CN110054881B

CN110054881B - High-fluidity polycarbonate modified material

Info

Publication number: CN110054881B
Application number: CN201910246734.0A
Authority: CN
Inventors: 傅永进; 叶根林
Original assignee: Starway International Home Living Co ltd
Current assignee: Starway International Home Living Co ltd
Priority date: 2019-03-29
Filing date: 2019-03-29
Publication date: 2022-01-11
Anticipated expiration: 2039-03-29
Also published as: CN110054881A

Abstract

The invention belongs to the technical field of high polymer materials, and provides a high-fluidity polycarbonate modified material. The composite material comprises the following raw materials in parts by weight: 60-80 parts of polycarbonate, 10-25 parts of polymethylpentene copolymer, 5-12 parts of acrylonitrile-styrene copolymer, 6-15 parts of ethylene-vinyl acetate copolymer, 0.2-0.6 part of halogen-free organic flame retardant, 0.3-0.8 part of lubricant, 0.2-0.7 part of antioxidant and 0.2-1 part of ultraviolet absorbent. The invention ensures the high transparency of the material to the maximum extent, and simultaneously, the high fluidity, the flexibility and the scratch-resistant rigidity of the material meet the requirements of the market on transparent plastic furniture materials.

Description

High-fluidity polycarbonate modified material

Technical Field

The invention belongs to the technical field of high polymer materials, relates to a polycarbonate modified material, and particularly relates to a high-fluidity polycarbonate modified material.

Background

In recent years, transparent plastic furniture is more and more popular among consumers due to various shapes, unique styles and extremely high transparency. However, the material requirements for producing transparent furniture are extremely high: the material has high transparency, good mechanical strength, weather resistance and aging resistance. Polycarbonates are amorphous polymers of a nearly colorless glassy state, have good optical properties, have high notched Izod impact strength, and have very low creep rates under load below 100 ℃. At present, the polycarbonate is one of hot door raw materials of transparent plastic furniture, however, the melting temperature of the polycarbonate is higher, the melt viscosity after melting is also higher, the fluidity is poorer, internal stress is easily generated, and a prepared product is easy to crack due to the internal stress, has poorer scratch resistance and can yellow after being exposed to ultraviolet rays for a long time.

The prior art discloses a modified polycarbonate with high fluidity and low-temperature toughness as Chinese patent No. CN105542176A, the polycarbonate is modified by reactive polydimethylsiloxane, the operation is complex, and the comprehensive cost is high; chinese patent No. CN104448760A discloses a scratch-resistant high-gloss PC/ABS material, however, PC is incompatible with ABS as a non-crystalline system, and a compatilizer is required to be added to influence the transparency of the material.

Disclosure of Invention

The present invention has been made in view of the above problems, and an object of the present invention is to provide a polycarbonate-modified material.

In order to achieve the purpose, the invention adopts the following technical scheme:

a high-fluidity polycarbonate modified material comprises the following raw materials in parts by weight: 60-80 parts of polycarbonate, 10-25 parts of polymethylpentene copolymer, 5-12 parts of acrylonitrile-styrene copolymer, 6-15 parts of ethylene-vinyl acetate copolymer, 0.2-0.6 part of halogen-free organic flame retardant, 0.3-0.8 part of lubricant, 0.2-0.7 part of antioxidant and 0.2-1 part of ultraviolet absorbent.

In the high-fluidity polycarbonate modified material, the light transmittance of the polymethylpentene copolymer is not less than 87%, the haze value is less than 2%, the styrene content of the acrylonitrile-styrene copolymer is 60-70%, and the vinyl acetate content of the ethylene-vinyl acetate copolymer is 40-50%.

In the high-fluidity polycarbonate modified material, the halogen-free organic flame retardant is composed of one or more of sulfonate halogen-free flame retardant, aromatic phosphate halogen-free flame retardant and organic silsesquioxane resin, and the lubricant is pentaerythritol stearate lubricant.

In the high-fluidity polycarbonate modified material, the antioxidant is hindered phenol antioxidant or a mixture prepared by compounding hindered phenol antioxidant and phosphite antioxidant, and the ultraviolet absorbent is one or more of benzoate ultraviolet absorbent and benzotriazole ultraviolet absorbent.

The high-fluidity polycarbonate modified material comprises the following raw materials in parts by weight: 72 parts of polycarbonate, 18 parts of polymethylpentene copolymer, 9 parts of acrylonitrile-styrene copolymer, 11 parts of ethylene-vinyl acetate copolymer, 0.4 part of halogen-free organic flame retardant, 0.6 part of lubricant, 0.4 part of antioxidant and 0.7 part of ultraviolet absorbent.

