CN112457649B

CN112457649B - PC/PBAT transparent composite material and preparation method thereof

Info

Publication number: CN112457649B
Application number: CN202011339638.XA
Authority: CN
Inventors: 万虎; 冯先强
Original assignee: Guangzhou Shiyuan Electronics Thecnology Co Ltd
Current assignee: Guangzhou Shiyuan Electronics Thecnology Co Ltd
Priority date: 2020-11-25
Filing date: 2020-11-25
Publication date: 2022-11-15
Anticipated expiration: 2040-11-25
Also published as: CN112457649A

Abstract

The invention relates to a PC/PBAT transparent composite material and a preparation method thereof. The PC/PBAT transparent composite material comprises PC, PBAT, a PC chain scission agent, a toughening agent, a main antioxidant, an auxiliary antioxidant and a lubricant, and has the advantages of higher impact strength, higher thermal deformation temperature, more excellent processability, resistance to corrosion of various chemical reagents and complete biodegradability by compounding two polymer resin materials of PC and PBAT; through the use of the PC chain scission agent, PC molecular chain scission is catalyzed to a certain extent, so that a terminal group with higher motion activity and capable of performing ester exchange reaction with PBAT is generated, the ester exchange reaction between PC and PBAT is promoted, the crystallization capability of PBAT is effectively inhibited, and the prepared composite material has higher transparency. The preparation method of the PC/PBAT transparent composite material has the advantages of reasonable design of process steps, simple operation, low requirements on equipment and energy consumption, contribution to reducing the production cost and meeting the requirements of industrial large-scale production.

Description

PC/PBAT transparent composite material and preparation method thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a PC/PBAT transparent composite material and a preparation method thereof.

Background

Polycarbonate (PC) is a kind of engineering plastics with excellent comprehensive properties, and has high impact strength, high heat distortion temperature, good dimensional stability, high transparency of more than 95%, excellent optical properties, high melt viscosity, and poor resistance to attack by various chemical agents due to non-crystalline polymers, which limits the application of the PC in some fields.

The poly (butylene adipate terephthalate) (PBAT) is a thermoplastic biodegradable material which has better ductility and processability, and is a crystalline polymer which has excellent chemical reagent corrosion resistance but low heat distortion temperature and impact strength, and has no optical property because of being a crystalline polymer.

From the advantages and disadvantages of PC and PBAT, after the two resins are compounded, the two resins can mutually make up for the deficiencies, and the composite material with excellent comprehensive performance is prepared.

Disclosure of Invention

Based on this, the object of the present invention is to provide a PC/PBAT transparent composite material which has the advantages of high impact strength, high heat distortion temperature, excellent optical properties, good ductility and processability and is biodegradable.

A PC/PBAT transparent composite material comprises the following raw material components in parts by weight:

according to the PC/PBAT transparent composite material provided by the embodiment of the invention, two polymer resin materials, namely PC and PBAT, are compounded, so that the advantages of the PC and PBAT are integrated, compared with single PBAT, the PC/PBAT transparent composite material has higher impact strength and heat distortion temperature, and compared with single PC, the PC/PBAT transparent composite material has more excellent processability, resistance to various chemical reagent attacks and complete biodegradability; secondly, by using the PC chain scission agent, the embodiment of the invention utilizes the characteristic that the PC chain scission agent can catalyze the PC molecular chain scission to a certain extent, so as to generate a certain amount of end groups with higher kinematic activity, the end groups with higher kinematic activity can perform ester exchange reaction with PBAT, so as to promote the ester exchange reaction between PC and PBAT, after the ester exchange reaction of PBAT, the crystallization capacity of the PBAT is inhibited, the crystallinity is reduced, the prepared composite material has higher transparency, and the composite material meets the application requirements in the special technical field; meanwhile, after the ester exchange reaction of the PC, the motion capability of the chain segment is improved, the internal stress between the formed molecular chains is reduced, the weakening effect of the internal stress on the light, heat and corrosion medium corrosion resistance of the prepared transparent composite material is reduced, and the chemical reagent corrosion resistance of the prepared transparent composite material is effectively improved; and the accurate control of the usage amount of the PC chain scission agent is further combined, the ester exchange reaction between PC and PBAT is effectively regulated, and the problem that the performance of the composite material is influenced due to excessive chain scission of PC can be avoided while the ester exchange reaction is promoted to be carried out. In addition, the impact resistance of the prepared transparent composite material is further improved by adding the toughening agent, and meanwhile, the use amount of the toughening agent is reasonably controlled, so that the influence of excessive addition on the light transmittance of the composite material and the influence on the transparency of the composite material are avoided.

