CN116285291A - A kind of polycarbonate composition and preparation method thereof - Google Patents

Abstract

The application discloses a polycarbonate composition and a preparation method thereof, comprising the following components in parts by weight: 10-190 parts of polycarbonate, 0.2-0.4 parts of a flow enhancer, and 0.1-0.3 parts of other auxiliary agents. The polycarbonate comprises a first polycarbonate with an end-capping rate of 0%-30% and a second polycarbonate with an end-capping rate of 80%-100%, and the flow promoter can be degraded by a reaction without an end-capping structure of the polycarbonate, the flow promoter cannot react to degrade the polycarbonate having an end-capped structure. The above polycarbonate composition has both high fluidity and high impact resistance.

Description

A kind of polycarbonate composition and preparation method thereof

technical field

The present application relates to the technical field of polymer materials, in particular to a polycarbonate composition and a preparation method thereof.

Background technique

Polycarbonate (polycarbonate, referred to as PC) is a transparent engineering plastic with excellent performance. It has strong impact resistance, good dimensional stability, and excellent dielectric properties. It is currently widely used in automobiles, electronic equipment, construction and other fields. However, due to the poor fluidity of polycarbonate with strong impact resistance, it is difficult to be directly applied to fine and thin-walled products.

In order to improve the shortcomings of polycarbonate's poor fluidity, polycarbonate and high fluidity resins, such as: acrylonitrile-butadiene-styrene copolymer (ABS), polybutylene terephthalate (PBT) ), polyethylene terephthalate (PET), polyethylene terephthalate-1,4-cyclohexanedimethanol (PCTG), polyethylene terephthalate-1, 4-cyclohexanedimethanol ester (PETG) is mixed to improve the fluidity of polycarbonate, but mixing other resins in polycarbonate will cause polycarbonate to lose its transparency and affect its use. There are also technicians who mix polycarbonate with high fluidity and polycarbonate with low fluidity to improve its fluidity, but this method will lead to poor impact resistance of the material.

Therefore, how to prepare a polycarbonate composition with high fluidity and high impact resistance has become a technical problem to be solved by those skilled in the art.

Contents of the invention

The present application provides a polycarbonate composition and a preparation method thereof. The polycarbonate composition can have the advantages of high fluidity and high impact.

The application provides the following scheme: a polycarbonate composition comprising the following components by weight:

10-190 parts of polycarbonate, 0.2-0.4 parts of flow accelerator, 0.1-0.3 parts of other additives, the end-capping rate of polycarbonate is 40%-65%, and the polycarbonate contains 0% end-capping rate -30% of the first polycarbonate and the second polycarbonate with an end-capping rate of 80%-100%; Agents cannot react to degrade the polycarbonate having an end-capped structure.

Further, the polycarbonate includes a first polycarbonate and a second polycarbonate, the first polycarbonate is 5-95 parts, and the second polycarbonate is 5-95 parts.

Further, the melt index of the first polycarbonate is 7-13, and the melt index of the second polycarbonate is 17-23.

Further, the polycarbonate includes at least one of aromatic polycarbonate, aliphatic polycarbonate, and aromatic-aliphatic polycarbonate.

Further, the polycarbonate is bisphenol A polycarbonate.

Further, the flow enhancer includes amide ester flow enhancer.

Further, the amide ester flow promoter includes at least one of branched alkyl primary amides, erucamide, and nonadecanoic acid amide.

Further, the other additives include antioxidants.

Further, the antioxidant includes at least one of antioxidant S2225P, antioxidant 168, antioxidant 1010, and antioxidant 1098.

Further, the weight-number ratio of the first polycarbonate and the second polycarbonate is (1.2-0.8):1.

Further, the ratio by weight of the first polycarbonate to the second polycarbonate is 1:1.

In addition, the present application also provides the preparation method of aforementioned polycarbonate composition, comprises the steps:

In parts by weight, 10-190 parts of polycarbonate, 0.2-0.4 parts of flow promoter and 0.1-0.3 parts of other additives are uniformly mixed through a mixer to obtain a mixture;

The mixture is added into a twin-screw extruder for melt blending, extruding strands;

The strips are cut into pellets by a pelletizer, dried by an elevator, and packaged to obtain the finished product.

