CN114590011A

CN114590011A - Composite film with high needle flame test tolerance time and high CTI value as well as preparation method and application thereof

Info

Publication number: CN114590011A
Application number: CN202210347578.9A
Authority: CN
Inventors: 单伟; 罗伟; 张丛见; 任月璋
Original assignee: Suzhou Omay Optical Materials Co ltd
Current assignee: Suzhou Omay Optical Materials Co ltd
Priority date: 2022-04-01
Filing date: 2022-04-01
Publication date: 2022-06-07
Anticipated expiration: 2042-04-01
Also published as: CN114590011B

Abstract

The invention provides a composite film with high needle flame test endurance time and high CTI value, and a preparation method and application thereof. The composite film with high needle flame test endurance time and high CTI value comprises a modified polycarbonate layer and a modified polyphenyl ether layer, wherein the modified polycarbonate layer and the modified polyphenyl ether layer are independently modified by a coupling agent. The composite film prepared by the invention has high needle flame test endurance time, the needle flame test of the composite film with the thickness of 0.3-3.6mm can endure more than 43 seconds, the vertical burning with the thickness of 0.3mm can reach UL94-V0 level, the composite film has high and stable CTI value and good mechanical property, wear resistance, chemical resistance and water resistance, and can be used for preparing battery insulating materials and other various high-performance insulating materials.

Description

Composite film with high needle flame test tolerance time and high CTI value, and preparation method and application thereof

Technical Field

The invention belongs to the technical field of composite films, relates to a composite film and a preparation method and application thereof, and particularly relates to a composite film with high needle flame test tolerance time and high CTI value and a preparation method and application thereof.

Background

Polycarbonate (PC), a tough thermoplastic resin, is now the second largest engineering plastic with second generation of polyamide, and has excellent impact resistance, heat resistance, good dimensional stability, electrical insulation properties, and the like, and thus is widely used in the fields of automobile parts, home appliances, electronic and electrical appliances, and the like. However, the PC has poor water resistance, poor chemical resistance, poor wear resistance and low Comparative Tracking Index (CTI), and the flame retardant performance of vertical burning needs to be further improved, especially the endurance time of the needle flame test is very short, so that the application field of the PC is greatly limited, and the improvement of the performance of the PC is urgently needed.

Polyphenylene Oxide (PPO) has the advantages of excellent water resistance, chemical resistance, heat resistance, good dimensional stability, good wear resistance, higher CTI value, difficult combustion and the like, but the endurance time of a needle flame test still needs to be further prolonged.

Therefore, the flame retardant performance and CTI value of the vertical burning of the polymer material can be improved by combining the two polymers, but the flame retardant performance of the vertical burning still needs to be improved, and meanwhile, the endurance time of the needle flame test needs to be further prolonged. In addition, since PPO and PC have low compatibility, delamination or fracture easily occurs at the junction, and the CTI value is unstable, it is necessary to improve the compatibility of PPO and PC.

CN102276907B discloses a synergistic flame-retardant thermoplastic resin and a preparation method thereof, wherein the flame-retardant thermoplastic resin comprises the following components: 40 to 45 weight percent of thermoplastic resin, 45 to 53 weight percent of modified magnesium hydroxide powder, and 2 to 15 weight percent of halogen-free phosphorus-containing flame retardant and initiator; the preparation method comprises the following steps: (1) drying the magnesium hydroxide powder modified by the coupling agent; preparing halogen-free phosphorus-containing flame retardant by using 9, 10-dihydro-9 oxa-10-phosphaphenanthrene-10-oxide and bismaleimide in equal mol; (2) adding halogen-free phosphorus-containing flame retardant and thermoplastic resin into an internal mixer, and heating to melt the mixture; and then cooling, adding an initiator, heating again, adding the modified magnesium hydroxide powder into an internal mixer, and continuously mixing to obtain the magnesium hydroxide powder. The flame-retardant thermoplastic resin has good flame-retardant property and high mechanical property; simple preparation, low cost and contribution to realizing industrial production.

CN106957520B discloses a halogen-free flame-retardant polyphenyl ether composition and a product prepared from the same, belonging to the technical field of high polymer materials. The composition consists essentially of: 50-75% of polyphenyl ether resin, 10-30% of polystyrene resin, 1-8% of hydrogenated styrene/butadiene/styrene block copolymer, 0-5% of ternary ethylene-acrylate-glycidyl acrylate copolymer, 3-12% of phosphate flame retardant, 0-3% of montmorillonite and 0-1% of modified polysiloxane; the total weight percent of all components in the composition is 100%. The composition has good flame retardant effect and good mechanical property, and a product prepared from the composition is selected from new energy automobile battery module shells.

