CN105733232A

CN105733232A - Core-shell particle toughened modified PC and PBT resin

Info

Publication number: CN105733232A
Application number: CN201410747406.6A
Authority: CN
Inventors: 张晋阁; 贾宇冲; 马俊杰
Original assignee: Heilongjiang Xinda Enterprise Group Co Ltd
Current assignee: Heilongjiang Xinda Enterprise Group Co Ltd
Priority date: 2014-12-10
Filing date: 2014-12-10
Publication date: 2016-07-06

Abstract

The invention discloses a test method and preparation process for a core-shell particle toughened modified polycarbonate (PC) and polybutylene terephthalate (PBT) macromolecular alloy and belongs to the field of macromolecular materials. The composite material contains 40% (by weight) of PC and 60% (by weight) of PBT, and each core-shell particle contains the ingredients in percentage by weight: 73.1% of styrene (St), 24.4% of methyl methacrylate (MMA) and 2.5% of glycidyl methacrylate (GMA). By adding core-shell particles, the compatibility of the PC and the PBT is improved, and the notch sensitivity of the PBT is lowered, so that the intrinsic defects of the material are overcome, the commercial value of the material is increased, and the composite material can be applied to a wide variety of fields such as automotive interior trim parts, electronic product markets, and the like.

Description

Use Toughened With Core-Shell Particles modification PC and PBT resin

Technical field

The invention belongs to macromolecular material and machine-shaping field thereof, use core-shell particles (MBS-g-GMA) toughening modifying polycarbonate (PC) and polybutylene terephthalate (PBT) resin, the invention still further relates to the synthesis of core-shell particles.

Background technology

PBT is referred to as polybutylene terephthalate.Being esterified with BDO by high purity terephthalic acid (TPA) or dimethyl terephthalate (DMT) (DMT), polycondensation, the linear polymer melt of synthesis, the fiber obtained is polyester fiber.

In production, commonly used organic titanium or tin compound and butyl titanate are catalyst, dimethyl terephthalate (DMT) and Isosorbide-5-Nitrae- Butanediol ester swaps reaction, under high temperature and vacuum condition, obtains the spinning melt of PBT fiber.

In the nineties in 20th century, polybutylene terephthalate (PBT) (PBT), it is a kind of new type polyester fiber, due to its special structure and excellent process based prediction model, receives more and more attention in engineering plastics field.Due to the plastics used, it would be desirable to essence and performance to PBT carry out in-depth study.

At present, the research of PBT crystallization behavior is concentrated mainly on the change of the crystal property of isothermal and non-isothermal kinetics, crystallization mechanism and copolymer, such as the polyester of polyethylene terephthalate (PET).Commercial Application all contains the material of nucleator.

Scientist's Field and the Dixon of PBT Shi Liangge Indonesia occur in the polyester patent delivered.PBT fibrous woven manufacturing industry started in late 1970s and the mid-80, first in Japan and the U.S..The manufacturer of Japan is that east is beautiful, Supreme Being people, Ke Dongli, Kanebo, You Nijika.Volume of production was at a fairly low at that time, for every company, the order of annual only 500 tons 600 tons.In 1984, Celanese Corp. of the U.S. managed in this field, had the ability producing PBT fiber 15000 tons per year.

The development trend of this fiber is optimistic, but in several years subsequently, the not such development of fiber (long filament and short fibre) as expected, its sales volume, compared with traditional product PET, was still new industry at that time.This causes due to some economic factor.First, price is substantially high than PET.Two, buying difficulty and the price of resin are significantly larger than fiber, and the fiber price top-priority factor that is manufacturer.

It should be pointed out that, from the technical point of view, the intensity of fiber and exploitation deep colour dyeing technology not in time are also the reasons causing problem simultaneously.Therefore, with this fault as starting point, in the later stage eighties 20th century, PBT fiber continues slowly development, until early 1990s, when many important manufacturers include: east is beautiful, Supreme Being people, again to this fiber interested till.It was found that they think at polymer in price, can significantly reduce, with close to traditional PET price (at least when producing in a large number).Meanwhile, Italy is the most actively studied, and is reached the project of leader by Nice at that time and causes bigger concern.