Further, the extrusion temperature of the aforementioned strand is 210-250°C.

Further, the screw speed of the aforementioned twin-screw extruder is 300-500 rpm.

According to the specific embodiments provided by the application, the application discloses the following technical effects:

The polycarbonate composition provided by the application is obtained by introducing a flow promoter and a polycarbonate comprising a first polycarbonate with an end-capping rate of 0%-30% and a second polycarbonate with an end-capping rate of 80%-100%. Ester is used to achieve the effect of high fluidity and high impact resistance of the material. Since the flow enhancer in this application can degrade polycarbonate with non-blocking structure, the fluidity of the material can be improved by reacting and degrading high-molecular-weight polycarbonate with non-blocking structure into low-molecular-weight polycarbonate. In addition, the flow promoter in the present application cannot react and degrade the polycarbonate with end-capped structure. Therefore, it is possible to increase the impact resistance of the material by adding an appropriate amount of polycarbonate with end-capped structure to the above-mentioned materials. sex. This application utilizes the difference in reactivity between flow promoters and polycarbonates with unblocked structures and polycarbonates with end-capped structures. In the process of blending and extrusion reactions, the degradation of flow promoters has different The polycarbonate with end-capped structure improves its fluidity, but does not react with polycarbonate with end-capped structure and maintains the original high impact resistance of this part of polycarbonate. Using this difference in reactivity, a high molecular weight and The low molecular weight polycarbonate composition finally meets the requirements of high fluidity and high impact resistance of the material.

Further, the flow enhancer in the present application includes amide ester flow enhancer, and the amide ester flow enhancer includes at least one of branched alkyl primary amides, erucamide, and nonadecanoic acid amide. The terminal amine group in the amide ester flow promoter reacts with the carbonic acid group in the polycarbonate with an unblocked structure, causing the molecular chain of the polycarbonate to break, and degrading the polycarbonate with a large molecular weight into a polycarbonate with a small molecular weight. Phenolic end-group compounds and stearyl carbamate end-group compounds enhance the fluidity of the original polycarbonate.

Of course, implementing any product of the present application does not necessarily need to achieve all the above-mentioned advantages at the same time.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the accompanying drawings required in the embodiments. Obviously, the accompanying drawings in the following description are only some of the present application. Embodiments, for those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

Fig. 1 is the mechanism diagram of the degradation reaction of nonadecanoic acid amide and polycarbonate with uncapped structure;

Fig. 2 is a flow chart of the preparation method of the polycarbonate composition provided by the present application.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments in this application belong to the protection scope of this application.

As mentioned in the background art, due to the poor fluidity of polycarbonate with strong impact resistance, it is difficult to be directly applied to fine and thin-walled products. In the prior art, polycarbonate is usually blended with high fluidity resins to improve its fluidity, but mixing other resins in polycarbonate will cause polycarbonate to lose its transparency and affect its use. In addition, there are technicians who mix polycarbonate with high fluidity and polycarbonate with low fluidity to improve its fluidity, but this method will lead to poor impact resistance of the material. In order to overcome the disadvantages of poor fluidity of polycarbonate with strong impact resistance, the application provides higher fluidity for the design of fine thin-walled products. The difference in reactivity between polycarbonates with end-capped structures, in the process of blending and extrusion reaction, the degradation of polycarbonates with un-capped structures through the reaction of flow promoters improves their fluidity, but not with the polycarbonates with capped structures. The polycarbonate of the terminal structure reacts to maintain the original high impact resistance of the polycarbonate, and utilizes this reactivity difference to form a polycarbonate composition with high molecular weight and low molecular weight, and finally satisfies the high fluidity of the material at the same time and high impact resistance requirements. Based on this, the application proposes a new polycarbonate composition and a preparation method thereof.

As a preferred embodiment, in the examples of the present application, according to parts by weight, the components of the polycarbonate composition include: 10-190 parts of polycarbonate, 0.2-0.4 parts of flow promoter, 0.1 -0.3 parts of other auxiliaries.

