WO2021036614A1 - Glass fiber-reinforced polycarbonate composite material and preparation method and use therefor - Google Patents

Abstract

A glass fiber-reinforced polycarbonate composite material and a preparation method and a use therefor, comprising the following components: component A: 40 parts - 90 parts of a polycarbonate; component B: 5 parts - 60 parts of a polysiloxane block copolymer; component C: 5 parts - 30 parts of a glass fiber; component D: 2 parts - 40 parts of a fluorine-containing compound; and component E: 1 part - 30 parts of silicone. Adding a specific amount of a polysiloxane block copolymer, a fluorine-containing compound, and silicone to the formula of the glass fiber-reinforced polycarbonate composite material is able to ensure that the composite material ultimately produced has a certain siloxane content and a certain mass ratio of fluorine and silicon, causing the composite material produced to have an excellent high modulus of elasticity and high toughness, and also have excellent processability. Unlike conventional reinforcement modification means, the present composite material is provided with both rigidity and toughness, and at the same time, is provided with high fluidity and markedly reduced dielectric loss, and is particularly suited for the 5G communications industry.

Description

Glass fiber reinforced polycarbonate composite material and preparation method and application thereof Technical field

The invention relates to the technical field of engineering plastics, in particular to a glass fiber reinforced polycarbonate composite material and a preparation method and application thereof.

Background technique

Polycarbonate resin PC is a thermoplastic engineering plastic with excellent comprehensive properties. In recent years, its high transparency, good flame retardancy, heat resistance, electrical insulation and dimensional stability, low water absorption and other characteristics have been widely used in the automotive, electronic and electrical, communication industries, construction industries, etc. field. With the expansion of its application fields, polycarbonate has higher requirements for its impact strength, flexural modulus, tensile strength, fluidity, dielectric loss and other properties. Simple polycarbonate or ordinary polycarbonate The material still cannot meet the requirements, therefore, the polycarbonate material needs to be modified. In order to improve the performance and grade of materials and meet the needs of final parts and customers, glass fiber reinforcement is generally used to improve its processability and modification.

However, the existing glass fiber reinforced polycarbonate composite material has the contradiction of high rigidity but low toughness, and the conventional toughening method is to directly add toughening agents, which will also greatly reduce the fluidity of the composite material, and the composite material The improvement of rigidity and toughness is also very limited, and due to the inherent dielectric loss application characteristics of polycarbonate, which severely limits its application in the automotive, electronic and electrical, communications industry, construction industry and other fields, especially the 5G communications industry .

Summary of the invention

In order to overcome the shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a glass fiber reinforced polycarbonate composite material with both rigidity and toughness, high fluidity and low dielectric loss.

Another object of the present invention is to provide a method for preparing the above-mentioned glass fiber reinforced polycarbonate composite material.

Another object of the present invention is to provide the use of the above-mentioned glass fiber reinforced polycarbonate composite material.

The present invention is realized through the following technical solutions:

A glass fiber reinforced polycarbonate composite material, in parts by weight, includes the following components:

Preferably, the glass fiber reinforced polycarbonate composite material, in parts by weight, includes the following composition:

Wherein, the percentage of siloxane content in the glass fiber reinforced polycarbonate composite material to the total weight of the composite material is 0.8 wt% to 18 wt%, preferably 3.5 wt% to 12.5 wt%.

Wherein, the weight ratio of fluorine element and silicon element in the glass fiber reinforced polycarbonate composite material is 1:(0.1-3), preferably 1:(0.5-2).

Wherein, the polycarbonate is selected from one or more of aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, and branched polycarbonate; preferably aromatic polycarbonate .

Preferably, the aromatic polycarbonate is an aromatic polycarbonate with a viscosity average molecular weight of 13,000 to 40,000, preferably an aromatic polycarbonate with a viscosity average molecular weight of 18,000 to 28,000. When the viscosity average molecular weight is within the above range, the mechanical strength is good and excellent moldability can be maintained. Among them, the viscosity average molecular weight is calculated by using dichloromethane as a solvent and the solution viscosity at a test temperature of 25°C.

The above-mentioned preparation method of polycarbonate can be prepared by interfacial polymerization method and transesterification method, and the content of terminal hydroxyl groups can be controlled in the process.

Preferably, the polysiloxane block copolymer includes a polydimethylsiloxane block and a polycarbonate block of bisphenol A, and has 0.8 wt% to 35 wt% of siloxane based on the weight of component B. content. After adding the siloxane block copolymer, the siloxane content of the glass fiber reinforced polycarbonate composite can be tested by the near-infrared analysis method. The test method is to weigh a fixed weight of glass fiber reinforced polycarbonate composite pellets. The material is tested after being evenly dissolved into flakes with methane.

Preferably, the fluorine-containing compound can be a fiber-shaped or non-fiber-shaped fluoropolymer, preferably a non-fiber-shaped fluoropolymer. In some embodiments, it is preferable to use an encapsulated fluoropolymer. Pre-blended with the second polymer, especially polyolefins, to form an agglomerated material. The encapsulated fluoropolymer includes a fluoropolymer with a melting point higher than 320°C, such as polyvinyl fluoride. The preferred encapsulated fluoropolymer is polyethylene encapsulated polytetrafluoroethylene, where PE is 40%, and PTFE Is 60%.

