CN113861653B

CN113861653B - Flame-retardant polycarbonate composite material and preparation method and application thereof

Info

Publication number: CN113861653B
Application number: CN202111145027.6A
Authority: CN
Inventors: 田征宇; 汪静; 刘志雄; 刘贤文; 董相茂
Original assignee: Shanghai Kingfa Science and Technology Co Ltd; Jiangsu Kingfa New Material Co Ltd
Current assignee: Shanghai Kingfa Science and Technology Co Ltd; Jiangsu Kingfa New Material Co Ltd
Priority date: 2021-09-28
Filing date: 2021-09-28
Publication date: 2023-09-12
Anticipated expiration: 2041-09-28
Also published as: CN113861653A

Abstract

The invention discloses a flame-retardant polycarbonate composite material, which comprises the following components in parts by weight: 80-100 parts of polycarbonate; 2-20 parts of flame retardant; 5-15 parts of PBAT and/or PBSA; 0.05-0.2 times of total weight of the PBAT and/or the PBSA. According to the invention, the technical defect of poor polycarbonate fluidity is improved by introducing the PBAT and/or the PBSA, and the technical defect of easy dripping of the PBAT and/or the PBSA during combustion is further improved by introducing the carbon nano tube, wherein the carbon nano tube has a relatively large length-diameter ratio, has a supporting effect on the combustion melt strength of the resin, has high monofilament strength, and further weakens the combustion dripping by combining the interfacial effect with the resin.

Description

Flame-retardant polycarbonate composite material and preparation method and application thereof

Technical Field

The invention relates to the technical field of high polymer materials, in particular to a flame-retardant polycarbonate composite material and a preparation method and application thereof.

Background

The polycarbonate PC product has the advantages of good transparency, high impact resistance, high heat resistance, good dimensional stability, good flame retardant property and the like, and is widely applied to the fields of automobiles, IT, electronic appliances, household appliances and the like.

However, polycarbonate also has the technical disadvantage of poor flowability. The prior art mainly improves the technical defect by the following two points: 1. by compounding high-flow polycarbonate (or other polyesters)/low-flow polycarbonate. 2. By adding inorganic fillers. However, other technical drawbacks are associated with the above-described method. Wherein, by compounding high-fluidity polycarbonate or other polyesters, dripping phenomenon easily occurs in the flame retardance or combustion process. The main method for solving the dripping phenomenon is anti-dripping agent, and the anti-dripping agent is a surface modifier, so that the surface property (such as laser marking property and the like) of the polycarbonate composite material is easy to change, and other technical problems are brought. The addition of the inorganic filler is susceptible to the influence of the weakly basic inorganic filler on the stability of the composition.

Therefore, it is of practical value to develop a new method for improving the technical defect of poor flowability of polycarbonate.

Disclosure of Invention

The invention aims to provide a flame-retardant polycarbonate composite material with good anti-dripping property.

The invention also aims to provide a preparation method of the flame-retardant polycarbonate composite material.

The invention is realized by the following technical scheme:

the flame-retardant polycarbonate composite material comprises the following components in parts by weight:

80-100 parts of polycarbonate;

2-20 parts of flame retardant;

5-15 parts of PBAT and/or PBSA;

carbon nanotubes in an amount of 0.05 to 0.2 times the total weight of the PBAT and/or PBSA;

in the PBAT chain segment repeating unit, the weight content of the butylene terephthalate unit is 50-70wt%, and the weight content of the butylene adipate unit is 30-50wt%;

in the PBSA chain segment repeating unit, the weight content of the butylene succinate unit is 66-89wt%, and the weight content of the adipic acid butylene succinate unit is 11-34wt%.

Preferably, the addition amount of the carbon nano tube is 0.08-0.16 times of the total weight part of the PBAT and/or the PBSA; more preferably, the carbon nanotubes are added in an amount of 0.1 to 0.13 times the total weight parts of PBAT and/or PBSA.

Preferably, the weight content of the polybutylene terephthalate unit in the PBAT chain segment repeating unit is 55-65wt%, and the weight content of the polybutylene adipate unit is 35-45wt%.

Preferably, the weight content of the butylene succinate unit in the PBSA is 75-80 wt%, and the weight content of the butylene adipate unit is 20-25wt%.

Due to the strong fluidity of the PBAT and the PBSA, the compatibility of the PBAT and the PBSA chain segment with the polycarbonate can be improved by adjusting the PBAT and the PBSA chain segment, and the dripping property is further improved.