The high-fluidity polycarbonate modified material is prepared by the following steps:

A. preparing the raw materials according to the parts by weight of the raw materials,

B. the polycarbonate and the acrylonitrile-styrene copolymer are dried separately,

C. adding polymethylpentene copolymer, acrylonitrile-styrene copolymer and ethylene-vinyl acetate copolymer into a high-speed mixer, uniformly mixing at a high speed of 800-1000 rpm,

D. adding the rest of the components except for the polycarbonate into the mixture, uniformly mixing at a low speed of 400-600 rpm,

E. and adding the mixture and the dried polycarbonate into a double-screw extruder, and extruding and granulating at the temperature of 240-270 ℃ to obtain the high-fluidity polycarbonate modified material.

In the preparation method of the high-fluidity polycarbonate modified material, the drying condition of the polycarbonate is that a vacuum drying oven is dried for 15-20 hours at 110-120 ℃, the dried polycarbonate is still placed in the drying oven, the drying condition of the acrylonitrile-styrene copolymer is that a hot air type circulating air dryer is dried for 2-4 hours at 80-100 ℃, and the temperature of a high-speed mixer is raised to 60-80 ℃ before the components are added into the high-speed mixer.

B. drying the polycarbonate in a vacuum drying oven at 110-120 ℃ for 15-20 h, drying the acrylonitrile-styrene copolymer in a hot air type circulating air dryer at 80-100 ℃ for 2-4 h,

C. pouring the dried polycarbonate, acrylonitrile-styrene copolymer and other residual components into an injection molding machine, setting the injection molding pressure to be 90-120 MPa, the temperature of a charging barrel to be 260-300 ℃, the temperature of a nozzle to be 5-10 ℃ lower than that of the charging barrel,

E. the mixture is melted and then injected into a mold cavity, medium and low speed processing and low-high-low multi-stage injection are adopted, the temperature of the mold is 70-100 ℃, cooling, demolding and molding are carried out,

F. and carrying out heat treatment on the molded product at the temperature of 100-120 ℃ for 15-30 min.

In the preparation method of the high-fluidity polycarbonate modified material, the raw material components except the polycarbonate are uniformly mixed in a high-speed mixer before the raw material components are filled into an injection molding machine.

Among the above-mentioned high-fluidity polycarbonate-modified materials, the high-fluidity polycarbonate-modified materials are used in household appliances.

Compared with the prior art, the invention has the advantages that:

1. the polymethylpentene copolymer, the acrylonitrile-styrene copolymer and the ethylene-vinyl acetate copolymer adopted by the invention are all high-gloss and high-light-transmittance materials, and no other compatilizer is needed to be added, so that the high transparency of the materials is ensured to the greatest extent. Meanwhile, the material prepared by the invention has high fluidity, flexibility and scratch-resistant rigidity, and meets the market demand on transparent plastic furniture materials.

2. At present, the polycarbonate in China, particularly the high-quality polycarbonate, mainly depends on import and has high cost. The invention can use common polycarbonate as raw material, the raw material price is relatively low, and the invention also has flame retardant property, and the operation is simple, the components and the preparation process are more environment-friendly, and the invention meets the market demand.

3. The invention can directly carry out injection molding, reduces the cost in the furniture production process by one-step injection molding, can flexibly adjust the raw material components according to the requirements, and is more suitable for the actual production requirements.

Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.

Detailed Description

Examples 1 to 6

The present invention will be described in further detail with reference to examples and comparative examples.

Polycarbonate No. 1 PC-1 is Bayer 2805, Germany.

Polycarbonate No. 2 is abbreviated as PC-2 and is selected from Jiaxingdi L-1250Z 100.

Polymethylpentene copolymer, homemade, abbreviated PMP. 4-methyl-1-pentene monomer is subjected to bulk polymerization, and initiators of 2, 2-dimethyl propionic acid and ferrous ions are adopted, so that the preparation method comprises the following steps:

4-methyl-1-pentene monomer was charged into an autoclave equipped with a stirrer under a nitrogen atmosphere. The pressure was increased to 1.03MPa with ethylene, and the nitrogen gas was displaced by repeating the evacuation 3 times. Then, the mixed solution of 2, 2-dimethylpropionic acid and ferrous ions was rapidly injected through the inlet at the top of the reactor. Sealing the autoclave, and immediately pressurizing to 1800-2300 Pa by using hydrogen; then pressurizing to 3200-4000 Pa (13 mol% hydrogen in gas phase) by using mixed gas, stirring for 30min, and continuously feeding 4-methyl-1-pentene monomer (hydrogen is not fed any more). And (3) keeping the temperature of the prepolymer at 160-200 ℃ in the synthesis stage, entering the molding stage, increasing the temperature to 280-320 ℃, and reducing the pressure of the discharged gas to below 120 Pa. After 3-4.5 h, the reaction is finished, and the polymethylpentene copolymer with the polymerization degree of 1200-1800 and the relative molecular weight of 18000-28000 g/mol is obtained. The light transmittance is 89-92%, the haze value is less than 2%,

acrylonitrile-styrene copolymer No. 1, AS-1 for short, having a styrene content of 60%.

