CN112724634B

CN112724634B - PC-PCTG alloy and preparation method and application thereof

Info

Publication number: CN112724634B
Application number: CN202011568836.3A
Authority: CN
Inventors: 吴兆启; 王冲
Original assignee: Shenzhen Liyue New Material Co ltd
Current assignee: Shenzhen Liyue New Material Co ltd
Priority date: 2020-12-25
Filing date: 2020-12-25
Publication date: 2023-01-31
Anticipated expiration: 2040-12-25
Also published as: CN112724634A

Abstract

The application relates to the field of polymer composite materials, and particularly discloses a PC-PCTG alloy and a preparation method and application thereof. A PC-PCTG alloy is prepared from 40-50 parts by weight of PC, 30-50 parts by weight of polyester PCTG, 10-20 parts by weight of polysiloxane, 0.9-3 parts by weight of antioxidant and 0.5-1.0 part by weight of nano zirconium phosphate; the preparation method comprises the following steps: weighing the raw materials according to the formula ratio, stirring and blending, and melting, extruding and granulating through a double-screw extruder to obtain the PC-PCTG alloy particles. The PC-PCTG alloy can be used for an in-mold insert injection molding process, has the advantages of high fluidity and low-temperature molding, and is high in yield of molded parts obtained by injection molding.

Description

PC-PCTG alloy and preparation method and application thereof

Technical Field

The application relates to the field of polymer composite materials, in particular to a PC-PCTG alloy and a preparation method and application thereof.

Background

PC (polycarbonate) is a high-strength high-light-transmittance thermoplastic resin material and has good impact resistance, good wear resistance, high transparency, no toxicity and other excellent properties, so that the PC is widely applied to the fields of household appliance industry, precision machinery, automobile alloys and the like as engineering plastic.

At present, PC is commonly used as injection molding glue for in-film insert injection molding process due to higher wear resistance and good transparency. Melting and injecting PC into the die cavity, bonding with Foil (film) printed with ink patterns in the die cavity, and forming a transparent protective layer on the surface of the film to protect the patterns on the film.

In the actual production process, when the temperature of the PC material is generally increased to 270-300 ℃, the melt index reaches 10g/10min, the PC material has certain fluidity, and injection molding can be performed within the temperature range, but the ink layer of the plastic part prepared by the method is easy to disperse, and the yield of the plastic part is low, namely only 65%.

Disclosure of Invention

In order to improve the yield of plastic parts, the application provides a PC-PCTG alloy and a preparation method and application thereof.

In a first aspect, the PC-PCTG alloy provided by the application adopts the following technical scheme:

a PC-PCTG alloy is prepared from the following raw materials in parts by weight:

40-50 parts of PC

30-50 parts of polyester PCTG

10-20 parts of polysiloxane

0.9-3 parts of antioxidant

0.5-1.0 part of nano zirconium phosphate.

By adopting the technical scheme, the PC has certain fluidity at high temperature (270-300 ℃) and can be molded by injection, and the ink layer of the film is impacted by high temperature and is easy to disperse, so that the yield of the plastic part is low, the PCTG and other additives are added to modify the PC, the prepared PC-PCTG alloy has good fluidity at 230-250 ℃, the injection molding temperature is reduced, the possibility that the ink layer on the film is dispersed is reduced, and the yield of the plastic part is improved;

when PCTG and PC are subjected to blending modification, the regularity of PC-PCTG molecular chains is reduced, and the regularity of PC-PCTG alloy molecular chains is reduced, so that the improvement of the fluidity of PC-PCTG alloy is facilitated, and the forming temperature of the PC-PCTG alloy is reduced;

meanwhile, the doped nano zirconium phosphate can have a synergistic effect with PCTG, so that the fluidity of the PC-PCTG alloy is obviously improved, the forming temperature of the PC-PCTG alloy is reduced, and the yield of plastic parts is improved.

In addition, the polysiloxane and the PCTG have a synergistic effect, and the chemical resistance of the PC-PCTG alloy can be obviously improved.

Preferably, the PC is a bisphenol a polycarbonate.

By adopting the technical scheme, the hydroxyphenyl group of the bisphenol A polycarbonate can be combined with PCTG, so that the fluidity of the PC-PCTG alloy is further improved, the molding difficulty of the PC-PCTG alloy is reduced, and the yield of plastic parts is improved.

Preferably, the mass ratio of the PC to the PCTG is 1 (0.9-1.1).