CN108148382A discloses a flame-retardant polycarbonate material, and the purpose of the invention is to provide a modified polycarbonate material for improving the inflammability of the polycarbonate material and a preparation method thereof. The flame-retardant polycarbonate material consists of the following raw materials in percentage by weight: 80-120, antioxidant: 0.8-1.2, colorant: 0.6-1.0, ultraviolet light absorber: 8.8-9.2, light stabilizer: 8.8-9.2, dispersed lubricant: 0.8-1.2, titanate coupling agent: 1.3-1.7, zinc borate: 9.8-10.2, antimony trioxide: 4.8-5.2. The invention can obviously improve the flame retardant property of the polycarbonate material, and the flame retardant grade of the polycarbonate material reaches V0.

CN112606504A discloses a high-CTI-value high-flame-retardant composite film and a preparation method thereof, the invention adopts a multi-layer co-extrusion preparation method, adopts a high-flame-retardant PPO material and a high-flame-retardant PC material, takes the PC as a main base material, and co-extrudes a PPO material with high flame retardance and high CTI value on the surface of the PC material, so as to realize that the 0.5mm film reaches the flame-retardant grade of UL94-V0, and meanwhile, the PPO material on the double-sided surface layer has the function of CTI 0, thereby realizing the high-flame-retardant and high CTI value of the product.

However, in the prior art, composite films prepared by compounding PPO and PC are only reported, wherein the composite film disclosed in CN112606504A has a very short needle flame test endurance time, the flame retardant performance of vertical combustion still needs to be further improved, and the CTI values in different areas have obvious fluctuation due to the layering phenomenon between PPO and PC. Therefore, it is necessary to provide a composite film with a high and stable CTI value and a preparation method thereof, wherein the composite film has a longer needle flame test endurance time, excellent vertical burning flame retardant performance and excellent compatibility.

Disclosure of Invention

Aiming at the defects of the prior art, the invention aims to provide a composite film with high needle flame test endurance time and high CTI value, a preparation method and application thereof.

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

one of the purposes of the invention is to provide a composite film with high needle flame test endurance time and high CTI value, which comprises a modified polycarbonate layer and a modified polyphenyl ether layer, wherein the modified polycarbonate layer and the modified polyphenyl ether layer are independently modified by a coupling agent.

After the modified polycarbonate layer and the modified polyphenyl ether layer are modified by the coupling agent, the two layers of films have good compatibility, and the prepared composite film has longer needle flame test tolerance time, more excellent vertical combustion flame retardant property and high and stable CTI value.

It should be particularly noted that the high needle flame test endurance time in the invention means that the needle flame test of the composite film with the thickness of 0.3-3.6mm can withstand more than 43 seconds, particularly the needle flame test of the composite film with the lowest thickness of 0.3mm can withstand 124 seconds, and the high CTI value in the invention means that the CTI value is 600V.

In the invention, the coupling agent is independently a silane coupling agent, a titanate coupling agent or a compound of the silane coupling agent and the titanate coupling agent.

Preferably, the mass ratio of the silane coupling agent to the titanate coupling agent in the compound is (1-99): (1-99), for example, 1:99, 2:98, 3:97, 4:96, 5:95, 6:94, 7:93, 8:92, 9:91, 10:90, 15:85, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10, 91:9, 92:8, 93:7, 94:6, 95:5, 96:4, 97:3, 98:2, 99:1, and the like. By adopting the two coupling agents in the proportion, the prepared composite film has higher needle flame test tolerance time and CTI value.

In the present invention, the modified polycarbonate layer comprises 60 to 99 parts by weight of polycarbonate and 1 to 40 parts by weight of a coupling agent. For example, the polycarbonate is 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts or 99 parts by weight, and the coupling agent is 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 33 parts, 35 parts, 33 parts, 35 parts, 33 parts, 35 parts, 33 parts, 35 parts, 33 parts, 35 parts, 33 parts, 35 parts, 33 parts, or 99 parts, 9 parts, 3 parts, 9 parts, 39 parts or 40 parts, etc.

The modified PC layer of the present invention has the following advantages: (1) the endurance time of the needle flame test is very long, and the thickness of 0.2mm can reach about 53 seconds; (2) excellent vertical burning flame retardance, wherein the flame retardance of about 0.2mm thickness can reach UL94-V0 grade, and does not contain halogen, the invention does not limit the concrete material, and the color is not limited; (3) the polymer has excellent compatibility with various high molecular polymers, and can prevent the generation of incompatible phenomena, thereby avoiding the instability of performance.