Further, the PC is bisphenol A polycarbonate which has higher impact strength and heat distortion temperature, excellent dimensional stability and high transparency; the PBAT is poly (butylene adipate terephthalate), can be completely biodegraded, has higher crystallization capacity, excellent chemical reagent etching resistance and better ductility and elongation at break.

Further, the PC chain scission agent is selected from one or more of hydrogen phosphate and bicarbonate, and can catalyze the degradation of PC, so that a terminal group with higher kinematic activity is generated, and the ester exchange reaction with PBAT is facilitated.

Further, the grain size of the toughening agent is not more than 700nm, and the toughening agent is selected from one or more of MBS toughening agent, acrylate toughening agent and silicone rubber toughening agent.

Further, the primary antioxidant is one or more of hindered phenol antioxidant 1010, hindered phenol antioxidant 1076 and hindered phenol antioxidant 245.

Further, the auxiliary antioxidant is selected from one or more of phosphite antioxidant 168 and phosphite antioxidant PEP-36. The main antioxidant and the auxiliary antioxidant are matched for use, so that the degradation of PC and PBAT in the production and processing process can be inhibited, and the stability of a system is ensured.

Further, the lubricant is selected from one or more of polyol ester lubricant, silicone lubricant and stearic acid lubricant, which can reduce the melt viscosity of PC and PBAT in the melt blending process, improve the processability, and improve the demolding performance of the system in the subsequent processing and forming process.

According to the PC/PBAT transparent composite material provided by the embodiment of the invention, two polymer resin materials, namely PC and PBAT, are compounded, so that the advantages of the PC and PBAT are integrated, compared with single PBAT, the PC/PBAT transparent composite material has higher impact strength and heat distortion temperature, and compared with single PC, the PC/PBAT transparent composite material has more excellent processability, resistance to various chemical reagent attacks and complete biodegradability; secondly, by using the PC chain scission agent, a certain amount of end groups with higher kinematic activity can be generated by utilizing the characteristic that the PC chain scission agent can catalyze the PC molecular chain scission to a certain degree, the end groups with higher kinematic activity can perform ester exchange reaction with PBAT so as to promote the ester exchange reaction between PC and PBAT, after the PBAT performs the ester exchange reaction, the crystallization capacity of the PBAT is inhibited, the crystallinity of the PBAT is reduced, the transparency of the prepared composite material is higher, the application requirements in the special technical field are met, and simultaneously, after the PC performs the ester exchange reaction, the chain segment kinematic capacity of the PC is improved, the internal stress between the molecular chains after molding is reduced, the weakening effect of the internal stress on the light, heat and corrosion medium corrosion resistance of the prepared transparent composite material is reduced, and the chemical reagent corrosion resistance of the prepared transparent composite material is effectively improved; and the accurate control of the usage amount of the PC chain scission agent is further combined, the transesterification reaction between PC and PBAT is effectively regulated, and the problem that the performance of the composite material is influenced due to excessive chain scission of PC can be avoided while the transesterification reaction is promoted to be carried out. In addition, the impact resistance of the prepared transparent composite material is further improved by adding the toughening agent, and meanwhile, the use amount of the toughening agent is reasonably controlled, so that the influence of excessive addition on the light transmittance of the composite material and the transparency of the composite material is avoided.

In addition, the dosage of each raw material component is reasonably adjusted through the comprehensive optimization design of the formula, and the specific selection of the raw material components is preferably limited in a further preferred embodiment, so that the raw materials of the components can be coordinated and promoted mutually, and the comprehensive performance of the prepared transparent composite material can be improved to the maximum extent by the formed integral technical scheme.