By adopting the technical scheme, the modification effect of PCTG on PC is optimal in the range, when the addition amount of PCTG is too low, the modification effect on PC is poor, the fluidity of PC-PCTG alloy is poor, and when the addition amount of PCTG is too high, the fluidity and chemical resistance of PC-PCTG alloy are not affected, but the high temperature resistance of PC-PCTG alloy is reduced, the PC-PCTG alloy is easy to decompose, and is difficult to mold during injection molding, so that the yield of plastic parts is reduced.

Preferably, the polysiloxane has a number average molecular weight of 1700 to 2700.

By adopting the technical scheme, the polysiloxane in the number average molecular weight range can ensure good compatibility in the PC-PCTG alloy and reduce the epoxy group content of the polysiloxane, so that the possibility of macromolecular reaction between the epoxy group of the polysiloxane and a PC-PCTG molecular chain is reduced, the PC-PCTG alloy has good fluidity, and the yield of plastic parts is improved.

Preferably, the antioxidant is selected from one or more of pentaerythritol stearate, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite.

By adopting the technical scheme, the compounds selected by the antioxidant all have macromolecular flexible chains and have good compatibility with the PC-PCTG alloy, so that the oxidation resistance and the toughness of the PC-PCTG alloy are increased.

Preferably, the antioxidant is prepared by mixing pentaerythritol stearate, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of 1.

By adopting the technical scheme, the pentaerythritol stearate can also be used as a lubricant, so that the friction force between PC-PCTG alloy chain segments is reduced, and the fluidity is improved; the tris [2, 4-di-tert-butylphenyl ] phosphite can be used as an internal lubricant, so that the intermolecular resistance when PC and PCTG are blended is reduced, the compatibility between PC and PCTG is improved, and the fluidity of PC-PCTG alloy is improved; the three components can play a synergistic role, so that the thermo-oxidative aging resistance of the PC-PCTG alloy is improved.

Preferably, the average particle size of the nano zirconium phosphate is 100-200nm.

By adopting the technical scheme, the zirconium phosphate has better compatibility with the PC-PCTG alloy in the average grain size range, and the PC-PCTG alloy has better fluidity.

In a second aspect, the application provides a preparation method of a PC-PCTG alloy, which adopts the following technical scheme:

a preparation method of PC-PCTG alloy comprises the following steps: weighing PC, polyester PCTG, polysiloxane, antioxidant and nano zirconium phosphate in the formula ratio, uniformly mixing to obtain a mixture, and putting the mixture into an extruder for fusion, extrusion and granulation to obtain the PC-PCTG alloy.

By adopting the technical scheme, the polymer is stirred, blended and enters the extruder for modification, and the prepared PC-PCTG alloy has better mechanical property and fluidity and is easy to process and form.

Preferably, the temperature settings of each zone of the screw in the extruder are respectively as follows: the temperature of the first zone is 220-240 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 240-250 ℃, the temperature of the fourth zone is 245-255 ℃, the temperature of the fifth zone is 245-255 ℃, the temperature of the sixth zone is 245-255 ℃, the temperature of the seventh zone is 245-255 ℃, the temperature of the eighth zone is 240-250 ℃ and the temperature of the ninth zone is 245-255 ℃.

By adopting the technical scheme, the temperature of each area is easy to control, and the forming effect is good.

In a third aspect, the present application provides a plastic part, which adopts the following technical scheme:

a plastic part comprises a film and a protective layer coated on the surface of the film, wherein the protective layer is prepared by adopting an in-mold insert injection molding process, and the injection plastic adopted by the protective layer of the in-mold insert injection molding process is the PC-PCTG alloy.

By adopting the technical scheme, the forming temperature of the PC-PCTG alloy is lower, the damage probability to the ink layer of the film is lower, and the yield of the obtained plastic part is higher.

In summary, the present application has the following beneficial effects:

1. as PCTG is adopted to modify PC, the prepared PC-PCTG alloy has better fluidity and lower molding temperature, and can obviously improve the yield when used as injection molding plastic.

2. Polysiloxane is preferably adopted in the application, and the polysiloxane and PCTG have synergistic effect on the chemical resistance of the PC-PCTG alloy, so that the chemical resistance of the PC-PCTG alloy can be obviously improved.

3. The antioxidant in the application preferably adopts pentaerythritol stearate, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite, so that the compatibility of the antioxidant and the PC-PCTG alloy can be increased, the flowability of the PC-PCTG alloy can be improved, and the thermal oxidation resistance of the PC-PCTG alloy can be obviously improved under the combined action of the antioxidant, the n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and the tris [2, 4-di-tert-butylphenyl ] phosphite.