The intrinsic viscosity of the PBAT is 1-3.5dL/g, and the test condition is 25 ℃; the intrinsic viscosity of the PBSA is 1-3 dL/g, and the test condition is 25 ℃.

The source of PBAT and PBSA can be self-made or commercially available.

The preparation method and the testing method of the intrinsic viscosity of the PBAT and the PBSA are as follows: firstly, 1, 4-butanediol, adipic acid, terephthalic acid (or succinic acid) and tetrabutyl titanate serving as a catalyst are firstly added into a reaction container according to the metering, the temperature is raised to 160-180 ℃ for 4-5 hours, and nitrogen is introduced in the process until no water is distilled out. And step two, raising the temperature to 220-240 ℃ and maintaining the vacuum degree to 20-30Pa. The vacuum degree and viscosity were observed, and when the viscosity reached the set point, the reaction was stopped to obtain the designed PBAT (or PBSA).

Intrinsic viscosity test: mixing phenol and tetrachloroethane with a ratio of 1:1 as a solvent, preparing a PBAT or PBSA solution with a mass concentration of 2.5g/L, standing for 24 hours, and measuring at 25 ℃ by using a Ubbelohde viscometer.

The carbon nanotube is at least one selected from a single-layer carbon nanotube and a multi-layer carbon nanotube, and the length-diameter ratio of the carbon nanotube is 50-6000, preferably 100-3000.

The average molecular weight of the polycarbonate is 12000-35000; from the viewpoint of suppressing the balance of dripping and melt fluidity, it is preferable that the average molecular weight of the polycarbonate is 16500 to 20000.

The flame retardant is at least one selected from brominated flame retardants, C1-C16 alkyl sulfonate flame retardants, carbonate flame retardants, fluorine-silver ion compounds, phosphorus flame retardants, metal hydroxides, flame retardant synergists of antimony-containing compounds or borate flame retardants; the brominated flame retardant is at least one selected from tetrabromobisphenol A, bromotriazine, brominated epoxy, decabromodiphenylethane, decabromodiphenyl ether, brominated polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate or brominated polyacrylate; the C1-C16 alkyl sulfonate flame retardant is at least one selected from potassium perfluorobutyl sulfonate, potassium perfluorooctane sulfonate, tetraethylammonium perfluoroethane sulfonate or potassium diphenylsulfone sulfonate;

the carbonic flame retardant is at least one of sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate or barium carbonate; the phosphorus flame retardant is at least one selected from phosphine flame retardant, phosphinite flame retardant, hypophosphite flame retardant, phosphonite flame retardant, phosphite flame retardant, phosphine oxide flame retardant, hypophosphite flame retardant, phosphate flame retardant or polyphosphate flame retardant; the metal hydroxide flame retardant is at least one selected from magnesium hydroxide or aluminum hydroxide; the borate flame retardant is at least one selected from anhydrous zinc borate, 3.5 zinc borate hydrate, alkali metal salts of boric acid or alkaline earth metal salts of boric acid.

The composition also comprises 0-1.2 parts by weight of ester interchange inhibitor; the transesterification inhibitor is at least one selected from sodium dihydrogen phosphate, octadecyl phosphate or triphenyl phosphate.

The preparation method of the flame-retardant polycarbonate composite material comprises the following steps: the components are uniformly mixed according to the proportion, extruded and granulated by a double-screw extruder, the temperature range of the screw is 220-250 ℃, and the rotating speed range is 350-600rpm, so that the flame-retardant polycarbonate composite material is obtained.

The flame-retardant polycarbonate composite material is applied to preparing automobile accessories and electronic and electric appliance shells.

The invention has the following beneficial effects:

the invention can improve the technical defect of poor flowability of polycarbonate by introducing PBAT and/or PBSA, but the flame retardant property is reduced (UL 94) due to the defect of easy dripping when PBAT and/or PBSA burns. Therefore, the invention can further improve the technical defect that PBAT and/or PBSA are easy to drip during combustion (or flame-retardant process) by introducing a certain amount of carbon nanotubes, and can reduce or even omit the addition of anti-dripping agents.

Detailed Description

The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.

The raw materials used in the examples and comparative examples of the present invention are as follows:

polycarbonate a: average molecular weight 1.5 ten thousand, light-emitting FN1500;

polycarbonate B: the average molecular weight is 1.7 ten thousand, mitsubishi H-3000F;

polycarbonate C: the average molecular weight is 2 ten thousand, mitsubishi H-2000F;

polycarbonate D: the average molecular weight is 3.5 ten thousand, mitsubishi E-1000F.