In addition, the embodiment of the invention provides a preparation method of the PC/PBAT transparent composite material, which comprises the following specific operation steps:

s1, weighing PC, PBAT, a PC chain scission agent, a toughening agent, a main antioxidant, an auxiliary antioxidant and a lubricant in formula amounts, sequentially adding into a mixing device, and uniformly mixing to obtain a premix;

and S2, carrying out melt blending and extrusion granulation on the premix obtained in the step S1 through an extruder to obtain the PC/PBAT transparent composite material.

Further, the blending conditions in step S1 are: firstly stirring at a high speed of 2000-6000 rpm for 1-6 min, then stirring at a low speed of 300-2000 rpm for 1-6 min, and discharging at a stirring speed of 300-2000 rpm.

Further, the rotation speed of the extruder host in the melt blending and extrusion granulation in the step S2 is 500-700 rpm, and the temperature of each zone is controlled within 250-270 ℃.

The preparation method of the PC/PBAT transparent composite material provided by the embodiment of the invention has the advantages of reasonable design of process steps, simplicity in operation, lower equipment requirements and energy consumption, contribution to reduction of production cost and accordance with the requirements of industrial large-scale production.

For a better understanding and practice, the present invention is described in detail below with reference to the accompanying drawings.

Drawings

FIG. 1 is an SEM image of a sample bar of the PC/PBAT transparent composite material described in example 1 obtained according to the preparation method of example 5.

Detailed Description

In order to make the aforementioned objects, features and advantages of the present invention more comprehensible, embodiments of the present invention are described in detail below.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described herein, and it will be apparent to those of ordinary skill in the art that the present invention may be practiced without departing from the spirit and scope of the present invention, and therefore the present invention is not limited by the examples disclosed below.

Example 1

The embodiment 1 of the invention provides a PC/PBAT transparent composite material, which comprises the following raw materials in parts by weight: 100 parts of PC, 50 parts of PBAT, 0.02 part of monocalcium phosphate, 3 parts of MBS toughening agent, 0.5 part of hindered phenol antioxidant 1010, 0.3 part of phosphite antioxidant 168 and 0.5 part of polyol lubricant. Wherein the PC is a bisphenol A polycarbonate; the PBAT is poly adipic acid/butylene terephthalate, and the particle size of the MBS toughening agent is not more than 700nm.

Example 2

The embodiment 2 of the invention provides a PC/PBAT transparent composite material, which comprises the following raw materials in parts by weight: 50 parts of PC, 30 parts of PBAT, 0.05 part of sodium bicarbonate, 7 parts of acrylate toughening agent, 1076.6 parts of hindered phenol antioxidant, 0.5 part of phosphite antioxidant PEP-36 and 0.8 part of stearic acid lubricant. Wherein the PC is a bisphenol A polycarbonate; the PBAT is poly adipic acid/butylene terephthalate, and the particle size of the acrylate toughening agent is not more than 700nm.

Example 3

The embodiment 3 of the invention provides a PC/PBAT transparent composite material, which comprises the following raw materials in parts by weight: 150 parts of PC, 100 parts of PBAT, 0.1 part of monocalcium phosphate, 8 parts of MBS toughening agent, 2 parts of silicone rubber toughening agent, 245 4 parts of hindered phenol antioxidant, 168 parts of phosphite antioxidant, 1 part of phosphite antioxidant PEP-36 and 2 parts of silicone lubricant. Wherein the PC is bisphenol A polycarbonate; the PBAT is poly adipic acid/butylene terephthalate, and the particle sizes of the MBS toughening agent and the silicon rubber toughening agent are not more than 700nm.

Example 4

The embodiment 4 of the invention provides a PC/PBAT transparent composite material, which comprises the following raw materials in parts by weight: 80 parts of PC, 90 parts of PBAT, 0.07 part of monocalcium phosphate, 10 parts of acrylate toughening agent, 5 parts of silicone rubber toughening agent, 1010 parts of hindered phenol antioxidant, 168 parts of phosphite antioxidant and 3 parts of polyol ester lubricant. Wherein the PC is a bisphenol A polycarbonate; the PBAT is poly adipic acid/butylene terephthalate, and the particle sizes of the acrylate toughening agent and the silicon rubber toughening agent are not more than 700nm.