4. In the application, the nanometer zirconium phosphate is preferably adopted, so that on one hand, the nanometer zirconium phosphate has a synergistic effect with PCTG to increase the fluidity of the PC-PCTG alloy, and on the other hand, the nanometer zirconium phosphate and an antioxidant have a synergistic effect on the thermal oxidation resistance of the PC-PCTG alloy, so that the thermal oxidation aging resistance of the PC-PCTG alloy is improved.

Detailed Description

Unless otherwise indicated, the starting materials used in the following examples and application examples are derived from the following table:

TABLE 1 sources of raw materials

Examples

Example 1

A PC-PCTG alloy is prepared by the following steps:

s1, weighing 40g of INFINO UF-1017, 30g of DN011, 10g of polydimethylsiloxane (with the number average molecular weight of 1800), 0.9gN, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine and 0.5g of nano zirconium phosphate (with the average particle diameter of 150 nm) and putting the materials into a high-speed stirrer for stirring and blending, wherein the stirring speed is 7200r/h, and premixing to obtain a mixture;

s2, putting the mixture obtained in the step 1 into a parallel double-screw extruder for melt extrusion, wherein the temperature of each zone of a screw in the extruder is respectively as follows: the first zone temperature is 230 ℃, the second zone temperature is 230 ℃, the third zone temperature is 245 ℃, the fourth zone temperature is 250 ℃, the fifth zone temperature is 250 ℃, the sixth zone temperature is 250 ℃, the seventh zone temperature is 250 ℃, the eighth zone temperature is 245 ℃, the ninth zone temperature is 250 ℃, the head temperature is 255 ℃, the main machine rotation speed is 1200rpm, a 2# screw is used, the water tank temperature is 60 ℃, and the granulator rotation speed is 1000rpm, so that the PC-PCTG alloy is prepared.

Example 2

A PC-PCTG alloy is prepared on the basis of the embodiment 1, and is different from the embodiment 1 in that: 40g of the aliphatic polycarbonate INFINO UF-1017 was replaced by an equal mass of bisphenol A polycarbonate PC-1100.

Examples 3 to 10

A PC-PCTG alloy is prepared on the basis of example 2, and is different from example 1 in that: the compositions of the PC-PCTG alloys are different, and the specific compositions are shown in the following table 2:

TABLE 2 composition of PC-PCTG alloy

Examples 11 to 17

A PC-PCTG alloy is prepared on the basis of the embodiment 10, and is different from the embodiment 10 in that: the specific composition of the antioxidant used was as shown in Table 3 below, depending on the type of antioxidant used.

TABLE 3 composition of antioxidants

Comparative example

Comparative example 1

A PC material is prepared by the following steps:

s1, weighing 70g of INFINO UF-1017, 10g of polydimethylsiloxane (the number average molecular weight is 1800) and 0.9gN, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylene diamine, and putting the weighed materials into a high-speed stirrer for stirring and blending, wherein the stirring speed is 7200r/h, and premixing to obtain a mixture;

s2, putting the mixture obtained in the step 1 into a parallel double-screw extruder for melt extrusion, wherein the temperature of each zone of a screw in the extruder is respectively as follows: the first zone temperature is 270 ℃, the second zone temperature is 270 ℃, the third zone temperature is 285 ℃, the fourth zone temperature is 300 ℃, the fifth zone temperature is 300 ℃, the sixth zone temperature is 300 ℃, the seventh zone temperature is 300 ℃, the eighth zone temperature is 285 ℃, the ninth zone temperature is 300 ℃, the head temperature is 310 ℃, the main machine rotation speed is 1200rpm, a 2# screw is used, the water tank temperature is 60 ℃, and the granulator rotation speed is 1000rpm, so that the PC-PCTG alloy particles are prepared.

Comparative example 2

A PC-PCTG alloy similar to the production method of example 1, differing from the production method of example 1 in that: the nano zirconium phosphate is replaced by PC with equal mass.

Comparative example 3

A PC-PCTG alloy, similar to the production method of example 1, different from the production method of example 1 in that: the polysiloxane was replaced by an equal mass of PC.

Application example

Application example 1

A plastic part is prepared by the following steps:

and (3) placing the film subjected to screen printing on the back side into a die cavity, heating the die to 110 ℃, heating a charging barrel to 250 ℃, injecting the PC-PCTG alloy prepared in the embodiment 1, drying the formed PC-PCTG alloy for 4 hours at 90 ℃, and opening the die to obtain a plastic part.

