CN114921024A - White shading halogen-free flame-retardant polypropylene material and preparation method thereof - Google Patents

White shading halogen-free flame-retardant polypropylene material and preparation method thereof Download PDF

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CN114921024A
CN114921024A CN202210480609.8A CN202210480609A CN114921024A CN 114921024 A CN114921024 A CN 114921024A CN 202210480609 A CN202210480609 A CN 202210480609A CN 114921024 A CN114921024 A CN 114921024A
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parts
retardant
halogen
flame
titanium dioxide
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CN114921024B (en
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陈新泰
龚文幸
刘鹏辉
黄方雁
佘豪杰
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Polyrocks Chemical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

Abstract

The invention discloses a white shading halogen-free flame-retardant polypropylene material and a preparation method thereof. A white shading halogen-free flame-retardant polypropylene material is prepared from 40-90 wt% of flame-retardant master batch and the balance of titanium dioxide master batch; the flame-retardant master batch comprises the following raw materials in parts by mass: 40-60 parts of polypropylene, 30-50 parts of P-N intumescent flame retardant, 2-5 parts of compatilizer, 1-5 parts of zinc oxide, 1-10 parts of filler, 0.2-0.5 part of anti-dripping agent, 0.2-0.5 part of lubricant and 0.2-0.4 part of antioxidant; the preparation raw materials of the titanium dioxide master batch comprise the following raw materials in parts by mass: 35-65 parts of polypropylene, 40-70 parts of titanium dioxide, 1-3 parts of coupling agent, 0.5-1.5 parts of PE wax grafted maleic anhydride and 0.2-0.5 part of antioxidant. The white shading halogen-free flame-retardant polypropylene material can achieve light-proof performance with the thickness of 0.75mm, achieves the flame-retardant performance of V0 level, and has excellent mechanical properties.

Description

White shading halogen-free flame-retardant polypropylene material and preparation method thereof
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a white shading halogen-free flame-retardant polypropylene material and a preparation method thereof.
Background
In the household appliance and lighting industry, faults such as short circuit and spark may occur in a circuit in photoelectric equipment, so that a fire disaster is caused, in order to ensure the use safety, the light transmission is required to be reduced or prevented, and certain requirements are required on the light shielding property and the flame retardance of materials.
The polypropylene has the characteristics of low cost and no moisture absorption, and simultaneously has good electrical property, corrosion resistance and high insulativity, so that the polypropylene becomes a favored material in the household appliance industry. In the lighting industry, the traditional shading polypropylene material does not require flame retardance or only requires the V2 grade, in recent years, with the continuous occurrence of fire accidents, the requirements on the used polypropylene material are more and more strict, and on the premise of achieving shading, the flame retardance also needs to achieve the V0 grade or higher white shading grade.
Patent application CN109438764A discloses a flame retardant polypropylene composition with high light shade, white or light color, which has flame retardant grade only reaching V2 grade and is added with a large amount of filler. As for the V0 grade lightproof polypropylene material, the most popular is the brominated flame retardant in the market, because titanium dioxide and filler have no influence on the flame retardant efficiency, but because the brominated flame retardant is expensive, toxic gas and dense smoke are generated during combustion, and the brominated flame retardant does not meet the halogen-free requirement in many fields, thereby limiting the application of the brominated flame retardant.
For halogen-free P-N type flame-retardant polypropylene materials, the titanium dioxide needs to be added to more than 12 percent to completely shield light with the thickness of 1.5mm, but the negative effect is that the flame retardance can not pass throughV0, even not up to the V2 rating. The influence of titanium dioxide on flame retardance mainly has two aspects: firstly, titanium white powder rigidity is very big, if through twin-screw granulation, can have very strong shearing action to halogen-free flame retardant, produces a large amount of shearing heats and leads to halogen-free flame retardant degradation, and fire-retardant efficiency reduces. Secondly, the main component of the titanium dioxide is titanium dioxide, titanium belongs to transition metal elements, and-OH and NH 4 + The group has stronger complexing ability, has better catalytic action on the dehydration, deamination and phosphorylation of the flame retardant, but when the titanium content is too high, the flame retardant can be dehydrated and deaminated earlier under a certain shearing action, so that the flame retardant is not matched with the degradation temperature of polypropylene, and the flame retardant efficiency is greatly reduced.
