WO2022100015A1 - Polycarbonate composition, preparation method therefor, and application thereof - Google Patents

Abstract

Disclosed is a polycarbonate composition with high reliability and good formability, comprising, in parts by weight, 100 parts of a polycarbonate resin and 0.15-1.5 parts of compound components. The compound components are the compounding of a hindered phenol aromatic hydrocarbon derivative, a phosphoric acid quencher, and a furanone derivative, wherein, based on the total weight of the compound components, the weight percentage of the hindered phenol aromatic hydrocarbon derivative is 5-15 wt%; the weight percentage of the phosphoric acid quencher is 10-30 wt%; the weight percentage of the furanone derivative is 55-85 wt%. The formability and demolding properties of the polycarbonate composition can be significantly improved by means of the specific compounding components. When a flame retardant is added, the flame retardancy can be significantly improved.

Description

A kind of polycarbonate composition and its preparation method and application technical field

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

Background technique

Polycarbonate (PC) is an engineering plastic with excellent performance. It has good comprehensive properties, high mechanical strength, good impact toughness, dimensional stability, good heat resistance, and good electrical insulation. It is used in home appliances, digital products, IT products, etc. and other fields have a wide range of applications.

In order to obtain good moldability, the prior art mainly improves the fluidity of the resin by adjusting the molecular weight and distribution of the resin, thereby improving the processability of the material. However, the polycarbonate obtained by this method will lead to a decline in mechanical properties such as impact, and the Disadvantages of greatly reduced stress cracking and poor solvent resistance. There are also studies to improve the processability of materials by adding low molecular weight oligomers to polycarbonate, for example, US 2003/0181603, US 2009/0312479, WO 2011/014778 and US 2015/0183986 describe the use of low molecular weight polyhydrocarbon resins As a flow modifier a composition with good impact toughness, flowability and thermal deformation stability. WO 2017/005739 discloses diglycerides as flow modifiers, characterized by good mechanical properties, very good rheological properties (easy flow) and high thermal shape stability. However, the above-mentioned methods of adding low-molecular-weight substances may lead to a decrease in the heat resistance of the material. In particular, the relatively long residence time results in a large amount of color components, resulting in discoloration during processing and molding. In addition, in the flame retardant system, the material will also be reduced. flame retardant properties.

In addition, in order to obtain good releasability, the existing technology mainly reduces the adhesion between the plastic and the metal mold by adding external lubricants, but it will increase the risk of precipitation and sticking, resulting in appearance defects in injection molding (instruction Figure 2), or affect the subsequent spraying or welding process. During the ejection stage of injection molding, the core of the part is usually separated mechanically by means of an ejector pin. When the demolding performance is poor, the ejection force of the mold is too large, and the ejector pin will whiten the part in light, and destroy the part in heavy; on the contrary, when the demolding force is too small, the part will easily slip off, which is not conducive to the operation of the robot in automation. Therefore, ensuring the proper mold release of the material is the key to ensuring normal production.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a polycarbonate composition with good moldability and good releasability.

Another object of the present invention is to provide a method for preparing the above-mentioned polycarbonate composition.

The present invention is achieved through the following technical solutions:

A polycarbonate composition, in parts by weight, comprising 100 parts of polycarbonate resin, 0.15-1.5 parts of compound components; the compound components are hindered phenol aromatic derivatives, phosphoric acid quencher, Compounding of furanone derivatives, wherein, based on the total weight of the compounding components, hindered phenol aromatic derivatives accounts for 5-15wt%; phosphoric acid quencher accounts for 10-30wt%; furan The weight percentage of ketone derivatives is 55-85 wt%.

The hindered phenol aromatic derivatives is selected from β-(4-hydroxy-3,5-di-tert-butylphenyl) propionic acid n-octadecyl ester, tetrakis[methyl-(3,5-di-tert-butyl) At least one of the group-4-hydroxyphenyl) propionate] pentaerythritol ester and triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-methylphenyl) propionate.

Preferably, the hindered phenol arene derivatives are selected from triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-methylphenyl)propionate.

The phosphoric acid quencher is selected from tris(2,4-di-tert-butylphenyl) phosphite, dioctadecyl pentaerythritol bisphosphite, bis(2,4-di-tert-butyl) pentaerythritol diphosphite. at least one of phosphites.

Preferably, the phosphoric acid quencher is selected from bis(2,4-di-tert-butyl) pentaerythritol diphosphite.

The furanone derivative is selected from xylyl dibutylbenzofuranone.

Preferably, based on the total weight of the compound components, the hindered phenol aromatic hydrocarbon derivatives account for 7-13wt%; the phosphoric acid quencher accounts for 15-25wt%; the furanone derivatives account for the weight% 62-78 wt%.

The content is preferably, the amount of the compound component is 0.3-0.9 part. When the addition amount of the compounding components reaches 0.3 parts, good demoldability and formability can be obtained, and when the addition amount reaches 0.9 parts, the demoulding force is not significantly improved.

The demoulding force refers to the resistance that needs to be overcome when the plastic part is released from the core. The schematic diagram is shown in Figure 1 of the following specification.