The polycarbonate includes a first polycarbonate and a second polycarbonate, wherein the first polycarbonate is a polycarbonate with an end-capping rate of 0%-30%, more specifically, the first polycarbonate Polycarbonate has end-capping ratios of 0%, 2%, 5%, 10%, 15%, 20%, 25%, and 30%, which are not listed here due to space limitations. The second polycarbonate is a polycarbonate with an end-capping rate of 80%-100%, more specifically, the second polycarbonate is a polycarbonate with an end-capping rate of 80%, 85%, 90%, 95%, 100%, due to space limitations, no exhaustive list here. Further, the first polycarbonate is prepared by a phosgene method, and the second polycarbonate is prepared by a melt transesterification method.

In the embodiment of the present application, the mass parts of the first polycarbonate is 5-95 parts, and the mass parts of the second polycarbonate is 5-95 parts. The melt index of the first polycarbonate is 7-13, more specifically, the melt index of the first polycarbonate is 7, 8, 9, 10, 11, 12, 13, preferably 10, limited by space Here is no longer exhaustive. The melt index of the second polycarbonate is 17-23, more specifically, the melt index of the second polycarbonate is 17, 18, 19, 20, 21, 22, 23, preferably 20, limited by space Here is no longer exhaustive.

The polycarbonate in the embodiments of the present application includes at least one of aromatic polycarbonate, aliphatic polycarbonate, and aromatic-aliphatic polycarbonate. Due to the low mechanical properties of aliphatic polycarbonate and aromatic-aliphatic polycarbonate, in the present application, the polycarbonate is preferably bisphenol A polycarbonate.

Due to the poor fluidity of polycarbonate with strong impact resistance and difficult processing, it is difficult to directly apply it to fine and thin-walled products. fluidity. In the process of blending extrusion granulation, the flow accelerator and polycarbonate with unblocked structure react at high temperature, causing the molecular chain of polycarbonate with unblocked structure to break, so as to improve the polycarbonate Purpose of ester fluidity. Among them, the reactivity of amine flow promoters is very strong, and generally only need to add 0.2-0.4 parts to make the melt index of polycarbonate with unblocked structure, that is, the fluidity, be improved to a large extent, but it causes the material The impact resistance is significantly reduced. In order to take into account the fluidity and impact resistance of polycarbonate, in the embodiment of the present application, the flow enhancer is an amide ester flow enhancer, and the amide ester flow enhancer can degrade polycarbonate with an unblocked structure, The fluidity of the material is improved by degrading the high molecular weight polycarbonate with unblocked structure into low molecular weight polycarbonate. Further, since the amide ester flow promoter cannot degrade the polycarbonate with an end-capped structure, an appropriate amount of polycarbonate with an end-capped structure can be added to the above materials to improve the impact resistance of the material . This application utilizes the difference in reactivity between amide ester flow promoters and different types of polycarbonate, and in the process of blending and extrusion reaction, the polycarbonate with unblocked structure is degraded by the reaction of amide ester flow promoters Improve its fluidity, but do not react with polycarbonate with end-capping structure and maintain the original high impact resistance of this part of polycarbonate, using this reactivity difference to form a combination of high molecular weight and low molecular weight polycarbonate material, and finally meet the requirements of high fluidity and high impact resistance of the material at the same time.

As an embodiment, the amide ester flow promoter includes at least one of branched-chain alkyl primary amides, erucamide, and nonadecanoic acid amide. In the examples of this application, the amide ester flow promoter The agent is preferably nonadecanoic acid amide.

Specifically, the mechanism of the degradation reaction between nonadecanoic acid amide and polycarbonate with an uncapped structure is shown in FIG. 1 . The terminal amine group of nonadecanoic acid amide reacts with the carbonic acid group, causing the molecular chain of polycarbonate to break, and the polycarbonate with large molecular weight is degraded into small molecular weight phenolic terminal compound and stearyl carbamate terminal. base compound, thus enhancing the fluidity of the original polycarbonate.