Example 5

Embodiment 5 of the present invention provides a method for preparing the PC/PBAT transparent composite material described in embodiments 1 to 4, which includes the following specific operation steps:

s1, weighing PC, PBAT, a PC chain scission agent, a toughening agent, a main antioxidant, an auxiliary antioxidant and a lubricant according to the formula of any one of embodiments 1 to 4, sequentially adding the weighed PC, PBAT, PC chain scission agent, toughening agent, main antioxidant, auxiliary antioxidant and lubricant into a mixing device, and uniformly mixing, wherein the mixing conditions are as follows: firstly stirring at a high speed of 2000rpm for 6min, then stirring at a low speed of 300rpm for 6min, and discharging at a stirring speed of 2000rpm to obtain a premix;

and S2, melting and blending the premix obtained in the step S1 through an extruder, and extruding and granulating, wherein the rotating speed of the extruder host is 500rpm, and the temperature of each zone is controlled within 250-270 ℃, so that the PC/PBAT transparent composite material is obtained.

Example 6

Embodiment 6 of the present invention provides a method for preparing the PC/PBAT transparent composite material described in embodiments 1 to 4, which comprises the following specific operation steps:

s1, weighing PC, PBAT, a PC chain scission agent, a toughening agent, a main antioxidant, an auxiliary antioxidant and a lubricant according to the formula of any one of embodiments 1 to 4, sequentially adding the weighed PC, PBAT, PC chain scission agent, toughening agent, main antioxidant, auxiliary antioxidant and lubricant into a mixing device, and uniformly mixing, wherein the mixing conditions are as follows: firstly, stirring at a high speed of 6000rpm for 1min, then stirring at a low speed of 2000rpm for 1min, and discharging at a stirring speed of 300rpm to obtain a premix;

and S2, melting and blending the premix obtained in the step S1 through an extruder, extruding and granulating, wherein the rotating speed of a host of the extruder is 700rpm, and the temperature of each zone is controlled within 250-270 ℃, so that the PC/PBAT transparent composite material is obtained.

Example 7

s1, weighing PC, PBAT, a PC chain scission agent, a toughening agent, a main antioxidant, an auxiliary antioxidant and a lubricant according to the formula of any one of the embodiments 1 to 4, sequentially adding the weighed PC, PBAT, PC chain scission agent, toughening agent, main antioxidant, auxiliary antioxidant and lubricant into mixing equipment, and uniformly mixing, wherein the mixing conditions are as follows: firstly, stirring at a high speed of 3000rpm for 4min, then stirring at a low speed of 1000rpm for 4min, and discharging at the stirring speed of 1000rpm to obtain a premix;

and S2, melting and blending the premix obtained in the step S1 through an extruder, and extruding and granulating, wherein the rotating speed of the extruder host is 600rpm, and the temperature of each zone is controlled within 250-270 ℃, so that the PC/PBAT transparent composite material is obtained.

Comparative example 1

Comparative example 1 comprises the following raw materials in parts by weight: 100 parts of PC, 1 part of monocalcium phosphate, 5 parts of MBS toughening agent, 1010 parts of hindered phenol antioxidant, 168 parts of phosphite antioxidant and 3 parts of polyol lubricant. Wherein the PC is bisphenol A polycarbonate; the particle size of the MBS toughening agent is not more than 700nm.

Comparative example 2

Comparative example 2 comprises the following raw materials in parts by weight: 100 parts of PBAT, 2 parts of monocalcium phosphate, 8 parts of acrylate toughening agent, 1076 parts of hindered phenol antioxidant, 1 part of phosphite antioxidant PEP-36 and 1 part of stearic acid lubricant. Wherein the PBAT is poly adipic acid/butylene terephthalate, and the particle size of the acrylate toughening agent is not more than 700nm.