In the present invention, the modified polyphenylene ether layer contains 60 to 99 parts by weight of polyphenylene ether and 1 to 40 parts by weight of a coupling agent. For example, the polyphenylene ether may be 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts or 99 parts by weight, and the coupling agent may be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 35 parts, 38 parts, 35 parts, 38 parts, 35 parts, 33 parts, 35 parts, 33 parts, 35 parts, 38 parts, 33 parts, 35 parts, or the like, 39 parts or 40 parts, etc.

The modified PPO layer of the invention has the following advantages: (1) the endurance time of the needle flame test is very long, and the thickness of 0.1mm can reach about 71 seconds; (2) excellent vertical burning flame retardance, wherein the thickness of about 0.1mm can realize UL94-V0 level, and the halogen-free flame retardant paint does not contain halogen and has no limit on color; (3) the CTI value reaches the voltage resistance requirement of 0 grade 600V; (4) can be used for extrusion molding; (5) the material has excellent compatibility with various high molecular polymers, and can prevent incompatibility, thereby avoiding unstable performance; (6) endows the two-layer composite film with excellent wear resistance, chemical resistance and water resistance.

In the invention, the chemical general formula of the silane coupling agent is RSiX₃。

Preferably, the R group is one of a vinyl group, an epoxy group or an amine group.

Preferably, the X group is an alkoxy group.

Preferably, the alkoxy group is methoxy or ethoxy.

Preferably, the silane coupling agent is a gamma-glycidoxypropyltrimethoxysilane coupling agent and/or a gamma-aminopropyltriethoxysilane coupling agent.

In the invention, the chemical general formula of the titanate coupling agent is RO_(4-n)Ti(OX-RY)_n。

Preferably, n is 1, 2 or 3.

Preferably, the RO group is a hydrolyzable alkoxy group.

Preferably, the OX group is a phosphorus group.

Preferably, the R group is an alkyl group.

Preferably, the Y group is a hydroxyl, amine or epoxy group.

Preferably, the titanate coupling agent is an isopropyl tri (dioctyl phosphoryloxy) titanate coupling agent and/or an isopropyl dioleate acyloxy (dioctyl phosphoryloxy) titanate coupling agent.

In the present invention, the thickness of the composite film is 0.3 to 3mm, for example, 0.3mm, 0.4mm, 0.5mm, 0.6mm, 0.7mm, 0.8mm, 0.9mm, 1mm, 1.1mm, 1.2mm, 1.3mm, 1.4mm, 1.5mm, 1.6mm, 1.7mm, 1.8mm, 1.9mm, 2mm, 2.1mm, 2.2mm, 2.3mm, 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm, 3mm, etc.; preferably 0.3-1 mm.

In the invention, the thickness of the modified polycarbonate layer accounts for 5-95% of the total thickness of the composite film, and the thickness of the modified polyphenylene oxide layer accounts for 5-95% of the total thickness of the composite film. For example, the thickness of the modified polycarbonate layer accounts for 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the total thickness of the composite film, the thickness of the modified polyphenylene ether layer accounts for 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the total thickness of the composite film, and the sum of the thicknesses of the modified polycarbonate layer and the modified polyphenylene ether layer is 100%.

The second purpose of the invention is to provide a preparation method of the composite film with high needle flame test endurance time, high flame retardance and high CTI value, which comprises the following steps:

1) preparation of modified polycarbonate: blending polycarbonate and a coupling agent, and extruding and granulating to obtain modified polycarbonate;

2) preparation of modified polyphenylene ether: blending polyphenyl ether and a coupling agent, and extruding and granulating to obtain modified polyphenyl ether;

3) and (2) carrying out two-layer co-extrusion compounding on the modified polycarbonate prepared in the step 1) and the modified polyphenyl ether prepared in the step 2) to obtain the halogen-free high-flame-retardant high-CTI (comparative tracking index) composite film.

In the step 1), the blending temperature is 25-35 ℃, the rotating speed is 10-200r/min, and the time is 10-60 min; the temperature of the extrusion granulation is 220-260 ℃, the rotating speed of a screw for the extrusion granulation is 100-400r/min, and the frequency of a main feeder is 100-400 Hz;

preferably, in the step 2), the blending temperature is 25-35 ℃, the rotating speed is 10-200r/min, and the time is 10-60 min; the temperature of the extrusion granulation is 270-300 ℃, the screw rotating speed of the extrusion granulation is 100-300r/min, and the frequency of the main feeding machine is 100-400 Hz.