Disclosure of Invention
In order to solve the problem that the polypropylene material in the prior art cannot simultaneously meet good shading and flame retardant properties, one purpose of the invention is to provide a white shading halogen-free flame retardant polypropylene material, and the other purpose of the invention is to provide a preparation method of the white shading halogen-free flame retardant polypropylene material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a white shading halogen-free flame-retardant polypropylene material, which is prepared from 40-90 wt% of flame-retardant master batch and the balance of titanium dioxide master batch;
the flame-retardant master batch comprises the following raw materials in parts by mass: 40-60 parts of polypropylene, 30-50 parts of P-N intumescent flame retardant, 2-5 parts of compatilizer, 1-5 parts of zinc oxide, 1-10 parts of filler, 0.2-0.5 part of anti-dripping agent, 0.2-0.5 part of lubricant and 0.2-0.4 part of antioxidant;
the preparation raw materials of the titanium dioxide master batch comprise the following raw materials in parts by mass: 35-65 parts of polypropylene, 40-70 parts of titanium dioxide, 1-3 parts of coupling agent, 0.5-1.5 parts of PE wax grafted maleic anhydride and 0.2-0.5 part of antioxidant.
Preferably, the preparation raw materials of the white shading halogen-free flame-retardant polypropylene material consist of 50 wt% -85 wt% of flame-retardant master batch and the balance of titanium dioxide master batch; further preferably, the preparation raw material consists of 60 wt% -85 wt% of the flame-retardant master batch and the balance of the titanium dioxide master batch.
Preferably, the preparation raw materials of the white shading halogen-free flame-retardant polypropylene material comprise the following raw materials in parts by mass: 45-55 parts of polypropylene, 30-45 parts of P-N intumescent flame retardant, 2-5 parts of compatilizer, 1-5 parts of zinc oxide, 2-8 parts of filler, 0.2-0.5 part of anti-dripping agent, 0.2-0.5 part of lubricant and 0.2-0.4 part of antioxidant.
Preferably, the preparation raw materials of the white shading halogen-free flame-retardant polypropylene material comprise the following raw materials in parts by mass: 35-60 parts of polypropylene, 45-70 parts of titanium dioxide, 1-3 parts of coupling agent, 0.5-1.5 parts of PE wax grafted maleic anhydride and 0.2-0.5 part of antioxidant.
Preferably, the white shading halogen-free flame-retardant polypropylene material has the melt index of 5-30g/10min under the conditions of 230 ℃ and 2.16 kg; it is further preferred that the polypropylene has a melt index of 10 to 30g/10min at 230 ℃ under 2.16 kg.
Preferably, in the white shading halogen-free flame-retardant polypropylene material, the P-N intumescent flame retardant is at least one of ammonium polyphosphate flame retardant and piperazine pyrophosphate flame retardant; more preferably, at least one of P-N intumescent flame retardant piperazine pyrophosphate flame retardant; in some preferred embodiments of the invention, the P-N intumescent flame retardant is at least one of EPFR-110DM, EPFR-110DL, EPFR-110DN of Posfolff-P chemistry.
Preferably, the phosphorus content of the P-N intumescent flame retardant is 18-22 wt%.
Preferably, the nitrogen content of the P-N intumescent flame retardant is 20-25 wt%.
Preferably, the average particle size of the P-N intumescent flame retardant of the white shading halogen-free flame retardant polypropylene material is 5-10 μm.