Calculation formula of release force: F release = f×P×A

f is the friction coefficient between the core and the part

P is the contact pressure

A is the contact area between the core and the part

The demolding force is characterized by measuring the force required to remove the cylinder on the core.

The weight average molecular weight of polycarbonate resins suitable for injection molding processing is 19,000-35,000.

In parts by weight, 0-30 parts of flame retardants are also included; the flame retardants are selected from C1-C16 alkyl sulfonate flame retardants, carbonate flame retardants, inorganic phosphate flame retardants, At least one of fluorine-silver ion complexes and phosphate ester flame retardants; the C1-C16 alkyl sulfonate flame retardants are selected from potassium perfluorooctane sulfonate, tetrafluoroethanesulfonate At least one of ethylammonium and potassium diphenylsulfone sulfonate; the carbonate flame retardant is selected from at least one of sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate and barium carbonate.

The preparation method of the above-mentioned polycarbonate composition includes the following steps: mixing the components uniformly, and then extruding and granulating through a twin-screw extruder to obtain the polycarbonate composition, wherein the temperature of the screw is 240° C. to 260° C. ℃, the rotation speed is 400～600rpm.

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

Compared with the conventional mold release system with lubricant as the main body in the prior art, the present invention can not only obtain a good antioxidant effect by selecting the compound of hindered phenol aromatic derivatives, phosphoric acid quenchers and furanone derivatives. , and can replace the addition of lubricant, and reduce the mold release force, improve the injection molding process performance. In addition, in the flame retardant polycarbonate system, the flame retardancy can be significantly improved.

Description of drawings

Figure 1: Schematic representation of demolding force.

Figure 2: Excessive demoulding force leads to wire drawing and uneven surface unevenness when the part is demolded.

Detailed ways

The present invention is described in more detail by the following examples, but the present invention is not limited by the following examples.

The raw materials used in the present invention are derived from commercially available products:

Polycarbonate resin: PC 1300 10NP, weight average molecular weight 22000.

Flame Retardant: FR2025, 3M Company.

Hindered phenol aromatic derivatives A: n-octadecyl β-(4-hydroxy-3,5-di-tert-butylphenyl) propionate;

Hindered phenol aromatic hydrocarbon derivative B: tetrakis[methyl-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester.

Hindered phenol aromatic derivative C: triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-methylphenyl)propionate.

Phosphoric Acid Quencher A: Tris(2,4-di-tert-butylphenyl)phosphite.

Phosphoric Acid Quencher B: Dioctadecyl pentaerythritol bisphosphite.

Phosphoric acid quencher C: bis(2,4-di-tert-butyl) pentaerythritol diphosphite.

Furanone Derivatives: Xylyldibutylbenzofuranone.

Antioxidant A: N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine.

Antioxidant B: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyloxyethyl)isocyanurate.

Antioxidant C: 3,9-bis[1,1-dimethyl-2-[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl]-2 ,4,8,10-Tetraoxaspiro[5.5]undecane.

Antioxidant D: 1,3,5-Tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-( 1H,3H,5H)-triketone.

Lubricant A: GLYCOLUBE-P, Lonza;

Lubricant B: A-C6A, Honeywell;

Lubricant C: MB50-002, Dow Corning;

Examples and comparative examples The preparation method of the polycarbonate composition: Mix the components uniformly, and then extrude and granulate through a twin-screw extruder to obtain a polycarbonate composition, wherein the temperature of the screw is 240 ℃ ~ 260 ℃ , the speed is 400 ~ 600rpm.

Various performance test methods:

(1) Demoulding force: In this study, the demolding force was mainly characterized by measuring the force required to remove the cylinder on the mold core. The parts are shown in the attached drawings.

Calculation formula of release force: F release = f*P*A

f is the friction coefficient between the core and the part

P is the contact pressure

A is the contact area between the core and the part

(2) Formability:

The appearance and the shape of the product after demolding were used to evaluate.

Grade 1: No visible silver wires on the outside, no sink marks on the outside, and no holes on the inside;

Level 2: A small amount of silver wire can be seen at the gate, no sink marks on the outside, and no holes on the inside;

Level 3: A small amount of silver wire can be seen on the whole part, no sink marks on the outside, and no holes on the inside;

Grade 4: A small amount of silver wire can be seen on the whole part, no sink marks can be seen on the outside, and the internal holes are less than 0.5cm;

Grade 5: A small amount of silver wire can be seen on the whole part, no sink marks on the outside, and internal holes > 0.5cm.

(3) Flame retardancy: vertical burning, test standard: UL94-2015, spline size: (125±5mm)×(13.0±0.5mm)×(1.5±0.15mm), 23±2℃, 50±5% RH adjustment for 48h, test steps:

The flame height is 20±1mm, the Bunsen burner is placed in the center of the sample, the mouth of the Bunsen burner is 10±1mm away from the bottom of the sample, the ignition time is 10±0.5s, and the speed is 300mm/s after 10±0.5s ignition. Remove the Bunsen burner by at least 150mm, and start recording the afterflame time t1 at the same time. When the afterflame stops, immediately ignite for 10±0.5s. After 10±0.5s, remove the Bunsen burner at least 150mm at a speed of 300mm/sec, and record at the same time. Afterflame time t2 and afterburn time t3.