In order not to reduce the impact resistance of the polycarbonate composition without reducing its fluidity, the present application further limits the ratio of parts by weight of the first polycarbonate, the second polycarbonate, and the flow promoter. Calculated in parts by weight, the first polycarbonate is 5-95 parts, more specifically, the first polycarbonate is 5, 10, 30, 49.75, 70, 95 parts, preferably 49.75 parts, limited to The space is not exhaustive here. Calculated in parts by weight, the second polycarbonate is 5-95 parts, more specifically, the second polycarbonate is 5, 10, 30, 49.75, 70, 95 parts, preferably 49.75 parts, limited to The space is not exhaustive here. Calculated in parts by weight, the flow enhancer is 0.2-0.4 parts, more specifically, the flow enhancer is 0.2, 0.3, 0.4 parts, which will not be exhaustive here due to space limitations.

In a preferred embodiment of the present application, the mass ratio of the first polycarbonate to the second polycarbonate is (1.2-0.8):1, more specifically, the first polycarbonate and the second polycarbonate The mass ratio of the second polycarbonate is 1.2:1, 1.1:1, 1:1, 0.9:1, 0.8:1, preferably 1:1, and will not be exhaustive here due to space limitations.

Wherein, the other additives include antioxidants.

Antioxidants can effectively reduce the thermal oxidation reaction speed of plastic macromolecules, delay the thermal and oxygen degradation process of plastic resins, significantly improve the heat resistance of plastic resins, and prolong the service life of plastic products. In the embodiment of the present invention, the antioxidant includes at least one of antioxidant S2225P, antioxidant 168, antioxidant 1010, and antioxidant 1098. Users can choose according to actual needs, and no specific restrictions are made here. .

Corresponding to the above polycarbonate composition, the present application also provides a preparation method of the polycarbonate composition. As shown in Figure 2, the preparation method of described polycarbonate composition comprises the steps:

S1: In parts by weight, 10-190 parts of polycarbonate, 0.2-0.4 parts of flow promoter and 0.1-0.3 parts of other additives are uniformly mixed through a mixer to obtain a mixture;

S2: adding the mixture into a twin-screw extruder for melt blending, and extruding strands;

S3: cutting the strips into pellets by a pelletizer, drying by an elevator, and packaging to obtain a finished product.

Preferably, the extrusion temperature of the strand is 210-250°C.

Preferably, the screw speed of the twin-screw extruder is 300-500 rpm.

All the above optional technical solutions may be combined in any way to form optional embodiments of the present application, which will not be repeated here.

The beneficial effects of the present application will be further described below in conjunction with examples and comparative examples.

The raw material used in embodiment and comparative example is described as follows now:

The first polycarbonate with a capping rate of 2%: produced by SABIC, LEXANResin131;

The first polycarbonate with a capping rate of 30%: produced by Luxi Chemical Industry, 1609T;

The second polycarbonate with a capping rate of 90%: produced by SABIC, Lexan OQ1050;

The second polycarbonate with an end-capping rate of 80%: produced by LG, 8000;

Nonadecanoic acid amide: produced by CRODA;

Antioxidant S2225P: produced by American Albemarle, S2225P.

Material performance test method:

1. Melt index test: according to the national standard GB/T3682-2000 method.

2. Notch impact strength test: test according to the national standard method GB/T1043-2008.

Comparative example 1

A kind of polycarbonate composition, calculates by weight, and the component of described material comprises:

99.5 parts of the first polycarbonate, 0.3 part of antioxidant S2225P, and 0.2 part of nonadecanoic acid amide, wherein the melt index of the first polycarbonate is 10, and the end-capping rate of the first polycarbonate is 2%.

The preparation method of above-mentioned polycarbonate composition comprises:

In parts by weight, 99.5 parts of the first polycarbonate, 0.3 part of antioxidant S2225P and 0.2 part of nonadecanoic acid amide are mixed uniformly by a mixer to obtain a mixture;

The mixture is added into a twin-screw extruder for melt blending, extruding strands;

The strips are cut into pellets by a pelletizer, dried by an elevator, and packaged to obtain the finished product.

Comparative example 2

Compared with Comparative Example 1, the difference lies in 99.3 parts of the first polycarbonate and 0.4 parts of nonadecanoic acid amide.

Comparative example 3

A kind of polycarbonate composition, calculates by weight, and the component of described material comprises:

99.5 parts of the second polycarbonate, 0.3 part of the antioxidant S2225P, and 0.2 part of nonadecanoic acid amide, wherein the melt index of the second polycarbonate is 20, and the end-capping rate of the second polycarbonate is 90%.