PBAT-a: the weight content of the butylene terephthalate unit is 50wt%, the weight content of the butylene adipate unit is 50wt%, the intrinsic viscosity is 1.5dL/g, and the self-made product is at 25 ℃;

PBAT-B: the weight content of the butylene terephthalate unit is 55wt%, the weight content of the butylene adipate unit is 45wt%, the intrinsic viscosity is 2.0dL/g, and the butylene adipate unit is available from AFC ecosystems under the brand name ANBIO BG1000;

PBAT-C: the weight content of the butylene terephthalate unit is 65wt%, the weight content of the butylene adipate unit is 35wt%, the intrinsic viscosity is 1.8dL/g, and the butylene adipate unit is self-made at 25 ℃;

PBAT-D: the weight content of the butylene terephthalate unit is 70wt%, the weight content of the butylene adipate unit is 30wt%, the intrinsic viscosity is 1.95dL/g, the temperature is 25 ℃, and the butylene adipate unit is purchased from KMI with the brand KM801;

PBAT-E: the weight content of the butylene terephthalate unit is 45wt%, the weight content of the butylene adipate unit is 55wt%, the intrinsic viscosity is 1.6dL/g, and the self-made product is at 25 ℃;

PBAT-F: the weight content of the butylene terephthalate unit is 75wt%, the weight content of the butylene adipate unit is 25wt%, the intrinsic viscosity is 1.4dL/g, and the butylene adipate unit is self-made at 25 ℃;

PBSA-A: the weight content of the butanediol succinate unit is 66wt%, the weight content of the butanediol adipate unit is 34wt%, the intrinsic viscosity is 1.6dL/g, and the butanediol succinate unit is self-made at 25 ℃;

PBSA-B: the weight content of the butanediol succinate unit is 75wt%, the weight content of the butanediol adipate unit is 25wt%, the intrinsic viscosity is 1.75dL/g, and the butanediol succinate unit is self-made at 25 ℃;

PBSA-C: the weight content of the butanediol succinate unit is 80wt%, the weight content of the butanediol adipate unit is 20wt%, the intrinsic viscosity is 2.0dL/g, and the butanediol succinate unit is self-made at 25 ℃;

PBSA-D: the weight content of the butanediol succinate unit is 89wt%, the weight content of the butanediol adipate unit is 11wt%, the intrinsic viscosity is 1.9dL/g, and the butanediol succinate unit is self-made at 25 ℃;

PBSA-E: the weight content of the butanediol succinate unit is 63wt%, the weight content of the butanediol adipate unit is 37wt%, the intrinsic viscosity is 1.8dL/g, and the butanediol succinate unit is self-made at 25 ℃;

PBSA-F: the weight content of the butanediol succinate unit is 92wt%, the weight content of the butanediol adipate unit is 8wt%, the intrinsic viscosity is 1.85dL/g, and the butanediol succinate unit is self-made at 25 ℃;

decabromodiphenyl ethane: israel dead sea, FR1410;

antimony trioxide: star antimony industry, S-12N;

potassium perfluorobutyl sulfonate: 3m, fr2025;

phosphate flame retardant: ai Dike, FP-600;

carbon nanotubes a: merck,698849, aspect ratio 500-2600;

carbon nanotubes B: TUBALL 01RW03, with aspect ratio of 3000-6000;

carbon nanotubes C: merck,412988, aspect ratio of 50-800-;

carbon nanotubes D: ACMEC, TCI-C2158, aspect ratio of 50-250.

Octadecyl phosphate: C18P, alcissi, transesterification inhibitors.

Examples and comparative examples method of making flame retardant polycarbonate composites: uniformly mixing polycarbonate, flame retardant, PBAT and/or PBSA, transesterification inhibitor and carbon nano tube according to the proportion, extruding and granulating by a double screw extruder, wherein the temperature range of the screw is 120-140 ℃ in a first region, 160-180 ℃ in a second region, 220-240 ℃ in a third region, 240-260 ℃ in a fourth region, 220-220 ℃ in a fifth region, 4, 220-240 ℃ in a sixth region, 240-260 ℃ in a seventh region, 220-240 ℃ in an eighth region, 220-240 ℃ in a ninth region, 200-220 ℃ in a tenth region, 350rpm in a rotating speed range and 450rpm in a rotating speed range, and obtaining the flame-retardant polycarbonate composite material.

The testing method comprises the following steps:

(1) Degree of combustion or flame retardant dripping: according to the UL94-2016 flame retardant standard test, whether dripping is observed in the process of igniting to extinguishing, and the dripping quantity is counted

(2) Melt flow stability: according to the melt index of the material tested according to ISO 1133-1-2011 standard at 260 ℃ and under the condition of 2.16kg, the melt index is a key index for measuring the flowability of the material.