PBT resin produces DMT method (dimethyl terephthalate (DMT) ester exchange) and TPA method (p-phthalic acid direct esterification).Batch process and continuity method is had in art production process.Owing to Isosorbide-5-Nitrae-butanediol is easily cyclized by the oxolane (THF) under hot conditions, therefore the commercial production of PBT resin commonly used DMT method.Until early 1990s, Ji Ma the company direct esterification successfully developed-polycondensation production Technology so that the commercial production of PBT resin begins to use TPA method.

In the ordinary course of things, batch (-type) ester-interchange method is relatively simple at Exchange Ester Process, and flexible operation, only one of which transesterification reactor and polycondensation reactor, low equipment investment, instant effect, and production cost is low, moderately viscous product In recent years, through improving, it is also possible to produce the product of viscosity grade.Continuous ester interchange method, in addition to can producing low, high-viscosity products, and the quality of product is also stable, the most excellent in performance.

The production method of Ji Ma company also can produce low, in, the resin of viscosity grade, its high efficiency produced, required equipment is few, and energy consumption is low, can be substantially reduced manufacturing cost, makes product price close to the level of PET.But the shortcoming of its maximum is, the content of side-product oxolane (THF) is of a relatively high, and mass fraction is typically up to 10% to 15%(relative to 1,4-butanediol), and the yield of product is the biggest, the growing amount of THF is the highest, and the generation of continuous ester interchange method oxolane typically only 2%.Therefore, Isosorbide-5-Nitrae-butanediol unit consumption that Ji Ma company produces is more much higher than ester-interchange method.

Intercepted by by four CH2 as it was previously stated, the difference of PBT and PET construction is the phenyl ring in the former chain, and the latter is intercepted by two CH3.Such difference allows for PBT and has the conduct of oneself uniqueness.First the feature of polymer is that the proportion of PBT is less than PET, but is greater than PBT and PBT6, next to that its glass transition and melt temperature are lower than PET, and roughly equal with PBT, the product of last PBT has faster crystalline rate, thus degree of crystallinity is much higher.Additionally, its bending rigidity (finished product) is lower than PET.

Summary of the invention

The invention discloses by Toughened With Core-Shell Particles modification polycarbonate and the test method of polybutylene terephthalate's high polymer alloy and preparation process, belong to polymeric material field.

(1) it is an object of the present invention to provide synthesis and polycarbonate (PC) and the preparation of polybutylene terephthalate (PBT) composite of core-shell particles (MBS-g-GMA), specifically comprise the following steps that

(1) Using emulsion polymerisation process synthesis MBS-g-GMA, reaction is carried out in 70 DEG C of water-baths, is separately added into deionized water, sodium pyrophosphate, glucose, ferrous sulfate, PBL latex, potassium hydroxide and CHP in there-necked flask.

(2) Being passed through nitrogen, be persistently added drop-wise in reactor by the monomer of St, MMA and CHP of preparing, about 3h drips complete, and rotating speed is 300r/min.

(3) Drip GMA and CHP monomer again, add a small amount of CHP, after 1h, add 60mL antioxidant, take out after 0.5h, be inverted (temperature is 65 DEG C) in Adlerika and carry out breakdown of emulsion, by filtration, obtain MBS-g-GMA graft copolymer.

(4) Finally, put it into 60 DEG C of air dry ovens are dried and obtain graft copolymer powder.

(2) another object of the present invention is polycarbonate (PC), polybutylene terephthalate (PBT), preparation method and subsequent treatment as follows:

(1) by PBT with PC in 4:6(wt%) ratio mixes, and PBT/PC blend is according to 230 DEG C, and 240 DEG C, 250 DEG C of three kinds of temperature are blended, and extrude with double screw extruder

(2) rate of feeding is 14rpm, and engine speed is 100rpm, by water-cooled, pelletize, the pellet after pelletize is put into drying 24h in 80 DEG C of vacuum drying ovens.

(3) pellet after finally drying is molded into standard batten through injection machine, and injection temperature is 240 DEG C.Every test is carried out again after batten stablizes 24h under the conditions of 23 DEG C.