Preferably, the white shading halogen-free flame-retardant polypropylene material has the compatilizer of at least one of maleic anhydride grafted polypropylene (PP-g-MAH), maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride grafted hydrogenated styrene-butadiene block copolymer (SEBS-g-MAH), maleic anhydride grafted polyolefin elastomer (POE-g-MAH) and maleic anhydride grafted ethylene propylene diene monomer (EPDM-g-MAH); further preferably, the compatilizer is at least one of PP-g-MAH and POE-g-MAH.
Preferably, the grafting rate of the compatilizer of the white shading halogen-free flame-retardant polypropylene material is 0.8-1.8%; further preferably, the grafting ratio of the compatibilizer is 1.0% to 1.5%.
Preferably, the zinc oxide of the white shading halogen-free flame-retardant polypropylene material is produced by an indirect method, and the purity is over 99.9 percent; further preferably, the zinc oxide is nano zinc oxide.
Preferably, the white shading halogen-free flame-retardant polypropylene material has at least one of talcum powder, mica powder, montmorillonite and barium sulfate as a filler; further preferably, the filler is at least one of talcum powder, mica powder and montmorillonite; still more preferably, the filler is at least one of talc powder and mica powder.
Preferably, the particle size of the filler of the white shading halogen-free flame retardant polypropylene material is 1.3-2.6 μm.
Preferably, the anti-dripping agent of the white shading halogen-free flame-retardant polypropylene material is polytetrafluoroethylene powder; further preferably, the anti-dripping agent is coated polytetrafluoroethylene powder.
Preferably, the lubricant of the white shading halogen-free flame-retardant polypropylene material is at least one of erucamide, oleamide, stearic acid, magnesium stearate, calcium stearate, zinc stearate, silicone powder, paraffin, polyethylene wax and ethylene bisstearamide; further preferably, the lubricant is at least one of silicone powder, polyethylene wax and ethylene bis stearamide.
Preferably, the antioxidant of the white shading halogen-free flame-retardant polypropylene material is at least one of hindered phenol antioxidant and phosphite antioxidant; more preferably, the antioxidant is at least one of antioxidant 168, antioxidant 245, antioxidant 626, antioxidant 1010, antioxidant 1075, antioxidant 1076, antioxidant 1098 and antioxidant 330; still more preferably, the antioxidant is antioxidant 1010 and antioxidant 168; more preferably, the antioxidant is an antioxidant 1010 and an antioxidant 168, wherein the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1: (1-3) compounding; in some preferred embodiments of the present invention, the antioxidant is an antioxidant 1010 and an antioxidant 168, wherein the mass ratio of the antioxidant to the antioxidant is 1: 2 is prepared by compounding.
Preferably, the titanium dioxide is rutile titanium dioxide in the white shading halogen-free flame-retardant polypropylene material.
Preferably, the coupling agent of the white shading halogen-free flame-retardant polypropylene material is at least one of titanate coupling agent, aluminate coupling agent and silane coupling agent; further preferably, the coupling agent is a silane coupling agent; still more preferably, the coupling agent is an aminosilane coupling agent.
Preferably, the grafting ratio of the PE wax grafted maleic anhydride of the white shading halogen-free flame-retardant polypropylene material is 5-9%; further preferably, the grafting rate of the PE wax grafted maleic anhydride is 6-8%; in some preferred embodiments of the invention, the grafting ratio of the PE wax grafted maleic anhydride is 7%; the addition of the high-grafting-rate PE wax grafted maleic anhydride not only has the effect of improving the compatibility, but also provides a particularly good internal and external lubricating effect, and can further reduce the shear heat caused by friction of titanium dioxide, thereby endowing the material with excellent flame retardant property.
Preferably, the white shading halogen-free flame-retardant polypropylene material has the light-proof performance of 0.75mm thickness and the flame-retardant grade of V0.