The preparation method of above-mentioned polycarbonate composition comprises:

In parts by weight, 99.5 parts of the second polycarbonate, 0.3 part of antioxidant S2225P and 0.2 part of nonadecanoic acid amide are mixed uniformly by a mixer to obtain a mixture;

The mixture is added into a twin-screw extruder for melt blending, extruding strands;

The strips are cut into pellets by a pelletizer, dried by an elevator, and packaged to obtain the finished product.

Comparative example 4

Compared with Comparative Example 3, the difference lies in 99.3 parts of the second polycarbonate and 0.4 parts of nonadecanoic acid amide.

Example 1

A kind of polycarbonate composition, calculates by weight, and the component of described material comprises:

49.75 parts of the first polycarbonate, 49.75 parts of the second polycarbonate, 0.3 part of antioxidant S2225P, 0.2 part of nonadecanoic acid amide, wherein, the melt index of the first polycarbonate is 10, the first polycarbonate The end-capping rate was 2%, the melt index of the second polycarbonate was 20, and the end-capping rate of the second polycarbonate was 90%.

The preparation method of above-mentioned polycarbonate composition comprises:

In parts by weight, 49.75 parts of the first polycarbonate, 49.75 parts of the second polycarbonate, 0.3 part of antioxidant S2225P and 0.2 part of nonadecanoic acid amide were mixed uniformly by a mixer to obtain a mixture;

The mixture is added into a twin-screw extruder for melt blending, extruding strands;

The strips are cut into pellets by a pelletizer, dried by an elevator, and packaged to obtain the finished product.

Example 2

Compared with Example 1, the difference is 45 parts of the first polycarbonate and 54.5 parts of the second polycarbonate.

Example 3

Compared with Example 1, the difference is 54 parts of the first polycarbonate and 45.5 parts of the second polycarbonate.

Example 4

Compared with Example 1, the difference is that the end-capping rate of the first polycarbonate is 30%.

Example 5

Compared with Example 1, the difference is that the end-capping rate of the second polycarbonate is 80%.

Example 6

Compared with Example 1, the difference is 0.3 parts of nonadecanoic acid amide.

Example 7

Compared with Example 1, the difference is 0.4 parts of nonadecanoic acid amide.

The performance test results of the first polycarbonate and the second polycarbonate are shown in Table 1.

Table 1 The first polycarbonate and the second polycarbonate performance test result

performance first polycarbonate Second polycarbonate Melt Index 10 20 Notched impact strength 8 10

Table 2 shows the performance test results of the polycarbonate compositions prepared in Examples 1-7 and Comparative Examples 1-4.

The polycarbonate composition property test result prepared by table 2 embodiment 1-7 and comparative example 1-4

From the test results in Table 1 and Table 2 above, it can be seen that:

1. From the test results of the first polycarbonate and comparative examples 1-2, it can be known that nonadecanoic acid amide can degrade with the polycarbonate with non-end-capped structure in the first polycarbonate. The first polycarbonate reaction degrades to lower molecular weight polymers to increase the melt index of the material. Within a certain range, as the mass of nonadecanoic acid amide increases, more of the first polycarbonate is degraded into low-molecular-weight polymers, so the melt index of the material increases even more. Although nonadecanoic acid amide can increase the melt index of the first polycarbonate, the notched impact strength of the material also decreases significantly thereupon.

2. From the test results of the first polycarbonate, the second polycarbonate and Comparative Examples 1-4, it can be known that nonadecanoic acid amide reacts differently with the first polycarbonate and the second polycarbonate. Because there are more polycarbonates with unblocked structure in the first polycarbonate, nonadecanoic acid amide can degrade the polycarbonate with unblocked structure in the first polycarbonate so that the melting of the first polycarbonate The index increased more. In the second polycarbonate, there are less polycarbonates with unblocked structures, and nonadecanoic acid amide improves the melt index of the second polycarbonate to a limited extent.

3. From the test results of Comparative Examples 1-4 and Example 1, it can be seen that nonadecanoic acid amide can effectively improve the quality of the material when the weight and number ratio of the first polycarbonate and the second polycarbonate is 1:1. Melt index, and retains the notched impact strength of the material.