Application examples 2 to 17

A plastic part is similar to the preparation method of the application example 1, and is different from the application example 1 in that the injection molding plastic material source and the injection molding process parameter are different, and the specific source is shown in the following table 4:

TABLE 4 sources of injected plastics and corresponding Process parameters

Comparative examples 1 to 3 were applied to the preparation of plastic parts, the preparation method of the plastic parts was similar to application example 1, and the prepared plastic parts were named as 1# plastic part, 2# plastic part, and 3# plastic part, wherein the specific process parameters in the preparation methods of 1# plastic part, 2# plastic part, and 3# plastic part are as shown in table 5 below:

TABLE 5 injection Molding Process parameters

Plastic part	Barrel temperature (. Degree.C.)	Mold temperature (. Degree. C.)
			No. 1 plastic part	300	140
2# Plastic part	264	130
			3# Plastic part	250	110

Performance test

Detection method

1. And (3) detecting the performance of the PC-PCTG alloy:

and (3) plastic part performance detection:

1. yield: taking 1000 plastic parts, wherein the plastic parts with the complete degree of appearance patterns of 99% or more are good products, and the good product rate is calculated according to the following formula:

good product rate = good product quantity/total plastic sample number × 100%

The result of the detection

The performance test data of examples 1-10, the specific test results are shown in table 6 below:

TABLE 6 test results of the properties of examples 1 to 10

The performance test data of examples 11-17, the specific test results are shown in table 7 below:

TABLE 7 results of the measurements of the properties of examples 11 to 17

The performance test data of comparative examples 1-3 show the following specific test results in table 8:

TABLE 8 Performance test results of comparative examples 1 to 3

The specific detection results of the data of the good product rate detection of the model 1-17 and model 1, model 2 and model 3 are shown in the following table 9:

TABLE 9 qualification Rate test data

Plastic part	Percent yield/%)	Plastic part	Percent yield/%)
				Application example 1	81.2	Application example 11	92.1
Application example 2	84.6	Application example 12	90.9
				Application example 3	83.0	Application example 13	91.5
Application example4	86.1	Application example 14	91.4
				Application example 5	86.7	Application example 15	91.3
Application example 6	84.1	Application example 16	93.8
				Application example 7	83.0	Application example 17	94.0
Application example 8	87.8	No. 1 plastic part	65.0
				Application example 9	89.7	2# Plastic part	76.4
Application example 10	89.3	3# Plastic part	81.6

The melt index reflects the fluidity of the PC-PCTG alloy and PC, and the higher the melt index is, the better the fluidity is;

the molding difficulty is reflected by the process parameters in table 5, and decreases as the charging barrel temperature and the mold temperature decrease;

the heat distortion temperature represents the thermal oxidation resistance of the PC-PCTG alloy and the PC, and the higher the heat distortion temperature is, the stronger the thermal oxidation resistance is; the longer the soaking time in a 10wt% carbon tetrachloride solution and glacial acetic acid is, the better the chemical resistance is;

as can be seen by combining examples 1 to 17 and comparative examples 1 to 3 with tables 5 to 9, as the melt index increases, the molding temperature of the PC-PCTG alloy decreases and the yield increases.

The following points can be seen by combining example 1, comparative examples 1-2 and tables 6 and 8:

firstly, the PC is modified by only adding PCTG, the melt index of the PC-PCTG alloy is improved from 10g/10min to 18g/10min, and the fluidity is increased by 1.8 times, and the reason that the PC is modified by PCTG to improve the fluidity of the material can be as follows: the glass transition temperature of the PCTG is low, the fluidity of the PCTG is good, and meanwhile, the PCTG increases the molecular chain irregularity degree of the PC-PCTG alloy, so that the fluidity of the PC-PCTG alloy is increased.

Secondly, the simultaneous addition of PCTG and zirconium phosphate has a synergistic effect on increasing the PC/PCG alloy, so that the melt index of the PC-PCTG alloy reaches 30g/10min, which is higher than that of the PC-PCTG alloy when PCTG and zirconium phosphate are added separately, and the possible reason for the synergistic effect of the zirconium phosphate and the PCTG is that: first, zirconium phosphate can increase the irregularity of segments of PC and PCTG; secondly, the zirconium phosphate has larger surface activity, can promote the compatibility of PC and PCTG, and the compatibility is enhanced, so that the melt index of the PC-PCTG alloy is increased, and the fluidity of the PC-PCTG alloy is higher.