The invention also aims to provide the application of the composite film with high needle flame test endurance time, high flame retardance and high CTI value, and the composite film is used for preparing battery insulating materials and other various high-performance insulating materials.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the composite film disclosed by the invention, the modified PC layer and the modified PPO layer have excellent compatibility, so that the composite film is fully ensured to have excellent overall mechanical properties;

(2) the composite film has high needle flame test tolerance time, the needle flame test of the composite film with the thickness of 0.3-3.6mm can resist more than 43 seconds, and particularly, the needle flame test tolerance time of the composite film with the thickness of 0.3mm can reach 124 seconds;

(3) the composite film can still realize the flame retardant grade of UL94-V0 with the thickness of 0.3mm under the halogen-free limiting condition;

(4) according to the composite film, the CTI value of the two layers of composite films can meet the voltage resistance requirement of 0-grade 600V by virtue of the modified PPO layer;

(5) according to the composite film disclosed by the invention, the modified PPO layer endows the two layers of composite films with excellent wear resistance, chemical resistance and water resistance.

Drawings

FIG. 1 is a schematic structural diagram of a preferred high needle flame test endurance, high CTI value composite film of the present invention;

FIG. 2 is a schematic diagram of the structure of another preferred high needle flame test time resistance, high CTI value composite film of the present invention;

FIG. 3 is a schematic diagram of a method for preparing a composite film with high needle flame test endurance time and high CTI value according to the present invention;

the reference numbers are as follows:

1-a modified polycarbonate layer; a 2-modified polyphenylene ether layer; 3-a first extruder; 4-a second extruder; 5-a distributor; 6-die head.

Detailed Description

The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached figures 1-3.

Unless otherwise specified, various starting materials of the present invention are commercially available or prepared according to conventional methods in the art.

As shown in fig. 1, a preferred composite film with high needle flame test endurance time and high CTI value of the present invention comprises a modified polycarbonate layer 1 and a modified polycarbonate layer 2 sequentially arranged from top to bottom, wherein the thickness of the modified polycarbonate layer 1 is greater than that of the modified polycarbonate layer 2.

As shown in fig. 2, another preferred high-needle-flame-test-endurance, high-CTI-value composite film of the present invention comprises a modified polycarbonate layer 2 and a modified polycarbonate layer 1, which are sequentially disposed from top to bottom, wherein the thickness of the modified polycarbonate layer 2 is greater than that of the modified polycarbonate layer 1.

As shown in the attached figure 3, the composite film with high needle flame test endurance time and high CTI value is prepared by the following preparation method: respectively extruding the modified PC and the modified PPO by a first extruder 3 and a second extruder 4; the extrusion capacity of the first extruder 3 and the second extruder 4 is accurately adjusted by a distributor 5, the first extruder 3 and the second extruder 4 extrude two layers of composite films by the same die head 6, and the modified PC layer and the modified PPO layer are effectively combined into a two-layer structure by roller pressing.

Example 1

Respectively adding 90 parts of PC material with the model of imperial L-1250Y and 10 parts of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 30 minutes to prepare a blend A1.

Adding the blend A1 into a double-screw extruder from a main feeder, carrying out melt extrusion granulation, wherein the screw rotation speed is 150 revolutions per minute, the frequency of the main feeder is 200Hz, the temperature of each section of the extruder is 250 ℃, and stretching, water cooling and granulating to obtain the modified PC granules.

90 parts of PPO material with the type of Asahi chemical formula L565V and 10 parts of gamma-aminopropyltriethoxysilane coupling agent are sequentially added into a low-speed mixer for blending, the mixing temperature is 28 ℃, the rotating speed is 80 revolutions per minute, and the mixing time is 42 minutes, so that a blend A2 is prepared.

Adding the blend A2 into a double-screw extruder from a main feeder, and carrying out melt extrusion granulation, wherein the rotating speed of the screws is 200 revolutions per minute, and the frequency of the main feeder is 300 Hz; the temperature of each section of the extruder is 280 ℃, and the modified PPO granules are prepared by cutting the strands into granules after water cooling.

Respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by means of a die head to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.2mm and 0.1mm in sequence.

Example 2

60 parts of Wanhua A1105 PC material and 40 parts of gamma-aminopropyltriethoxysilane coupling agent are respectively added into a low-speed mixer for blending, the mixing temperature is 25 ℃, the rotating speed is 10 r/min, and the mixing time is 10 min, so that a blend A1 is prepared.

Adding the blend A1 into a double-screw extruder from a main feeder, carrying out melt extrusion granulation, wherein the screw rotation speed is 100 revolutions per minute, the frequency of the main feeder is 100Hz, the temperature of each section of the extruder is 220 ℃, and stretching, water cooling and granulating to obtain the modified PC granules.

90 parts of PPO material with the type of Saber GTX830 and 10 parts of isopropyl dioleate acyloxy (dioctyl phosphate acyloxy) titanate coupling agent are sequentially added into a low-speed mixer to be mixed, the mixing temperature is 25 ℃, the rotating speed is 10 revolutions per minute, and the mixing time is 10 minutes, so that a mixture A2 is prepared.