Concrete application example:

The following examples will assist in those of ordinary skill in the art and is further appreciated by the present invention, but limits the present invention the most in any form.

Embodiment 1

By following formula synthetic kernel shell particles (MBS-g-GMA)

Monomer	Content (wt%)
		St	73.1
MMA	24.4
		GMA	2.5

(1) Preparation method: using emulsion polymerisation process synthesis MBS-g-GMA, reaction is carried out in 70 DEG C of water-baths, is separately added into deionized water, sodium pyrophosphate, glucose, ferrous sulfate, PBL latex, potassium hydroxide and CHP in there-necked flask.

Embodiment 2

Polycarbonate (PC) is synthesized, polybutylene terephthalate (PBT) by following instance:

(1) By PBT with PC in 4:6(wt%) ratio mixes, and PBT/PC blend is according to 230 DEG C, and 240 DEG C, 250 DEG C of three kinds of temperature are blended, and extrudes with double screw extruder, each district temperature such as chart 1

The setting of the double screw extruder extrusion temperature at a temperature of table 1 blend different mixture

Temperature

One district

2nd district

3rd district

4th district

5th district

6th district

7th district

Solution temperature

230℃

200℃

220℃

230℃

240℃

210℃

230℃

240℃

250℃

220℃

240℃

250℃

Claims

1. use the modified polycarbonate (PC) of core-shell particles (MBS-g-GMA) and polybutylene terephthalate (PBT) composite and preparation method thereof, by by the mixture of polycarbonate and p-phthalic acid butanediol fat and core-shell particles according to required ratio melt blending and post-processing approach, the addition of polycarbonate makes the notch sensitivity of polybutylene terephthalate significantly reduce, the addition of modifying agent core-shell particles simultaneously makes the compatibility of polycarbonate and polybutylene terephthalate obtain good improvement, the hot strength of material itself simultaneously, impact strength, and the toughness of material also can be maintained.

The modified polycarbonate (PC) of use core-shell particles (MBS-g-GMA) the most according to claim 1 and polybutylene terephthalate (PBT) composite and preparation method thereof, the proportioning of core-shell particles (MBS-g-GMA) modifying agent preparation monomer used is as Figure 1-1

Monomer ratio in table 1-1 core-shell modifiers

。

The most according to claim 1 described: Merlon (PC), polybutylene terephthalate (PBT), 4:6(wt% pressed by two kinds of material) mixing.

The most according to claim 2, preparation method and the purification of core-shell particles (MBS-g-GMA) comprises the steps of:

Using emulsion polymerisation process synthesis MBS-g-GMA, reaction is carried out in 70 DEG C of water-baths, is separately added into deionized water, sodium pyrophosphate, glucose, ferrous sulfate, PBL latex, potassium hydroxide and CHP in there-necked flask；

Being passed through nitrogen, be persistently added drop-wise in reactor by the monomer of St, MMA and CHP of preparing, about 3h drips complete, and rotating speed is 300r/min；

Drip GMA and CHP monomer again, add a small amount of CHP, after 1h, add 60mL antioxidant, take out after 0.5h, be inverted (temperature is 65 DEG C) in Adlerika and carry out breakdown of emulsion, by filtration, obtain MBS-g-GMA graft copolymer；

Finally, put it into 60 DEG C of air dry ovens are dried and obtain graft copolymer powder.

The most according to claim 1 described, polycarbonate (PC), polybutylene terephthalate (PBT), preparation method and subsequent treatment as follows:

By PBT with PC in 4:6(wt%) ratio mixes, and PBT/PC blend is according to 230 DEG C, and 240 DEG C, 250 DEG C of three kinds of temperature are blended, and extrudes with double screw extruder, and each district temperature is arranged as shown in table 1-2；

The setting of the double screw extruder extrusion temperature at a temperature of table 1-2 blend different mixture

Rate of feeding is 14rpm, and engine speed is 100rpm, by water-cooled, pelletize, the pellet after pelletize is put into drying 24h in 80 DEG C of vacuum drying ovens；

Pellet after finally drying is molded into standard batten through injection machine, and injection temperature is 240 DEG C, carries out every test after batten stablizes 24h under the conditions of 23 DEG C again.