Preferably, the molecular weight of the silicone is 50,000 to 300,000. Among them, the molecular weight of the silicone is too large, and the compatibility with the matrix is not good, which is likely to cause the performance degradation of the composition, and the molecular weight of the silicone is too small, and it is easy to precipitate and cause surface defects.

The glass fiber reinforced polycarbonate composite material of the present invention, based on the weight of the glass fiber reinforced polycarbonate composite material, may also include component F: 0-10 parts of other additives; the other additives are selected from stabilizers, One or more of flame retardants, lubricants, mold release agents, plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.

Suitable stabilizers may include organic phosphites, such as triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tris-nonylphenyl phosphite, dimethylbenzene Phosphonates, trimethyl phosphate, etc., organic phosphites, alkylated monohydric phenols or polyhydric phenols, alkylation reaction products of polyhydric phenols and dienes, butylation of p-cresol or dicyclopentadiene Reaction products, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds, polyol esters, benzotriazoles, benzophenones One or more combinations.

Suitable flame retardants may include phosphate-based flame retardants or sulfonate flame retardants. Preferred phosphate flame retardants include bisphenol A diphosphate tetraphenyl ester, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, bisphenol A diphosphate tetraphenyl ester, resorcinol tetra( 2,6-Dimethylphenyl ester) and tetramethylbenzylpiperidine amide; sulfonates can also be selected as flame retardants, such as Rimar salt potassium perfluorobutanesulfonate, KSS potassium diphenylsulfone sulfonate, benzenesulfonate Sodium and the like are suitable.

The preparation method of the glass fiber reinforced polycarbonate composite material includes the following steps:

1) Weigh polycarbonate, polysiloxane block copolymer, fluorine-containing compound, silicone, and other additives according to the ratio, stir and blend for 1-3 minutes in a high-mixer to obtain a premix;

2) Place the obtained premix in the main feed port of the twin-screw extruder, add glass fiber to the side feed port for melt extrusion, pelletize and dry, and get ready.

Wherein, the length-to-diameter ratio of the twin-screw extruder is 46:1-50:1; the temperature of the twin-screw extruder from the feeding section to the die is as follows: the temperature of the first zone is 120℃-160℃, and the temperature of the twin-screw extruder is 120℃-160℃. Zone temperature 200℃-230℃, three zone temperature 200℃-230℃, four zone temperature 200℃-220℃, five zone temperature 200℃-220℃, six zone temperature 200℃-220℃, seven zone temperature 200℃- 220℃, eight zone temperature 200℃-220℃, nine zone temperature 200℃-220℃, ten zone temperature 200℃-220℃, eleven zone temperature 200℃-220℃, machine head temperature 220℃-240℃, host The rotation speed is 350 rpm-700 rpm.

The application of the glass fiber reinforced polycarbonate composite material obtained by the above preparation method in the automobile, electronic and electrical, communication industries, and the construction industry is preferably the application in the 5G communication industry.

Compared with the prior art, the present invention has the following beneficial effects:

The invention chooses to add a specific content of polysiloxane block copolymer, fluorine-containing compound and silicone to the glass fiber reinforced polycarbonate composite material formula, so as to ensure that the prepared composite material has a specific content of siloxane Content and specific weight ratio of fluorine element and silicon element, the prepared composite material not only has excellent high modulus and high toughness characteristics, but also has excellent processing performance. Compared with conventional reinforcement modification methods, the composite material has both Rigidity and toughness, while having significantly reduced dielectric loss, suitable for automotive, electronic and electrical, communications industry, construction industry and other fields, especially suitable for 5G communications industry.

detailed description

The present invention will be further explained by specific embodiments below. The following examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the following examples.

Test standards or methods for each performance:

Izod notched impact strength test method: according to ASTM D256-2010 standard;

Izod unnotched impact strength test method: according to ASTM D256-2010 standard;

Tensile strength test method: According to ASTM D638-2014 standard, the tensile speed is 10mm/min;

The test method of flexural modulus is based on ASTM D790-2010 standard, and the bending speed is 2mm/min;

Liquidity test method: According to ASTM D1238-2013, the melting temperature is 300℃;

Dielectric loss test method: According to ASTM D150-11 standard.