4. From the test results of Examples 1-3, it can be seen that different mass ratios of the first polycarbonate and the second polycarbonate have different effects on the melt index and notched impact strength of the material. The higher the mass ratio of the first polycarbonate in the whole (that is, the lower the mass ratio of the second polycarbonate in the whole), the higher the melt index and the lower the notched impact strength. This is because the first polycarbonate The ester capping rate is low, the open groups are more, and the reaction degradation is more.

5. From the test results of Example 1 and Examples 4-5, it can be seen that the capping ratios of the first polycarbonate and the second polycarbonate have an influence on the melt index and the notched impact strength of the material. The higher the end-capping rate of the first polycarbonate and the second polycarbonate, the lower the melt index and the higher the notched impact strength. more.

6. From the test results of Example 1 and Examples 6-7, it can be seen that the quality of nonadecanoic acid amide has an influence on the melt index and notched impact strength of the material. When the addition amount is within 0.3%, the higher the quality of nonadecanoic acid amide, the higher the melt index and the lower the notched impact strength; when the addition amount exceeds 0.3%, the higher the quality of nonadecanoic acid amide, the higher the melt index and the The impact strength remains unchanged. This is because the more mass of nonadecanoic acid amide when the amount added is within 0.3%, the stronger the degradation reaction will be. When the added amount exceeds 0.3%, nonadecanoic acid amide will be saturated and no longer promote the degradation reaction.

Above, a kind of polycarbonate composition provided by the application and its preparation method have been introduced in detail. In this paper, specific examples have been used to illustrate the principle and implementation of the application. The description of the above examples is only used to help Understand the method and its core idea of the present application; at the same time, for those of ordinary skill in the art, according to the idea of the present application, there will be changes in the specific implementation and application scope. In summary, the contents of this specification should not be construed as limiting the application.

Claims (10)

1. The polycarbonate composition is characterized by comprising the following components in parts by weight:

10-190 parts of polycarbonate, 0.2-0.4 part of flow promoter and 0.1-0.3 part of other auxiliary agents, wherein the polycarbonate comprises a first polycarbonate with the end capping rate of 0-30% and a second polycarbonate with the end capping rate of 80-100%; the flow promoter can reactively degrade the polycarbonate having an unblocked structure, and the flow promoter cannot reactively degrade the polycarbonate having an unblocked structure.

2. The polycarbonate composition of claim 1, wherein the polycarbonate comprises a first polycarbonate and a second polycarbonate, wherein the first polycarbonate is 5-95 parts and the second polycarbonate is 5-95 parts.

3. The polycarbonate composition of claim 1, wherein the polycarbonate comprises at least one of an aromatic polycarbonate, an aliphatic polycarbonate, and an aromatic-aliphatic polycarbonate.

4. The polycarbonate composition of claim 3, wherein the polycarbonate is a bisphenol a type polycarbonate.

5. The polycarbonate composition of any of claims 1-4, wherein the flow promoter comprises an amide-based flow promoter.

6. The polycarbonate composition of claim 5, wherein the amide-ester flow promoter comprises at least one of a branched alkyl primary amide, an erucamide, and a nonadecanoic acid amide.

7. The polycarbonate composition of claim 1, wherein the other auxiliary agent comprises an antioxidant.

8. The polycarbonate composition of claim 1, wherein the weight ratio of the first polycarbonate to the second polycarbonate is (1.2 to 0.8) to 1.

9. The polycarbonate composition of claim 8, wherein the first polycarbonate and the second polycarbonate are present in a weight ratio of 1:1.

10. A method of preparing the polycarbonate composition of claim 1, wherein the method of preparing comprises:

according to the weight portions, 10 to 190 portions of polycarbonate, 0.2 to 0.4 portion of flow promoter and 0.1 to 0.3 portion of other auxiliary agent are evenly mixed by a mixer to obtain a mixture;

adding the mixture into a double-screw extruder for melt blending, and extruding a material strip;

and (3) granulating the material strips by a granulator, drying by a lifter, and packaging to obtain a finished product.

Images