Adding the blend A2 into a double-screw extruder from a main feeder, and carrying out melt extrusion granulation, wherein the rotating speed of the screws is 100 revolutions per minute, and the frequency of the main feeder is 100 Hz; the temperature of each section of the extruder is 270 ℃, and the bracing strips are cooled by water and then cut into particles to prepare the modified PPO granules.

Respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by means of a die head to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.05mm and 0.95mm in sequence.

Example 3

99 parts of PC material with the type of light-emitting MD1500 and 1 part of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent are respectively added into a low-speed mixer to be mixed, the mixing temperature is 35 ℃, the rotating speed is 200r/min, and the mixing time is 60min, so that a mixture A1 is prepared.

Adding the blend A1 into a double-screw extruder from a main feeder, carrying out melt extrusion granulation, wherein the screw rotation speed is 400r/min, the frequency of the main feeder is 400Hz, the temperature of each section of the extruder is 260 ℃, and stretching, water cooling and granulating to obtain the modified PC granules.

95 parts of PPO material with the type of Asahi Kasei DG235 and 5 parts of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent are sequentially added into a low-speed mixer to be mixed, the mixing temperature is 28 ℃, the rotating speed is 80 r/min, and the mixing time is 42 minutes, so that a mixture A2 is prepared.

Adding the blend A2 into a double-screw extruder from a main feeder, and carrying out melt extrusion granulation, wherein the rotating speed of the screws is 200r/min, and the frequency of the main feeder is 300 Hz; the temperature of each section of the extruder is 280 ℃, and the modified PPO granules are prepared by cutting the strands into granules after water cooling.

Respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by virtue of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.2mm and 0.1mm in sequence.

Example 4

99 parts of PC material of LG 1201HP and 1 part of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent are respectively added into a low-speed mixer to be mixed, the mixing temperature is 35 ℃, the rotating speed is 200r/min, and the mixing time is 60min, so that a mixture A1 is prepared.

99 parts of PPO material with the type of Sabourne N110 and 1 part of gamma-glycidoxypropyltrimethoxysilane coupling agent are sequentially added into a low-speed mixer for blending, the mixing temperature is 35 ℃, the rotating speed is 200r/min, and the mixing time is 60min, so that a blend A2 is prepared.

Adding the blend A2 into a double-screw extruder from a main feeder, and carrying out melt extrusion granulation, wherein the rotating speed of the screws is 300 revolutions per minute, and the frequency of the main feeder is 400 Hz; the temperature of each section of the extruder is 300 ℃, and the modified PPO granules are prepared by cutting the strands into granules after water cooling.

Respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by virtue of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.95mm and 0.05mm in sequence.

Example 5

Respectively adding 90 parts of PC material with the model number of imperial L-1250Z, 5 parts of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent and 5 parts of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 30 minutes, so as to obtain a blend A1.

95 parts of Asahi-1951B-poly (p-phenylene oxide) material and 5 parts of isopropyl tris (dioctylphosphonoxy) titanate coupling agent were mixed in a low-speed mixer at 28 ℃ and 80 rpm for 42 minutes to obtain blend A2.

Respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by virtue of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.35mm and 0.75mm in sequence.

Example 6

Respectively adding 90 parts of PC material with the model of Mitsubishi S-1000R, 0.1 part of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent and 9.9 parts of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 30 minutes to prepare a blend A1.

95 parts of PPO material with the type of Saber GTX974 and 5 parts of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent are sequentially added into a low-speed mixer for blending, the mixing temperature is 28 ℃, the rotating speed is 80 revolutions per minute, and the mixing time is 42 minutes, so that a blend A2 is prepared.

And respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by means of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.4mm and 0.4mm in sequence.

Example 7

Respectively adding 90 parts of PC material with the model number of light-emitting HQ2200, 9.9 parts of gamma-glycidoxypropyltrimethoxysilane coupling agent and 0.1 part of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 30 minutes, so as to obtain a blend A1.

95 parts of a PPO material with a type of saber N110 and 5 parts of an isopropyl tris (dioctylphosphate acyloxy) titanate coupling agent are sequentially added into a low-speed mixer to be mixed, the mixing temperature is 28 ℃, the rotating speed is 80 revolutions per minute, and the mixing time is 42 minutes, so that a mixture A2 is prepared.

And respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by means of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.3mm and 0.6mm in sequence.

Example 8

Respectively adding 90 parts of a PC material with the model number of Mitsubishi HL-3000, 0.1 part of gamma-glycidoxypropyltrimethoxysilane coupling agent and 9.9 parts of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 30 minutes, so as to prepare a blend A1.