Polycarbonate used in the present invention:

Component A-1: Aromatic polycarbonate with a viscosity average molecular weight of 19,000, Idemitsu, Japan;

Component A-2: Aromatic polycarbonate with a viscosity average molecular weight of 28000, Idemitsu, Japan;

The polysiloxane block copolymer used in the present invention:

Component B-1: a polysiloxane block copolymer with a siloxane content of 9wt%, Idemitsu, Japan;

Component B-2: Polysiloxane block copolymer with a siloxane content of 30% by weight, Idemitsu, Japan;

Glass fiber used in the present invention:

Component C-1: Toyobo;

Fluorine-containing compounds used in the present invention:

Component D-1: non-fiber shaped fluoropolymer, Guangzhou Entropy Energy;

Component D-2: Polytetrafluoroethylene encapsulated by polyethylene, in which PE is 40%, PTFE is 60%, and Guangzhou Entropy Energy;

Silicone used in the present invention:

Component E-1: silicone with a molecular weight of 50,000, Dow Corning;

Component E-2: silicone with a molecular weight of 280,000, Dow Corning;

Other additives used in the present invention:

Component F-1: Stabilizer: 2112, Adike;

Component F-2: Flame retardant: BDP, Adike.

Examples 1-8 and Comparative Examples 1-6: Preparation of glass fiber reinforced polycarbonate composite materials

Weigh the polycarbonate, polysiloxane block copolymer, fluorine-containing compound, silicone, and other additives according to the ratio, stir and blend for 1-3 minutes in a high-mixer to obtain a premix; combine the obtained premix The material is placed in the main feed port of the twin-screw extruder, glass fiber is added to the side feed port for melt extrusion, granulated and dried, and the glass fiber reinforced polycarbonate composite material is obtained. The Izod notched impact strength, Izod unnotched impact strength, tensile strength, flexural modulus, fluidity, and dielectric loss of the above-mentioned glass fiber reinforced polycarbonate composite materials were tested.

Table 1 Specific proportions (parts by weight) of Examples 1-8 and Comparative Examples 1-6 and their test performance results

Continued Table 1

Note: The "-" in Table 1 means that the test cannot be performed at all.

Claims (12)

1. A glass fiber reinforced polycarbonate composite material, in parts by weight, includes the following components:

   
2. The glass fiber reinforced polycarbonate composite material according to claim 1, in parts by weight, comprising the following components:

   
3. The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the siloxane content in the glass fiber reinforced polycarbonate composite material accounts for 0.8 wt% to 18 wt% of the total weight of the composite material. %, preferably 3.5wt%-12.5wt%.
4. The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the weight ratio of fluorine element and silicon element in the glass fiber reinforced polycarbonate composite material is 1: (0.1-3), Preferably it is 1: (0.5-2).
5. The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the polycarbonate is selected from aromatic polycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, One or more of branched polycarbonates; preferably aromatic polycarbonate; the aromatic polycarbonate is an aromatic polycarbonate with a viscosity average molecular weight of 13,000-40000, preferably a viscosity average molecular weight of 18,000-28,000 Of aromatic polycarbonate.
6. The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the polysiloxane block copolymer comprises polydimethylsiloxane block and bisphenol A polycarbonate The block has a siloxane content of 0.8 wt% to 35 wt% based on the weight of component B.
7. The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the fluorine-containing compound is selected from one of fiber forming, non-fiber forming fluoropolymer, and encapsulated fluoropolymer. One or more; the encapsulated fluoropolymer is preferably polyethylene encapsulated polytetrafluoroethylene, wherein PE is 35 wt% to 45 wt%, and PTFE is 55 wt% to 65 wt%.
8. The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, wherein the molecular weight of the silicone is 50,000 to 300,000.
9. The glass fiber reinforced polycarbonate composite material according to claim 1 or 2, characterized in that, based on the weight of the glass fiber reinforced polycarbonate composite material, further comprising component F: 0-10 parts of other additives; The auxiliary agent is selected from one or more of stabilizers, flame retardants, lubricants, mold release agents, plasticizers, fillers, antistatic agents, antibacterial agents, and colorants.
10. A method for preparing glass fiber reinforced polycarbonate composite material according to any one of claims 1-9, characterized in that it comprises the following steps:

    1) Weigh polycarbonate, polysiloxane block copolymer, fluorine-containing compound, silicone, and other additives according to the ratio, stir and blend for 1-3 minutes in a high-mixer to obtain a premix;

    2) Place the obtained premix in the main feed port of the twin-screw extruder, add glass fiber to the side feed port for melt extrusion, pelletize and dry, and get ready.
11. The method for preparing glass fiber reinforced polycarbonate composite material according to claim 10, wherein the length to diameter ratio of the twin-screw extruder is 46:1-52:1; The temperature from the feeding section to the machine head is as follows: the temperature in the first zone is 120℃-160℃, the temperature in the second zone is 200℃-230℃, the temperature in the third zone is 200℃-230℃, the temperature in the fourth zone is 200℃-220℃, and the temperature in the fifth zone 200℃-220℃, six zone temperature 200℃-220℃, seven zone temperature 200℃-220℃, eight zone temperature 200℃-220℃, nine zone temperature 200℃-220℃, ten zone temperature 200℃-220℃ , The temperature of the eleven zone is 200℃-220℃, the temperature of the machine head is 220℃-240℃, and the main engine speed is 350rpm-700rpm.
12. The application of the glass fiber-reinforced polycarbonate composite material obtained by the preparation method of claim 10 in the automobile, electronic and electrical, communication industries, and construction industries, preferably in the 5G communication industry.