Comparative example 3

Comparative example 3 comprises the following raw materials in parts by weight: 100 parts of PC, 50 parts of PBAT, 1 part of MBS toughening agent, 2 parts of silicone rubber toughening agent, 245 parts of hindered phenol antioxidant, 0.5 part of phosphite antioxidant PEP-36 and 0.5 part of silicone lubricant. Wherein the PC is bisphenol A polycarbonate; the PBAT is poly adipic acid/butylene terephthalate, and the particle sizes of the MBS toughening agent and the silicon rubber toughening agent are not more than 700nm.

Comparative example 4

Comparative example 4 comprises the following raw materials in parts by weight: 100 parts of PC, 50 parts of PBAT, 3 parts of monocalcium phosphate, 30 parts of MBS toughening agent, 1010.7 parts of hindered phenol antioxidant, 168.3 parts of phosphite antioxidant and 0.1 part of polyol ester lubricant. Wherein the PC is bisphenol A polycarbonate; the PBAT is poly adipic acid/butylene terephthalate, and the particle size of the MBS toughening agent is not more than 700nm.

Preparing corresponding sample particles by using the raw material component formula described in examples 1 to 4 and comparative examples 1 to 4 according to the method of example 5, further preparing corresponding sample strips by using injection molding, processing the sample strips obtained by using the PC/PBAT transparent composite material according to the preparation method of example 5 by using dichloromethane, scanning and imaging by using a Scanning Electron Microscope (SEM), and further testing the impact strength, the thermal deformation temperature, the light transmittance and the acid and alkali erosion resistance of the obtained sample strips, wherein the impact strength is measured according to ISO-related test standards, the thermal deformation temperature is measured at 1.8, the acid erosion resistance is measured by using Mpa test that the sample particles or the sample strips are immersed in glacial acetic acid for 5 hours, the alkali erosion resistance is measured by using the sample particles or the sample strips are immersed in NaOH solution with the concentration of 3wt% for 5 hours, and then the tensile strength is measured according to ISO-related test standards, and the corresponding test data are shown in the following table:

referring to fig. 1, fig. 1 is an SEM image of a sample strip of the PC/PBAT transparent composite material of example 1 obtained according to the preparation method of example 5, as shown in the figure, after dichloromethane treatment, the PC resin is partially dissolved, and as seen from the SEM image, the PBAT resin is mainly seen, and it can be seen that a layer of dense PBAT crystallites is formed at the outermost layer of the sample strip, which can effectively resist the attack of chemical reagents such as acid and alkali, and the prepared PC/PBAT transparent composite material has excellent chemical reagent attack resistance, the PBAT ratio decreases from the surface layer to the core layer, the PC ratio increases, and the two resins are not uniformly mixed.

As can be seen from the test data in the table, the PBAT is not included in the formulation of comparative example 1, the sample strip prepared by simply adding PC has poor chemical resistance, and the tensile strength retention is low after being etched by glacial acetic acid and NaOH solution; the formulation of comparative example 2 does not include PC, and the sample strip prepared by simply adding PBAT has lower impact properties, heat distortion temperature and transparency; the formula of the comparative example 3 does not contain a PC chain scission agent, and the detection data shows that the prepared sample strip has low light transmittance and no transparent property; the addition amount of the toughening agent in the formula of the comparative example 4 is higher than that defined in the examples of the invention, and as can be seen from the detection data, although the impact performance of the prepared sample strip is higher, the light transmittance is lower, and the sample strip does not have the transparency, so that the requirement on the transparency of the transparent composite material is not met.

According to the PC/PBAT transparent composite material and the preparation method thereof, the prepared sample has good impact property, high thermal deformation temperature, good light transmission property and excellent actually-measured comprehensive performance, the PC/PBAT transparent composite material can be prepared into a transparent film and various devices with required structures by adopting different processing and forming processes according to requirements, and the PC/PBAT transparent composite material is applied to the technical fields of film materials, electronic and electrical appliances and mechanical equipment, has high added value of products and good market scene.