The second aspect of the invention provides a preparation method of the white shading halogen-free flame-retardant polypropylene material, which comprises the following steps:
1) preparing a flame-retardant master batch: mixing, extruding and granulating preparation raw materials of the flame-retardant master batch to obtain the flame-retardant master batch;
2) preparing titanium dioxide master batch: performing surface treatment on titanium dioxide by using a coupling agent in a titanium dioxide master batch preparation raw material; mixing the surface-treated titanium dioxide, polypropylene, PE wax grafted maleic anhydride and an antioxidant, extruding and granulating to obtain titanium dioxide master batch;
3) preparing a white shading halogen-free flame-retardant polypropylene material: mixing the flame-retardant master batch obtained in the step 1) and the titanium dioxide master batch obtained in the step 2), and performing injection molding to obtain the white shading halogen-free flame-retardant polypropylene material.
Preferably, the preparation method of the white shading halogen-free flame-retardant polypropylene material adopts a double-screw extruder to prepare the flame-retardant master batch, the titanium dioxide master batch and the white shading halogen-free flame-retardant polypropylene material; further preferably, the vacuum degree of the double-screw extruder is more than or equal to 0.8MPa, and the rotating speed of the double-screw extruder is 300-; the processing temperature of the double-screw extruder is 180-220 ℃.
Preferably, in the step 2), the temperature for performing surface treatment on the titanium dioxide by using the coupling agent is 90-120 ℃, and the reaction time is 1.5-2.5 h.
The beneficial effects of the invention are:
1. the white shading halogen-free flame-retardant polypropylene material can achieve light-proof performance with the thickness of 0.75mm, achieves the flame-retardant performance of V0 level, and has excellent mechanical properties.
2. The zinc oxide is added into the white shading halogen-free flame-retardant polypropylene material, and the zinc oxide can play a certain shading effect while endowing the material with high flame-retardant efficiency, so that the using amount of titanium dioxide can be reduced.
3. The white shading halogen-free flame-retardant polypropylene material is added with proper filler, so that the shading effect of the material can be further improved, and the using amount of titanium dioxide can be reduced.
4. The white shading halogen-free flame-retardant polypropylene material is added with a proper compatilizer, so that the alloy material can have excellent mechanical property and flame retardant property.
5. The invention adopts the coupling agent to carry out surface treatment on the titanium dioxide, and can improve the compatibility of the titanium dioxide and the polypropylene resin, thereby improving the shading effect of the titanium dioxide.
6. According to the invention, the titanium dioxide is firstly prepared into the master batch and then is subjected to batch mixing and injection molding with the halogen-free flame-retardant master batch, so that the problem of high shear heat caused in the co-granulation process of the titanium dioxide and the halogen-free flame-retardant master batch is effectively solved, and meanwhile, because the halogen-free flame retardant and the titanium dioxide are not subjected to twin-screw granulation together, the catalytic action of the titanium dioxide is greatly weakened, and the flame-retardant efficiency of the flame retardant can be effectively maintained.
7. The reproducible P-N intumescent flame retardant is added in the white shading halogen-free flame-retardant polypropylene material, and compared with the bromine flame retardant, the production cost is reduced by 6000-8000 yuan/ton.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration only. The specific process parameters and the like of the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific data of the following examples. The starting materials used in the examples were obtained from conventional commercial sources, unless otherwise specified.
