CN102838850B - Preparation method for hydrolysis-resistant PBT resin - Google Patents
Preparation method for hydrolysis-resistant PBT resin Download PDFInfo
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- CN102838850B CN102838850B CN201210280340.5A CN201210280340A CN102838850B CN 102838850 B CN102838850 B CN 102838850B CN 201210280340 A CN201210280340 A CN 201210280340A CN 102838850 B CN102838850 B CN 102838850B
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Abstract
The invention discloses a preparation method for a hydrolysis-resistant PBT resin. The preparation method comprises the step of co-blending the PBT resin, polycarbodiimide and an antioxidant. The hydrolysis-resistant PBT resin prepared by the method has good hydrolysis-resistant performance. The synthesized polycarbodiimide contains -NCO groups which can react with end carboxyl groups of the PBT resin, thereby enabling a hydrolysis-resistant stabilizer not to be migrated out from the resin matrix.
Description
Technical field
The present invention relates to a kind of preparation method of resistant to hydrolysis PBT resin.
Background technology
PBT is the polymkeric substance that terephthalic acid and at high temperature dehydration esterification reaction polycondensation of butyleneglycol form, thereby also can be because of the existence of the water inefficacy of degrading.When the water content of material is high, use temperature is during higher than the second-order transition temperature (60 DEG C) of PBT, the ester chain of PBT can be degraded by water erosion, resolve into alcohol and the acid of one end contain-OH group, one end contain-COOH group, and carboxyl increase more can accelerated material degraded.Therefore,, as long as have water and high temperature to exist, carboxyl end group concentration will increase, molecular weight and molecular weight.When molecular weight is reduced to certain degree, the intensity of material will reduce, and occurs fragility, end of life.
PBT, as the fastest engineering plastics of domestic development, has extraordinary chemical stability, mechanical strength, electrical insulating property, and the electrical property that caused by moisture absorption changes very little, and insulation voltage is very high, and forming stability and dimensional precision good.But the facile hydrolysis of PBT resin causes, it stops at automobile engine accessory, the high-end markets such as loose sleeve pipe for optical cable.
For PBT facile hydrolysis characteristic, the companies such as external Bayer, GE, Dong Li all actively synthesize and suppress the additive of hydrolysis and develop resistance to hydrolysis PBT material.If toray company is with the basis that is improved to resin in production process, PBT content of carboxyl end group is significantly reduced.Structure, just PBT is carried out the chemical modification of " correction ", effectively controlled carboxylic end group concentration.But the method has impact, disposable having high input to the synthesis technique of PBT.Physical modified method, carries out " later stage " with the form of additive to PBT material and processes.The method flexible operation, accords with the present situation that the synthetic enterprise of China PBT resin separates with PBT resin modified enterprise especially.The artificial wet and heat ageing resistant performance that improves PBT matrix material such as Xiao Yinghong, fiber surface is carried out to special processing, but PBT resin hydrolyzing is far longer than the close-burning variation of fiber and PBT resin boundary surface on the impact of material property, and the method effect is general.Float and wait employing resistant to hydrolysis stablizer D to play the effect that resistant to hydrolysis is stable side ten thousand, but the effect of this stablizer tackify is strong, affects the flow rate of resin melt, causes difficulty of processing increase.
Summary of the invention
The object of this invention is to provide a kind of preparation method of resistant to hydrolysis PBT resin.
The technical solution used in the present invention is:
A preparation method for resistant to hydrolysis PBT resin, comprises the following steps: by PBT resin, polycarbodiimide, oxidation inhibitor blend.
A preparation method for resistant to hydrolysis PBT resin, comprises the following steps: by PBT resin, polycarbodiimide, oxidation inhibitor with 100:(0.5-3): quality (0-1.5) is than blend.
The preparation method of described polycarbodiimide is: under oxygen free condition, hydrogenation MDI is warming up to 150-220 DEG C, adds catalyzer to carry out polycondensation.
Described oxygen free condition is realized by passing into shielding gas.
The time of polycondensation is 2-8h.
Described catalyzer is phospha cyclopentene oxide.
The consumption of described catalyzer is the 0.1-1.5% of hydrogenation MDI quality.
Described oxidation inhibitor comprises 1010,300,245,1035,1076,168, DLTP, 626, TNPP, P-EPQ, TNPP.
The invention has the beneficial effects as follows: the resistant to hydrolysis performance of resistant to hydrolysis PBT resin prepared by the present invention is good, due to contain in synthetic polycarbodiimide-NCO group, it can react with the end carboxyl of PBT resin, thereby makes this stabilizer against hydrolysis be difficult for moving out from resin matrix.