As can be seen by combining example 1, comparative example 1 and comparative example 3, and by combining tables 6 and 8, the PC-PCTG alloy doped with both polysiloxane and PCTG had a soaking time of 10min in a 10wt% carbon tetrachloride solution and a soaking time of 20min in glacial acetic acid, which was much higher than the chemical resistance of the PC-PCTG alloy doped with polysiloxane and PCTG alone; the principle that the silicone and PCTG can act synergistically may be: when the PC-PCTG alloy contacts with a chemical reagent, the PCTG can resist the corrosion of the chemical reagent, and meanwhile, the polysiloxane is a flexible macromolecular chain segment, so that the toughness of the PC-PCTG alloy is improved, the energy of the internal stress of the PC-PCTG alloy caused by the chemical reagent is absorbed by the polysiloxane, the PC-PCTG alloy is difficult to crack, and the chemical resistance of the PC-PCTG alloy is better.

When the PC is bisphenol A polycarbonate and the mass ratio of the PC to the PCTG is 1.

In combination with examples 10 to 17 and in combination with tables 6 to 7, it can be seen that:

first, when the antioxidant contains pentaerythritol stearate and tris [2, 4-di-t-butylphenyl ] phosphite, the PC-PCTG alloy has a high melt index and good fluidity.

Secondly, when the antioxidant contains beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, the thermal deformation temperature of the PC-PCTG alloy is higher and can reach 114 ℃, and the thermal oxidation resistance is better.

Thirdly, when the antioxidant contains pentaerythritol stearate, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and tris [2, 4-di-tert-butylphenyl ] phosphite at the same time, the fluidity and the thermal oxidation resistance of the PC-PCTG alloy are both significantly improved.

It can be seen from the combination of examples 1 to 7 and application examples 1 to 17 and tables 6 to 9 that the best preparation method of the PC-PCTG alloy is the preparation method of example 17, the best preparation process of the plastic part is the preparation process of application example 17, and the yield of the plastic part is improved from 65% to 94% under the preparation process.

The specific embodiments are only for explaining the present application and are not limiting to the present application, and those skilled in the art can make modifications to the embodiments without inventive contribution as required after reading the present specification, but all the embodiments are protected by patent law within the scope of the claims of the present application.

Claims

1. A PC/PCTG alloy characterized in that: the composite material is prepared from the following raw materials in parts by weight:

40-50 parts of PC

30-50 parts of polyester PCTG

10-20 parts of polysiloxane

0.9 to 3 portions of antioxidant

0.5-1.0 part of nano zirconium phosphate;

the polysiloxane has a number average molecular weight of 1700-2700;

the average grain diameter of the nano zirconium phosphate is 100-200nm.

2. The PC/PCTG alloy of claim 1, wherein: the PC is bisphenol A polycarbonate.

3. The PC/PCTG alloy of claim 2, wherein: the mass ratio of the PC to the PCTG is 1 (0.9-1.1).

4. The PC/PCTG alloy of claim 1, wherein: the antioxidant is one or more of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester and tri [2, 4-di-tert-butylphenyl ] phosphite.

5. The method for producing a PC/PCTG alloy according to any one of claims 1 to 4, characterized in that: the method comprises the following steps: weighing PC, polyester PCTG, polysiloxane, antioxidant and nano zirconium phosphate according to the formula ratio, uniformly mixing to obtain a mixture, and putting the mixture into an extruder for fusion, extrusion and granulation to obtain the PC/PCTG alloy.

6. The method for producing a PC/PCTG alloy according to claim 5, characterized in that: the temperature setting of each area of the screw in the extruder is respectively as follows: the temperature of the first zone is 220-240 ℃, the temperature of the second zone is 220-240 ℃, the temperature of the third zone is 240-250 ℃, the temperature of the fourth zone is 245-255 ℃, the temperature of the fifth zone is 245-255 ℃, the temperature of the sixth zone is 245-255 ℃, the temperature of the seventh zone is 245-255 ℃, the temperature of the eighth zone is 240-250 ℃ and the temperature of the ninth zone is 245-255 ℃.

7. A plastic part, which is characterized in that: the plastic part comprises a rubber sheet and a protective layer coated on the surface of the rubber sheet, the protective layer is prepared by adopting an in-mold insert injection molding process, and the protective layer of the in-mold insert injection molding process adopts injection molding plastic as the PC/PCTG alloy in any one of claims 1-5.