Table 1: examples 1-7 flame retardant polycarbonate composite Each component (parts by weight) and test results

	Example 1	Example 2	Example 3	Example 4	Example 5	Example 6	Example 7
								Polycarbonate A	80
Polycarbonate B		80			80	80	80
								Polycarbonate C			80
Polycarbonate D				80
								PBAT-A	10	10	10	10	5	15	12
Decabromodiphenyl ethane	10	10	10	10
								Antimony trioxide	2	2	2	2
Potassium perfluorobutyl sulfonate					3	3	3
								Phosphate flame retardant					1	1	1
Carbon nanotube A	1	1	1	1	0.5	1.5	0.8
								Transesterification inhibitors	0.02	0.02	0.02	0.02	0.02	0.02
Degree of dripping, drip	2	1	1	0	0	1	1
								Melt index, g/10min	27.2	14.3	6.8	2.6	13.1	15.6	14.4

As is clear from examples 1 to 4, the average molecular weight of polycarbonate was 16500 to 20000 from the viewpoint of balance between processability and drip-suppressing property, as the average molecular weight of polycarbonate was increased in the range of 12000 to 35000, and the drip-suppressing property was increased. It is evident from examples 5-6 that the melt index can be raised by adding PBAT.

Table 2: examples 8-12 flame retardant polycarbonate composite Each component (parts by weight) and test results

	Example 8	Example 9	Example 10	Example 11	Example 12
						Polycarbonate B	80	80	80	80	80
PBAT-A	10	10	10	10	10
						Decabromodiphenyl ethane	10	10	10	10	10
Antimony trioxide	2	2	2	2	2
						Carbon nanotube A	0.5	0.8	1.3	1.6	2
Transesterification inhibitors	0.02	0.02	0.02	0.02	0.02
						Degree of dripping, drip	2	1	0	1	2
Melt index, g/10min	11.4	10.7	9.8	9.5	9.1

As is clear from examples 2/8-12, the preferred PBAT/carbon nanotube formulation has better drip resistance.

Table 2: examples 13-15 flame retardant polycarbonate composite Components (parts by weight) and test results

	Example 13	Example 14	Example 15
				Polycarbonate B	80	80	80
PBAT-A	10	10	10
				Decabromodiphenyl ethane	10	10	10
Antimony trioxide	2	2	2
				Carbon nanotube B	1
Carbon nanotube C		1
				Carbon nanotube D			1
Transesterification inhibitors	0.02	0.02	0.02
				Degree of dripping, drip	2	2	2
Melt index, g/10min	11.1	11.3	12.5

As is clear from examples 2/13/14/15, carbon nanotubes having an aspect ratio of 100 to 3000 are preferable.

Table 3: examples 16-22 flame retardant polycarbonate composite Each component (parts by weight) and test results

	Example 16	Example 17	Example 18	Example 19	Example 20	Examples21	Example 2
								Polycarbonate B	80	80	80	80	80	80	80
PBAT-B	10
								PBAT-C		10
PBAT-D			10
								PBSA-A				10
PBSA-B					10
								PBSA-C						10
PBSA-D							10
								Ethane of decabromodiphenyl	10	10	10	10	10	10	10
Antimony trioxide	2	2	2	2	2	2	2
								Carbon nanotube A	1	1	1	1	1	1	1
Transesterification inhibitors	0.02	0.02	0.02	0.02	0.02	0.02	0.02
								Degree of dripping, drip	0	1	3	3	2	1	2
Melt index, g/10min	11.0	10.4	9.7	10.6	10.8	10.1	10.3

As can be seen from examples 2/16-22, the PBAT/PBSA repeat units affect their compatibility with polycarbonate resins, and thus affect the degree of dripping during combustion or flame retardance.

Table 4: comparative example flame retardant polycarbonate composite Each component (parts by weight) and test results

	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5	Comparative example 6	Comparative example 7
								Polycarbonate B	80	80	80	80	80	80	80
PBAT-A	10						10
								PBAT-E			10
PBAT-F				10
								PBSA-A		10
PBSA-E					10
								PBSA-F						10
Ethane of decabromodiphenyl	10	10	10	10	10	10	10
								Antimony trioxide	2	2	2	2	2	2	2
Carbon nanotube A	0	0	1	1	1	1	3
								Transesterification inhibitors	0.02	0.02	0.02	0.02	0.02	0.02	0.02
Degree of dripping, drip	5	5	3	5	4	3	4
								Melt index, g/10min	12.6	10.6	11.3	13.9	10.9	10.5	8.8

As is clear from comparative examples 3 to 6, PBAT/PBSA repeat units outside the scope of the present invention affect the compatibility with polycarbonate and are easily melted and dropped by heat.