The raw materials used in the examples and comparative examples are as follows:
polypropylene: SZ30S, majesty petrochemical; EP548R, zhonghai shell brand;
ammonium polyphosphate system flame retardant: EPFR-100D/EPFR-100C, Puseofur Chemicals, Kyowa;
piperazine pyrophosphate system flame retardant: EPFR-110DL/EPFR-110DM/EPFR-110DN, Puseofurofosmin Chemicals, Inc., Qingdao;
titanium dioxide: r103, dupont;
titanate coupling agent: KR-38S, Kenreqi, USA;
aluminate coupling agent: DL-411, mountain one plastification;
silane coupling agent: KH550, dao kang ning;
PE wax grafted maleic anhydride: PE-4430, a Yitian new material;
talc powder: BHS-718A (1250 mesh), BHS-934071(4000 mesh), Asaheng;
mica powder: HY-PM2(400 mesh), HY-PM3(2500 mesh), and Haiyang powder;
anti-dripping agent: SN3308, guangzhou entropy energy;
lubricant: PE wax BN500, bangni chemical; calcium stearate CV500, zinc stearate AV-300, Hanwei;
antioxidant: antioxidant 1010, antioxidant 168, basf;
example 1
Preparing the flame-retardant master batch: feeding 49 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant into a main feed of a double-screw extruder, adding 38 parts of ammonium polyphosphate system flame retardant (EPFR-100D) and 5 parts of talcum powder (BHS-718A) from a side feed, extruding and granulating to obtain the halogen-free flame-retardant master batch.
Preparing a titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; and (3) putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw, and extruding and granulating to obtain the titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Example 2
The difference from the example 1 is that the flame-retardant master batch uses the piperazine pyrophosphate system flame retardant, and the addition amount is reduced by 2%.
Preparing the flame-retardant master batch: 51 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of talcum powder (BHS-718A) are added from a side feed, and the mixture is extruded and granulated to obtain the halogen-free flame-retardant master batch.
Preparing titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; and (3) putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw, and extruding and granulating to obtain the titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Example 3
The difference from example 2 is that the filler used in the flame retardant masterbatch is mica powder (HY-PM 3).
Preparing the flame-retardant master batch: 51 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of mica powder (HY-PM3) are added from a side feed, and the mixture is extruded and granulated to obtain the halogen-free flame-retardant master batch.
Preparing titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw to extrude and granulate to obtain titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: and (2) mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Example 4
The difference from example 2 is that the PP used is a copolymeric PP (EP548R) and the compatibilizer used is SEBS-g-MAH.
Preparing the flame-retardant master batch: 51 parts of PP (EP548R), 5 parts of SEBS-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of talcum powder (BHS-718A) are added from a side feed, and the mixture is extruded and granulated to obtain the halogen-free flame-retardant master batch.
Preparing titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S)), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by a titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw to extrude and granulate to obtain titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Example 5
The difference from the example 2 is that the titanium dioxide master batch uses a silane coupling agent.
Preparing the flame-retardant master batch: 51 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of talcum powder (BHS-718A) are added from a side feed, and the mixture is extruded and granulated to obtain the halogen-free flame-retardant master batch.
Preparing titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of silane coupling agent (KH-550), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; and (3) putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by a silane coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw, and extruding and granulating to obtain the titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Example 6
The difference from the example 2 is that the titanium dioxide master batch uses an aluminate coupling agent.
Preparing the flame-retardant master batch: 51 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant are fed into a double-screw extruder to be fed by a main feed, 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of talcum powder (BHS-718A) are added from a side feed, and the halogen-free flame-retardant master batch is obtained through extrusion and granulation.
Preparing a titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of aluminate coupling agent (DL-411), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by an aluminate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw to extrude and granulate to obtain titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Comparative example 1
As with the example 1 formulation, the only difference was the use of a one-step process.
Feeding 39.2 parts of PP (SZ30S), 7.64 parts of PP (EP548R), 4 parts of PP-g-MAH, 30.4 parts of EPFR-100D, 4 parts of talcum powder (BHS-718A), 1.6 parts of zinc oxide and 12 parts of surface-treated titanium dioxide (2 parts of titanate coupling agent (KR-38S)) to 100 parts of titanium dioxide (R103) for surface treatment at the reaction temperature of 105 ℃ for 2 hours, 0.3 parts of PE wax grafted maleic anhydride, 0.24 parts of anti-dripping agent (SN3308), 0.32 parts of PE wax (BN500) and 0.3 parts of antioxidant into a double-screw extruder for extrusion and granulation to obtain the shading halogen-free flame-retardant polypropylene material.
