150 ℃ of vacuum-dryings after 6 hours, with the TGIC (three-glycidyl based isocyanate) of PET quality 1% do mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 4.
Comparative Examples 3
With polyethylene terephthalate (PET, F20S, toray company) 150 ℃ of vacuum-dryings after 6 hours, with the MP-20 (GMA type multipolymer) of PET quality 1% do mix after, extrude through twin screw extruder and to obtain blended slice.Forcing machine feed zone temperature is 210 ℃, and the temperature of all the other sections is 260 ℃, and screw speed is 500 rev/mins.Analyze the end carboxyl concentration change of gained resin hydrolyzing test front and back, the result is as shown in table 4.
The resin hydrolyzing test-results of table 4 Comparative Examples 1-3
Can find out by above embodiment and Comparative Examples; Through the PET behind the bisphenol type epoxy compound blending and modifying; The carboxyl concentration increase of hydrolysis experiment rear end seldom; Unmodified PET then increases very big, and it improves effect and compare also not inferiorly with effective hydrolysis agent TGIC, proves that thus the polyester and resin composition among the present invention has preferable hydrolytic resistance.
Claims (3)
1. hydrolysis resistant polyester resin composition, it is characterized in that: said composition is made up of polyethylene terephthalate and terminal group end-capping reagent, and wherein the quality of terminal group end-capping reagent is 0.1～5% of a polyethylene terephthalate;
Wherein, described terminal group end-capping reagent is a bisphenol A type epoxy resin, and its molecular formula can be expressed as:
Wherein n is 4～20; The number-average molecular weight of described bisphenol A type epoxy resin is 1000～5000.
2. the preparation method of a hydrolysis-resistant polyester composition; It is characterized in that: polyethylene terephthalate and terminal group end-capping reagent melt blending are prepared hydrolysis-resistant polyester composition, or add the terminal group end-capping reagent at the polyreaction back segment of polyethylene terephthalate and carry out blend and prepare hydrolysis-resistant polyester composition;
Wherein, described terminal group end-capping reagent is a bisphenol A type epoxy resin, and its molecular formula can be expressed as:
Wherein n is 4～20.
3. preparation method according to claim 2 is characterized in that: the temperature during blend is 210～300 ℃.
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| CN 200810124530 CN101654546B (en) | 2008-08-22 | 2008-08-22 | Hydrolysis resistant polyester resin composition and preparation method thereof |
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| CN 200810124530 CN101654546B (en) | 2008-08-22 | 2008-08-22 | Hydrolysis resistant polyester resin composition and preparation method thereof |
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| CN101654546B true CN101654546B (en) | 2012-12-26 |
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| TWI490264B (en) | 2013-06-25 | 2015-07-01 | Ind Tech Res Inst | Polyester composition, and polyester article prepared therefrom |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312327A (en) * | 2000-03-08 | 2001-09-12 | 财团法人工业技术研究院 | A kind of hydrolysis-resistant polyester composition and preparation method thereof |
| CN1757673A (en) * | 2004-10-07 | 2006-04-12 | 胜技高分子株式会社 | Polybutylene terephthalate resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312327A (en) * | 2000-03-08 | 2001-09-12 | 财团法人工业技术研究院 | A kind of hydrolysis-resistant polyester composition and preparation method thereof |
| CN1757673A (en) * | 2004-10-07 | 2006-04-12 | 胜技高分子株式会社 | Polybutylene terephthalate resin composition |
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