As is clear from comparative example 7, if the content of carbon nanotubes is too high, the drop resistance is reduced.

Claims

1. The flame-retardant polycarbonate composite material is characterized by comprising the following components in parts by weight:

80-100 parts of polycarbonate;

2-20 parts of flame retardant;

5-15 parts of PBAT and/or PBSA;

in the PBSA chain segment repeating units, the weight content of the butylene succinate units is 66-89wt%, and the weight content of the butylene adipate units is 11-34wt%;

the intrinsic viscosity of the PBAT is 1-3.5dL/g, and the test condition is 25 ℃; the intrinsic viscosity of the PBSA is 1-3 dL/g, and the test condition is 25 ℃;

the average molecular weight of the polycarbonate is 12000-35000.

2. The flame retardant polycarbonate composite material of claim 1, wherein the carbon nanotubes are added in an amount of 0.08-0.16 times the total weight parts of PBAT and/or PBSA.

3. The flame retardant polycarbonate composite material of claim 2, wherein the carbon nanotubes are added in an amount of 0.1 to 0.13 times the total weight parts of PBAT and/or PBSA.

4. The flame retardant polycarbonate composite of claim 1, wherein the weight content of butylene terephthalate units in the PBAT segment repeat units is 55-65wt% and the weight content of butylene adipate units is 35-45wt%.

5. The flame retardant polycarbonate composite of claim 1, wherein the weight content of butylene succinate units in PBSA is 75-80 wt% and the weight content of butylene adipate units is 20-25wt%.

6. The flame retardant polycarbonate composite material of claim 1, wherein the carbon nanotubes are at least one selected from the group consisting of single-layer carbon nanotubes and multi-layer carbon nanotubes, and the aspect ratio of the carbon nanotubes is in the range of 50-6000.

7. The flame retardant polycarbonate composite of claim 1, wherein the carbon nanotubes have an aspect ratio in the range of 100 to 3000.

8. The flame retardant polycarbonate composite of claim 1, wherein the polycarbonate has an average molecular weight of 16500-20000.

9. The flame retardant polycarbonate composite material of claim 1, wherein the flame retardant is at least one selected from the group consisting of brominated flame retardants, C1-C16 alkyl sulfonate flame retardants, carbonate flame retardants, fluorine-silver ion complexes, phosphorus flame retardants, metal hydroxides, antimony-containing compound flame retardant synergists, and borate flame retardants; the brominated flame retardant is at least one selected from tetrabromobisphenol A, bromotriazine, brominated epoxy, decabromodiphenylethane, decabromodiphenyl ether, brominated polyimide, brominated polystyrene, polybrominated styrene, brominated polycarbonate or brominated polyacrylate; the C1-C16 alkyl sulfonate flame retardant is at least one selected from potassium perfluorobutyl sulfonate, potassium perfluorooctane sulfonate, tetraethylammonium perfluoroethane sulfonate or potassium diphenylsulfone sulfonate;

the carbonic flame retardant is at least one of sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate or barium carbonate; the phosphorus flame retardant is at least one selected from phosphazene flame retardant, hypophosphite flame retardant, phosphonite flame retardant, phosphite flame retardant, phosphine oxide flame retardant, hypophosphite flame retardant, phosphate flame retardant or polyphosphate flame retardant; the metal hydroxide flame retardant is at least one selected from magnesium hydroxide or aluminum hydroxide; the borate flame retardant is at least one selected from anhydrous zinc borate, 3.5 zinc borate hydrate, alkali metal salts of boric acid or alkaline earth metal salts of boric acid.

10. The flame retardant polycarbonate composite of claim 1, further comprising 0 to 1.2 parts by weight of a transesterification inhibitor; the transesterification inhibitor is at least one selected from sodium dihydrogen phosphate, octadecyl phosphate or triphenyl phosphate.

11. The method for preparing a flame retardant polycarbonate composite material as defined in any one of claims 1 to 10, comprising the steps of: the components are uniformly mixed according to the proportion, extruded and granulated by a double-screw extruder, the temperature range of the screw is 220-250 ℃, and the rotating speed range is 350-600rpm, so that the flame-retardant polycarbonate composite material is obtained.

12. Use of a flame retardant polycarbonate composite according to any of claims 1-10 for the preparation of automotive parts, electrical and electronic housings.