In summary, the PC/PBAT transparent composite material of the embodiment of the invention combines the advantages of PC and PBAT by compounding two polymer resin materials, compared with PBAT alone, the PC/PBAT transparent composite material has higher impact strength and thermal deformation temperature, and compared with PC alone, the PC/PBAT transparent composite material has more excellent processability, resistance to various chemical reagent attacks, and complete biodegradability; secondly, by using the PC chain scission agent, the embodiment of the invention can generate a certain amount of end groups with higher kinematic activity by utilizing the characteristic that the PC chain scission agent can catalyze the PC molecular chain scission to a certain degree, the end groups with higher kinematic activity can perform ester exchange reaction with PBAT so as to promote the ester exchange reaction between PC and PBAT, after the PBAT performs the ester exchange reaction, the crystallization capacity of the PBAT is inhibited, the crystallinity of the PBAT is reduced, the transparency of the prepared composite material is higher, the application requirement in the special technical field is met, meanwhile, after the PC performs the ester exchange reaction, the chain segment kinematic capacity of the PC is improved, the internal stress between the molecular chains after molding is reduced, the weakening effect of the internal stress on the light, heat and corrosion medium corrosion resistance of the prepared transparent composite material is reduced, and the chemical reagent corrosion resistance of the prepared transparent composite material is effectively improved; and the accurate control of the usage amount of the PC chain scission agent is further combined, the ester exchange reaction between PC and PBAT is effectively regulated, and the problem that the performance of the composite material is influenced due to excessive chain scission of PC can be avoided while the ester exchange reaction is promoted to be carried out. In addition, the impact resistance of the prepared transparent composite material is further improved by adding the toughening agent, and meanwhile, the use amount of the toughening agent is reasonably controlled, so that the influence of excessive addition on the light transmittance of the composite material and the transparency of the composite material is avoided.

In addition, the embodiment of the invention reasonably adjusts the dosage of each raw material component through the comprehensive optimization design of the formula, and preferably limits the specific selection of the raw material components in the further preferred embodiment, so that the raw materials of each component can be coordinated and promoted mutually, and the overall technical scheme formed can maximally improve the comprehensive performance of the prepared transparent composite material.

The preparation method of the PC/PBAT transparent composite material provided by the embodiment of the invention has the advantages of reasonable design of process steps, simplicity in operation, lower equipment requirements and energy consumption, contribution to reduction of production cost and capability of meeting the requirements of industrial large-scale production.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.

Claims

1. The PC/PBAT transparent composite material is characterized by comprising the following raw material components in parts by weight:

the PC is bisphenol A polycarbonate; the PBAT is poly (butylene adipate terephthalate); the PC chain scission agent is selected from one or more of hydrogen phosphate and bicarbonate; the grain size of the toughening agent is not more than 700nm, and the toughening agent is selected from one or more of MBS toughening agent, acrylate toughening agent and silicone rubber toughening agent; the main antioxidant is one or more of hindered phenol antioxidant 1010, hindered phenol antioxidant 1076 and hindered phenol antioxidant 245; the lubricant is selected from one or more of polyalcohol ester lubricant, silicone lubricant and stearic acid lubricant.

2. The preparation method of the PC/PBAT transparent composite material according to claim 1, which is characterized by comprising the following specific operation steps:

s1, weighing PC, PBAT, a PC chain scission agent, a toughening agent, a main antioxidant, an auxiliary antioxidant and a lubricant according to the formula ratio, sequentially adding the components into a mixing device, and uniformly mixing to obtain a premix;

and S2, melting and blending the premix obtained in the step S1 through an extruder, and extruding and granulating to obtain the PC/PBAT transparent composite material.

3. The method for preparing a PC/PBAT transparent composite material according to claim 2, characterized in that the blending conditions in step S1 are: firstly stirring at a high speed of 2000-6000 rpm for 1-6 min, then stirring at a low speed of 300-2000 rpm for 1-6 min, and discharging at a stirring speed of 300-2000 rpm.

4. The method for preparing the PC/PBAT transparent composite material according to claim 2, wherein the rotation speed of the extruder host in the melt blending and extrusion granulation in the step S2 is 500-700 rpm, and the temperature of each zone is controlled within 250-270 ℃.