90 parts of PPO material of Asahi-converted DG235, 0.1 part of gamma-glycidoxypropyltrimethoxysilane coupling agent and 9.9 parts of isopropyltris (dioctylphosphatoxy) titanate coupling agent are sequentially added into a low-speed mixer to be mixed, the mixing temperature is 28 ℃, the rotating speed is 80 r/min, and the mixing time is 42 min, so that a blend A2 is prepared.

Example 9

Respectively adding 90 parts of PC material LG 1201HP, 0.1 part of gamma-glycidoxypropyltrimethoxysilane coupling agent and 9.9 parts of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 30 minutes, so as to obtain a blend A1.

Adding the blend A1 into a double-screw extruder from a main feeder, carrying out melt extrusion granulation, wherein the rotating speed of the screw is 150 r/min, the frequency of the main feeder is 200Hz, the temperature of each section of the extruder is 250 ℃, and the modified PC granules are prepared by drawing strips, cooling in water and then cutting into granules.

90 parts of PPO material with the model number of Saber GTX830, 9.9 parts of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent and 0.1 part of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent are sequentially added into a low-speed mixer to be mixed, the mixing temperature is 28 ℃, the rotating speed is 80 revolutions per minute, and the mixing time is 42 minutes, so that a mixture A2 is prepared.

And respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by means of a die head to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 1.2mm and 2.4mm in sequence.

Example 10

Respectively adding 90 parts of Wanhua A1105 PC material, 4 parts of gamma-glycidoxypropyltrimethoxysilane coupling agent and 6 parts of gamma-aminopropyltriethoxysilane coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 30 minutes, thus obtaining a blend A1.

90 parts of PPO material of Asahi Kasei 1951B, 9.9 parts of gamma-glycidoxypropyltrimethoxysilane coupling agent and 0.1 part of isopropyltris (dioctylphosphatoxy) titanate coupling agent are sequentially added into a low-speed mixer to be mixed, the mixing temperature is 28 ℃, the rotating speed is 80 r/min, and the mixing time is 42 min, so that a blend A2 is prepared.

Adding the blend A2 into a double-screw extruder from a main feeder, and carrying out melt extrusion granulation, wherein the rotating speed of the screws is 200 revolutions per minute, and the frequency of the main feeder is 300 Hz; the temperature of each section of the extruder is 280 ℃, and the strand is cooled by water and then cut into granules to prepare the modified PPO granules.

And respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by means of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.2mm and 0.3mm in sequence.

Example 11

80 parts of PC material with the model of imperial L-1250Z and 20 parts of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent are respectively added into a low-speed mixer to be mixed, the mixing temperature is 30 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 40 minutes, so that a mixture A1 is prepared.

70 parts of PPO material with the type of Saber GTX974 and 30 parts of isopropyl tri (dioctyl phosphate acyloxy) titanate coupling agent are sequentially added into a low-speed mixer for blending, the mixing temperature is 32 ℃, the rotating speed is 100 revolutions per minute, and the mixing time is 50 minutes, so that a blend A2 is prepared.

Adding the blend A2 into a double-screw extruder from a main feeder, and carrying out melt extrusion granulation, wherein the rotating speed of the screws is 200 revolutions per minute, and the frequency of the main feeder is 300 Hz; the temperature of each section of the extruder is 290 ℃, and the modified PPO granules are prepared by cutting the strands into granules after water cooling.

Respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by virtue of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.6mm and 0.4mm in sequence.

Example 12

Respectively adding 85 parts of PC material with the model number of light-emitting HQ2200 and 15 parts of gamma-glycidoxypropyltrimethoxysilane coupling agent into a low-speed mixer for blending, wherein the mixing temperature is 32 ℃, the rotating speed is 160 r/min, and the mixing time is 58 min, so as to obtain a blend A1.

Adding the blend A1 into a double-screw extruder from a main feeder, carrying out melt extrusion granulation, wherein the screw rotating speed is 350 r/min, the frequency of the main feeder is 290Hz, the temperature of each section of the extruder is 255 ℃, and stretching, water cooling and granulating to obtain the modified PC granules.

72 parts of PPO material with the type of Asahi Kasei (Asahi Kasei) L565V and 28 parts of isopropyl tris (dioctylphosphonoxy) titanate coupling agent are sequentially added into a low-speed mixer to be mixed, the mixing temperature is 34 ℃, the rotating speed is 190 revolutions per minute, and the mixing time is 59 minutes, so that a mixture A2 is prepared.

Adding the blend A2 into a double-screw extruder from a main feeder, and carrying out melt extrusion granulation, wherein the rotating speed of the screws is 270 revolutions per minute, and the frequency of the main feeder is 350 Hz; the temperature of each section of the extruder is 295 ℃, and the modified PPO granules are prepared by carrying out water cooling on the bracing strips and then carrying out granulation.