Brief description of the drawings
Fig. 1 is the infared spectrum of the product that obtains of embodiment 4.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1:
the preparation of polycarbodiimide:
Under nitrogen protection; raw material hydrogenation methylenebis phenyl isocyanate 100 gram liter temperature are stirred; control temperature at 180-190 DEG C; drip 0.25g catalyzer 3-methyl isophthalic acid-phenyl-2-ring fourth phosphorus alkene-1-oxide compound and carry out polycondensation to reaction system, reaction 1h, then drips oneself interior acyl chlorides of 1.5g and poisons catalyzer; stable system discharging while hot after question response 1-2h; obtain polycarbodiimide, after tested, its number-average molecular weight is 3130.
embodiment 2:
the preparation of polycarbodiimide:
Under nitrogen protection; raw material hydrogenation methylenebis phenyl isocyanate 100 gram liter temperature are stirred; control temperature at 180-190 DEG C; drip 0.25g catalyzer 3-methyl isophthalic acid-phenyl-2-ring fourth phosphorus alkene-1-oxide compound and carry out polycondensation to reaction system, reaction 3h, then drips oneself interior acyl chlorides of 1.5g and poisons catalyzer; stable system discharging while hot after question response 1-2h; obtain polycarbodiimide, after tested, its number-average molecular weight is 5673.
embodiment 3:
the preparation of polycarbodiimide:
Under nitrogen protection; raw material hydrogenation methylenebis phenyl isocyanate 100 gram liter temperature are stirred; control temperature at 180-190 DEG C; drip 0.25g catalyzer 3-methyl isophthalic acid-phenyl-2-ring fourth phosphorus alkene-1-oxide compound and carry out polycondensation to reaction system, reaction 4h, then drips oneself interior acyl chlorides of 1.5g and poisons catalyzer; stable system discharging while hot after question response 1-2h; obtain polycarbodiimide, after tested, its number-average molecular weight is 10173.
embodiment 4:
the preparation of resistant to hydrolysis PBT resin:
In PBT resin, add that to account for PBT resin quality be in rheometer, to carry out banburying after 0.2% antioxidant 1010 mixes, banburying temperature is 220 DEG C;
Product prepared by embodiment 1 joins (add-on is the 3wt% of PBT resin quality) in PBT resin, carries out banburying, banburying time 10min, rotor speed 30r/min in Brabender rheometer;
After discharging, pulverize, obtain product.
The infared spectrum of product as shown in Figure 1.
embodiment 5:
the preparation of resistant to hydrolysis PBT resin:
In PBT resin, add that to account for PBT resin quality be in rheometer, to carry out banburying after 0.2% antioxidant 1076 mixes, banburying temperature is 240 DEG C;
Product prepared by embodiment 2 joins in PBT resin (add-on be PBT resin quality 3%), carries out banburying, banburying time 15min, rotor speed 20r/min in Brabender rheometer;
After discharging, pulverize, obtain product.
embodiment 6:
the preparation of resistant to hydrolysis PBT resin:
In PBT resin, add that to account for PBT resin quality be in rheometer, to carry out banburying after 0.2% antioxidant 1076 mixes, banburying temperature is 240 DEG C;
Product prepared by embodiment 3 joins in PBT resin (add-on be PBT resin quality 3%), carries out banburying, banburying time 15min, rotor speed 20r/min in Brabender rheometer;
After discharging, pulverize, obtain product.
embodiment 7:
the preparation of resistant to hydrolysis PBT resin:
In PBT resin, add that to account for PBT resin quality be in rheometer, to carry out banburying after 0.2% irgasfos 168 mixes, banburying temperature is 240 DEG C;
Product prepared by embodiment 2 joins in PBT resin (add-on be PBT resin quality 0.5%), carries out banburying, banburying time 15min, rotor speed 20r/min in Brabender rheometer;
After discharging, pulverize, obtain product.
Resin prepared by embodiments of the invention 4-7, at 120 DEG C, carries out hydrothermal aging in the autoclave sterilizer of relative humidity 100%, thermogravimetic analysis (TGA) is carried out in sampling (to be respectively 0h, 24h, 72h, 148h, 256h) at set intervals, and detected result is in table 1.
Claims (1)
1. a preparation method for resistant to hydrolysis PBT resin, is characterized in that: comprise the following steps: by PBT resin, polycarbodiimide, oxidation inhibitor with 100: (0.5-3): quality (0-1.5) is than blend; The preparation method of described polycarbodiimide is: under oxygen free condition, hydrogenation MDI is warming up to 150-220 DEG C, adds catalyzer to carry out polycondensation; Described oxygen free condition is realized by passing into shielding gas; The time of polycondensation is 2-8h; Described catalyzer is phospha cyclopentene oxide; The consumption of described catalyzer is the 0.1-1.5% of hydrogenation MDI quality; Described oxidation inhibitor comprises 1010,300,245,1035,1076,168, DLTP, 626, TNPP, P-EPQ, TNPP.
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CN104845299A (en) * | 2015-05-27 | 2015-08-19 | 佛山市顺德区美的洗涤电器制造有限公司 | Glass fiber reinforced flame-retardant PBT material for washing pump and washing pump |
CN112646331B (en) * | 2020-12-15 | 2023-06-16 | 江苏金发科技新材料有限公司 | Polybutylene terephthalate mixture and preparation method thereof |
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JP5405862B2 (en) * | 2008-03-31 | 2014-02-05 | ウィンテックポリマー株式会社 | Multilayer tube |
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Non-Patent Citations (2)
Title |
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Investigation of Polycarbodiimide Additive Effects on the acid-catalyzed hydrolysis of PBT;Richard.M.LUM et al;《polymer chemistry》;19790930;第17卷(第9期);3017-302 * |
Richard.M.LUM et al.Investigation of Polycarbodiimide Additive Effects on the acid-catalyzed hydrolysis of PBT.《polymer chemistry》.1979,第17卷(第9期),3017-302. * |
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