Acrylonitrile-styrene copolymer No. 2, AS-2 for short, having a styrene content of 70%.

Ethylene-vinyl acetate copolymer No. 1, self-made, abbreviated as VAE-1, having a vinyl acetate content of 40%.

Ethylene-vinyl acetate copolymer No. 2, self-made, abbreviated as VAE-2, having a vinyl acetate content of 50%.

The halogen-free organic flame retardant is F-535 from Arichem (SLOSS) of America.

PETS of Longsha Co Ltd is selected as the lubricant.

The antioxidant is B215 of New Material Co, Ltd.

The ultraviolet ray is German BASF UV-P.

The feed compositions of examples 1-6 are shown in Table 1.

TABLE 1 raw Material compositions

Comparative examples 1 to 3

Comparative examples 1 to 3 the raw materials were the same as in examples.

Comparative examples 1 to 3 the raw material components are shown in Table 1.

Application example 1

High-fluidity polycarbonate modified materials were prepared according to examples 1 to 6 and comparative examples 1 to 3:

B. drying the polycarbonate in a vacuum drying oven at 110-120 ℃ for 15-20 h, and then still placing the dried polycarbonate in the drying oven; and drying the acrylonitrile-styrene copolymer in a hot air type circulating air dryer at the temperature of 80-100 ℃ for 2-4 h.

C. And (3) raising the temperature of the high-speed mixer to 60-80 ℃. Adding polymethylpentene copolymer, acrylonitrile-styrene copolymer and ethylene-vinyl acetate copolymer into a high-speed mixer, uniformly mixing at a high speed of 800-1000 rpm,

And drying the granules at 90 ℃ for 5 hours, and then performing injection molding on the granules by using an injection molding machine to obtain a standard sample strip, wherein the injection molding temperature is 210-240 ℃. After the sample is formed, the sample is adjusted for 24 hours in the environment with (23 +/-2) DEG C and (50 +/-5)% humidity.

The obtained test sample strips of examples 1-6 and proportions 1-3 have the test correlation properties shown in Table 2:

melt flow rate was measured according to ASTM D-1238 under test conditions of 300 ℃ and 1.2 kg; the tensile strength was measured according to ASTM D-638 under test conditions of 5 mm/min; the flexural strength was measured according to ASTM D-790 under test conditions of 2.8 mm/min; the notched Izod impact strength was tested according to ASTM D-256, test condition 1/4 inch; rockwell hardness was measured according to ASTM D-785; the light transmittance is tested according to DIN 5036-1, and the test condition is 2 mm; the haze is tested according to ISO 14782, and the test condition is 2 mm; the test condition is that the flame retardant rating is tested according to UL94, and the test condition is 3.2 mm; the heat distortion temperature was tested according to ISO75A-1, -2 under test conditions of 1.80MPa, unannealed.

TABLE 2 test results of sample band Performance parameters

As can be seen from Table 2, the performances of the examples 1-6 are far better than those of the comparative example, the light transmittance and the haze of the examples are far better than those of the comparative example, and the examples have excellent visual and aesthetic effects; the tensile strength and the bending strength show that the toughness of the embodiment is superior to that of the comparative example, and the requirement of plastic furniture on high toughness of the material is met; the excellent notched izod impact strength and rockwell hardness of the examples indicate that the materials prepared by the invention overcome the defect that polycarbonate is not wear resistant. Meanwhile, the test result also shows the scientificity of the formula.

Application example 2

Transparent equal-thickness integral armchairs prepared in example 5, example 6 and comparative examples 1-3:

C. raw material components except the polycarbonate are mixed uniformly in a high-speed mixer. Pouring the dried polycarbonate, acrylonitrile-styrene copolymer and other residual components into an injection molding machine, setting the injection molding pressure to be 90-120 MPa, the temperature of a charging barrel to be 260-300 ℃, the temperature of a nozzle to be 5-10 ℃ lower than that of the charging barrel,

Carrying out performance test on the obtained transparent equal-thickness integral armchair sample; the test results are shown in Table 3.