Rating of flame level:

Judgment condition	V-0	V-1	V-2
Each independent sample burns for a duration t1 or t2	≤10s	≤30s	≤30s
Total burn duration t1+t2 for five samples of any treatment group	≤50s	≤250s	≤250s
After the second flame application, each individual sample burn duration and scorch burn time t2+t3	≤30s	≤60s	≤60s
Whether any sample continues to burn and burns hot to the clamp holding the sample	no	no	no
Whether burning particles or drips ignite absorbent cotton	no	no	Yes

Table 1: Component content (parts by weight) and test results of the polycarbonate compositions of Examples 1-8

It can be seen from Examples 1-4 that when the dosage of the compounding component reaches 0.3 part, the demoulding force can be reduced to nearly 3800, and when the dosage reaches 0.9 part, the demolding force can be decreased slowly by continuing to add.

As can be seen from Examples 1-8, the phosphoric acid quencher is preferably bis(2,4-di-tert-butyl) pentaerythritol diphosphite, and the hindered phenol aromatic hydrocarbon derivative is preferably triethylene glycol ether-bis(3-tert-butyl-) 4-Hydroxy-methylphenyl)propionate.

Table 2: Component content (parts by weight) and test results of the polycarbonate compositions of Examples 9-14

It can be seen from Examples 9-12 that the demolding force is lower under the preferred ratio.

It can be seen from Examples 13/14 and Comparative Examples 1-6 that the compound components of the present invention can also improve the flame retardancy.

Table 3: Comparative Example 1-7 Polycarbonate composition component content (parts by weight) and test results

Table 4: Comparative Example 8-14 Polycarbonate composition component content (parts by weight) and test results

It can be seen from the comparative examples 1-11 that the existing commonly used antioxidants and compounding can not well achieve the technical effect of the present invention.

It can be seen from Comparative Examples 12-14 that although commonly used lubricants are often used as mold release agents, they are insufficient in improving the formability of materials.

Claims (10)

1. A polycarbonate composition is characterized in that, in parts by weight, it comprises 100 parts of polycarbonate resin and 0.15-1.5 parts of compound components; the compound components are hindered phenol aromatic hydrocarbon derivatives, phosphoric acid Compounding of quencher and furanone derivative; wherein, based on the total weight of compound components, hindered phenol aromatic derivatives accounts for 5-15wt%; phosphoric acid quencher accounts for 10-15wt% 30wt%; the weight percentage of furanone derivatives is 55-85wt%.
2. The polycarbonate composition according to claim 1, wherein the hindered phenol aromatic hydrocarbon derivative is selected from n-octadecanoate of β-(4-hydroxy-3,5-di-tert-butylphenyl)propionic acid Carbon alcohol ester, tetrakis[methyl-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester, triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-methyl) At least one of phenyl) propionate; preferably, the hindered phenol aromatic hydrocarbon derivative is triethylene glycol ether-bis(3-tert-butyl-4-hydroxy-methylphenyl) propionate.
3. The polycarbonate composition according to claim 1, wherein the phosphoric acid quencher is selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphite, dioctadecyl pentaerythritol bis At least one of phosphite and bis(2,4-di-tert-butyl) pentaerythritol diphosphite; preferably, the phosphoric acid quencher is bis(2,4-di-tert-butyl) pentaerythritol diphosphite .
4. The polycarbonate composition according to claim 1, wherein the furanone derivative is xylyl dibutylbenzofuranone.
5. The polycarbonate composition according to claim 1, wherein, based on the total weight of the compounded components, the hindered phenol aromatic derivatives accounts for 7-13wt%; the phosphoric acid quencher accounts for the weight% It is 15-25wt%; the weight percentage of furanone derivatives is 62-78wt%.
6. The polycarbonate composition according to claim 1, wherein the weight part of the compounding components is 0.3-0.9 part.
7. The polycarbonate composition according to claim 1, wherein the weight average molecular weight of the polycarbonate resin is 19000-35000.
8. The polycarbonate composition according to claim 1, further comprising 0-30 parts by weight of a flame retardant; the flame retardant is selected from the group consisting of C1-C16 alkyl sulfonates. At least one of flame retardants, carbonate flame retardants, inorganic phosphate flame retardants, fluorine-silver ion composites, and phosphate ester flame retardants; the C1-C16 alkyl sulfonate flame retardants At least one selected from potassium perfluorooctanesulfonate, tetraethylammonium perfluoroethanesulfonate, potassium diphenylsulfonesulfonate; the carbonate flame retardant is selected from sodium carbonate, potassium carbonate, At least one of magnesium carbonate, calcium carbonate and barium carbonate.
9. The method for preparing a polycarbonate composition according to claims 1-8, comprising the following steps: mixing the components uniformly, and then extruding and granulating through a twin-screw extruder to obtain the polycarbonate composition , wherein the temperature of the screw is 240°C to 260°C, and the rotational speed is 400 to 600 rpm.
10. The application of the polycarbonate composition of claims 1-8, characterized in that it is used to prepare products with smooth surfaces.

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