And respectively extruding a modified PC layer and a modified PPO layer through a first extruder and a second extruder by means of die heads to jointly form a two-layer co-extruded composite film, wherein the thicknesses of the modified PC layer and the modified PPO layer are 0.6mm and 0.6mm in sequence.

Example 13

This example differs from example 1 in that the modified polyphenylene ether layer comprises 90 parts of polyphenylene ether and 10 parts of isopropyl tris (dioctylphosphonoxy) titanate coupling agent, all other things being equal to example 1.

Example 14

This example differs from example 1 in that the modified polycarbonate layer comprises 90 parts of polycarbonate and 10 parts of isopropyl tris (dioctylphosphonoxy) titanate coupling agent, all other things being equal to example 1.

Example 15

This example differs from example 1 in that the modified polycarbonate layer comprises 90 parts of polycarbonate and 10 parts of isopropyl tris (dioctylphosphonoxy) titanate coupling agent; the modified polyphenylene ether layer comprised 90 parts of polyphenylene ether and 10 parts of isopropyldioleacyloxy (dioctylphosphatoxy) titanate coupling agent. The rest is the same as in example 1.

Comparative example 1

This comparative example is different from example 1 in that the composite film layer was not modified with a coupling agent, and the others were the same as those of example 1.

Comparative example 2

This comparative example differs from example 1 in that the modified PC layer was modified with a coupling agent, the polyphenylene ether layer was not modified with a coupling agent, and the rest was the same as example 1.

Comparative example 3

This comparative example is different from example 1 in that the modified polyphenylene ether layer was modified with a coupling agent, the PC layer was not modified with a coupling agent, and the other examples were the same as example 1.

Comparative example 4

This comparative example differs from example 1 in that the coupling agent was replaced with the aluminate coupling agent DL-411-A, and is otherwise identical to example 1.

Comparative example 5

This comparative example differs from example 1 in that the modified polycarbonate layer comprises 50 parts of polycarbonate and 50 parts of coupling agent, the remainder being the same as in example 1.

Comparative example 6

This comparative example differs from example 1 in that the modified polyphenylene ether layer comprises 50 parts of polyphenylene ether and 50 parts of a coupling agent, and the other is the same as in example 1.

Comparative example 7

The comparative example differs from example 2 in that the modified polyphenylene ether layers differ in composition and the modified polycarbonate layers are the same;

the method specifically comprises the following steps: respectively adding 60 parts of Wanhua A1105 PC material and 40 parts of gamma-aminopropyl triethoxysilane coupling agent into a low-speed mixer for blending to obtain blend A1;

55 parts of a PPO material with a type of saber GTX830 and 45 parts of an isopropyldioleate acyloxy (dioctylphosphonoxy) titanate coupling agent were sequentially added to a low-speed mixer and blended to prepare a blend a2, the rest being the same as in example 2.

Comparative example 8

The comparative example is different from example 1 in that the modified polycarbonate layer is different, specifically 55 parts of PC material with type imperial L-1250Y and 45 parts of gamma-glycidyl ether oxypropyl trimethoxy silane coupling agent are respectively added into a low-speed mixer to be mixed, the mixing temperature is 30 ℃, the rotating speed is 100 r/min, the mixing time is 30 min, and the blend A1 is prepared, and the rest is the same as that of example 1.

The composite membranes prepared in examples 1 to 15 and comparative examples 1 to 8 were subjected to performance tests, and the test results are shown in table 1.

Wherein the needle flame test is carried out according to IEC 60695-11-5 standard, the vertical combustion flame retardancy test is carried out according to UL94 standard, and the CTI value test is carried out according to IEC 60112 standard.

TABLE 1

As can be seen from Table 1, the composite films prepared in the embodiments 1 to 12 of the present invention have a very long endurance time in the needle flame test, excellent vertical burning flame retardant property, a high and stable CTI value, good mechanical properties, wear resistance, chemical resistance and water resistance, and can be used for preparing battery insulating materials and other various high performance insulating materials; specifically, under the halogen-free limiting condition, the flame retardant grade of UL94-V0 with the thickness of 0.3mm can still be realized; the CTI value of the two layers of composite films can meet the voltage resistance requirement of 0-grade 600V by means of the modified PPO layer; by means of the excellent compatibility of the modified PPO layer and the modified PC layer, the composite film has a high and stable CTI value.

Example 13 the silane-based coupling agent in the modified polyphenylene ether layer was changed to a titanate-based coupling agent, which decreased the duration of the pin flame test.

Example 14 modification of the silane-based coupling agent to a titanate-based coupling agent in the polycarbonate layer results in a decrease in the duration of the pin flame test.