The appearance of the plastic part is tested according to the table 3 in GB/T32487 & 2016 general technical conditions for plastic furniture; resistance to ageing according to GB/T16422.2-1999 Plastic laboratory light Exposure test method part 2: testing xenon arc lamps; the tensile strength is tested according to GB/T1040-; the stability and the strength are tested according to GB/T10357.3-1989 intensity and durability of furniture mechanical property tests; flame retardancy the part 2 of the burning behaviour was determined according to GB/T2406.2-2009 "oxygen index for plastics: room temperature test (RT test). The evaluation method is according to GB/T32487-2016 general technical conditions for plastic furniture.

TABLE 3 Performance testing of transparent equal thickness integral arm chair samples

From the viewpoint of the overall performance of the furniture article, the sample produced by the present invention is excellent in properties, particularly aging resistance, and durability. After 600h test, the degree of discoloration is still kept at a low level, the tensile strength is still kept at a good retention rate, the comparative example can only be maintained within 500h at most, and the tensile strength is obviously lower than that of the example. The durability still meets the standard under the condition that the test level is 4 grades, and the comparative example can only meet the standard under the condition that the test level is 2-3 grades. The material of the invention is an excellent transparent plastic furniture material.

The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.

Although the terms polycarbonate, polymethylpentene, acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, halogen-free organic flame retardant, lubricant, antioxidant, ultraviolet absorber, colorant, high-speed mixer, twin-screw extruder, injection molding machine, etc., are used more extensively herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention and they are to be interpreted as any additional limitation which is not in accordance with the spirit of the present invention.

Claims

1. The high-fluidity polycarbonate modified material is characterized by comprising the following raw materials in parts by weight: 60-80 parts of polycarbonate, 10-25 parts of polymethylpentene copolymer, 5-12 parts of acrylonitrile-styrene copolymer, 6-15 parts of ethylene-vinyl acetate copolymer, 0.2-0.6 part of halogen-free organic flame retardant, 0.3-0.8 part of lubricant, 0.2-0.7 part of antioxidant and 0.2-1 part of ultraviolet absorbent,

the light transmittance of the polymethylpentene copolymer is not less than 87%, the haze value is less than 2%, the styrene content of the acrylonitrile-styrene copolymer is 60-70%, and the vinyl acetate content of the ethylene-vinyl acetate copolymer is 50-60%.

2. The high-fluidity polycarbonate modified material as defined in claim 1, wherein the halogen-free organic flame retardant comprises one or more of sulfonate halogen-free flame retardants, aromatic phosphate halogen-free flame retardants and organic silsesquioxane resins, and the lubricant is pentaerythritol stearate lubricant.

3. The high-fluidity polycarbonate modified material as defined in claim 1, wherein the antioxidant is a hindered phenol antioxidant or a mixture of a hindered phenol antioxidant and a phosphite antioxidant, and the ultraviolet absorber is one or more of a benzoate ultraviolet absorber and a benzotriazole ultraviolet absorber.

4. The high-fluidity polycarbonate modified material according to claim 1, which is characterized by comprising the following raw materials in parts by weight: 72 parts of polycarbonate, 18 parts of polymethylpentene copolymer, 9 parts of acrylonitrile-styrene copolymer, 11 parts of ethylene-vinyl acetate copolymer, 0.4 part of halogen-free organic flame retardant, 0.6 part of lubricant, 0.4 part of antioxidant and 0.7 part of ultraviolet absorbent.

5. The preparation method of the high-fluidity polycarbonate modified material according to any one of claims 1 to 4, characterized by comprising the following steps:

6. The method for preparing the high-fluidity polycarbonate modified material as described in claim 5, wherein the drying conditions of the polycarbonate are that the polycarbonate is dried in a vacuum drying oven at 110-120 ℃ for 15-20 h and then is still placed in the drying oven, the acrylonitrile-styrene copolymer is dried in a hot air type circulating air dryer at 80-100 ℃ for 2-4 h, and the temperature of the high-speed mixer is raised to 60-80 ℃ before the components are added into the high-speed mixer.

7. The preparation method of the high-fluidity polycarbonate modified material according to any one of claims 1 to 4, characterized by comprising the following steps:

E. the mixture is melted and then injected into a mold cavity, medium and low speed processing and low-high-low multi-stage injection are adopted, the temperature of the mold is 90-100 ℃, cooling, demolding and molding are carried out,

8. The method for preparing a high flow polycarbonate modified material as claimed in claim 7, wherein the raw material components other than polycarbonate are mixed in a high mixing machine before the raw material components are injected into an injection molding machine.