Example 15 after the silane-based coupling agent in both the modified polycarbonate layer and the modified polyphenylene ether layer was changed to the titanate-based coupling agent, the endurance time in the needle flame test was further reduced on the basis of examples 13 and 14.

Examples 13-15 demonstrate that the addition of silane-based coupling agents provides a better extension of the resistance time to the needle flame test than titanate-based coupling agents.

Comparative example 1 the composite film layer was not modified with a coupling agent, which resulted in delamination at the interface between the modified PC layer and the modified PPO layer.

Comparative example 2 the modified PC layer was modified with a coupling agent and the polyphenylene ether layer was not modified with a coupling agent, which caused the risk of delamination at the junction of the modified PC layer and the modified PPO layer.

Comparative example 3 the modified polyphenylene ether layer was modified with a coupling agent and the PC layer was not modified with a coupling agent, which caused the risk of delamination at the junction of the modified PC layer and the modified PPO layer.

Comparative example 4 replacement of the coupling agent with the aluminate coupling agent DL-411-a decreased the endurance time of the composite film pin flame test and the flame retardant properties of the vertical burn.

Comparative example 5 when the amount of the coupling agent used in the modified polycarbonate layer was increased, the endurance time in the needle flame test and the flame retardancy in the vertical burning were deteriorated.

Comparative example 6 when the amount of the coupling agent used in the modified polyphenylene ether layer was increased, the endurance time in the pin flame test and the flame retardancy in the vertical burning were deteriorated.

Comparative example 7 when the amount of the titanate-based coupling agent in the modified polyphenylene ether layer was increased, the needle flame test duration, the vertical burning flame retardancy, and the CTI value were decreased.

Comparative example 8 adding the silicon-based coupling agent in an excessive amount, the needle flame holding time was rather significantly reduced.

The present invention is illustrated by the above-mentioned examples, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, i.e. it is not meant to imply that the present invention must rely on the above-mentioned detailed process equipment and process flow to be practiced. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that, in the above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, the present invention does not separately describe various possible combinations.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. The composite film with high needle flame test endurance time and high CTI value is characterized by consisting of a modified polycarbonate layer and a modified polyphenyl ether layer, wherein the modified polycarbonate layer and the modified polyphenyl ether layer are independently modified by a coupling agent;

the modified polycarbonate layer comprises 60-99 parts by weight of polycarbonate and 1-40 parts by weight of coupling agent;

the modified polyphenylene ether layer comprises 60-99 parts by weight of polyphenylene ether and 1-40 parts by weight of a coupling agent;

the coupling agent in the modified polycarbonate layer and the coupling agent in the modified polyphenyl ether layer are independently silane coupling agents, titanate coupling agents or a compound of the silane coupling agents and the titanate coupling agents.

2. The composite film according to claim 1, wherein the mass ratio of the silane coupling agent to the titanate coupling agent in the formulation is (1-99) to (1-99).

3. The composite film according to claim 1 or 2, wherein the silane-based coupling agent has a chemical formula of RSiX₃；

The R group is one of vinyl, epoxy or amino;

the X group is an alkoxy group;

the alkoxy is methoxy or ethoxy;

4. The composite film according to claim 1 or 2, wherein the titanate-based coupling agent has a chemical formula of RO_(4-n)Ti(OX-RY)_nN is 1, 2 or 3;

the RO group is a hydrolyzable alkoxy group;

the R group is alkyl;

the OX group is a phosphorus group;

the Y group is hydroxyl, amino or epoxy;

5. Composite film according to one of claims 1 to 4, characterized in that the thickness of the composite film is 0.3 to 3mm, preferably 0.3 to 1 mm.

6. The composite film according to any one of claims 1 to 5, wherein the modified polycarbonate layer has a thickness of 5 to 95% of the total thickness of the composite film, and the modified polyphenylene ether layer has a thickness of 5 to 95% of the total thickness of the composite film.

7. A method for preparing a composite film with high needle flame test endurance and high CTI value according to any one of claims 1 to 6, comprising the following steps:

8. The preparation method of claim 7, wherein in the step 1), the blending temperature is 25-35 ℃, the rotation speed is 10-200r/min, and the time is 10-60 min; the temperature of the extrusion granulation is 220-260 ℃, the screw rotating speed of the extrusion granulation is 100-400r/min, and the frequency of the main feeding machine is 100-400 Hz.

9. The preparation method of claim 7, wherein in the step 2), the blending temperature is 25-35 ℃, the rotation speed is 10-200r/min, and the time is 10-60 min; the temperature of the extrusion granulation is 270-300 ℃, the screw rotating speed of the extrusion granulation is 100-300r/min, and the frequency of the main feeding machine is 100-400 Hz.

10. Use of a high needle flame test withstand time, high CTI value composite film according to any one of claims 1 to 6 in the preparation of battery insulation.