Comparative example 2
The only difference from example 3 is that the flame retardant masterbatch did not use zinc oxide.
Preparing the flame-retardant master batch: feeding 53 parts of PP (SZ30S), 5 parts of PP-g-MAH, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant into a main feed of a double-screw extruder, adding 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of mica powder (HY-PM3) from a side feed, extruding and granulating to obtain the halogen-free flame-retardant master batch.
Preparing titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw to extrude and granulate to obtain titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Comparative example 3
The only difference from example 3 is that the flame retardant masterbatch is not added with a filler.
Preparing the flame-retardant master batch: feeding 56 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant into a main feed of a double-screw extruder, adding 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) from a side feed, extruding and granulating to obtain the halogen-free flame-retardant master batch.
Preparing titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; and (3) putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw, and extruding and granulating to obtain the titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Comparative example 4
The only difference from example 3 is that the flame retardant masterbatch is not added with a compatibilizer.
Preparing the flame-retardant master batch: feeding 56 parts of PP (SZ30S), 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant into a main feed of a double-screw extruder, adding 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of mica powder (HY-PM3) from a side feed, extruding and granulating to obtain the halogen-free flame-retardant master batch.
Preparing a titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; putting 38.2 parts of PP (EP548R), 60 parts of titanium dioxide treated by titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw to extrude and granulate to obtain titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: and (2) mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Comparative example 5
The only difference from example 3 is that the titanium dioxide has not been treated with a coupling agent.
Preparing the flame-retardant master batch: 51 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of mica powder (HY-PM3) are added from a side feed, and the mixture is extruded and granulated to obtain the halogen-free flame-retardant master batch.
Preparing titanium dioxide master batch: and (3) adding 38.2 parts of PP (EP548R), 60 parts of titanium dioxide, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride into a double screw, and extruding and granulating to obtain the titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
Comparative example 6
The only difference from example 3 is that no PE wax grafted maleic anhydride was added.
Preparing the flame-retardant master batch: 51 parts of PP (SZ30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN3308), 0.4 part of PE wax (BN500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate system flame retardant (EPFR-110DN) and 5 parts of mica powder (HY-PM3) are added from a side feed, and the mixture is extruded and granulated to obtain the halogen-free flame-retardant master batch.
Preparing a titanium dioxide master batch: firstly, carrying out surface treatment on 100 parts of titanium dioxide (R103) by using 2 parts of titanate coupling agent (KR-38S), wherein the reaction temperature is 105 ℃, and the reaction time is 2 hours; and (3) adding 39.7 parts of PP (EP548R), 60 parts of titanium dioxide treated by a titanate coupling agent and 0.3 part of antioxidant into a double screw for extrusion granulation to obtain the titanium dioxide master batch.
Preparing a white shading halogen-free flame-retardant polypropylene material: mixing the halogen-free flame-retardant master batch and the titanium dioxide master batch obtained in the previous two steps according to the mass ratio of 4: 1, and performing injection molding to obtain the shading halogen-free flame-retardant polypropylene material.
The raw materials are weighed according to the raw material compositions of the examples 1-6 and the comparative examples 1-6 respectively, and extruded and granulated, wherein the screw rotation speed is 400r/min, the processing temperature is 190-.
And (3) testing the material performance:
the white shading halogen-free flame-retardant polypropylene materials prepared in the examples 1 to 6 and the comparative examples 1 to 6 are subjected to the following performance tests:
density: testing according to ASTM D792 standard;
flame retardant property: testing according to the detection standard of UL-94;
tensile strength, elongation at break: testing according to ASTM D638;
flexural strength, flexural modulus: testing was performed according to ASTM D790;
impact strength: testing according to ASTM D256;
dispersion situation: tabletting, which is to put the particles on a mould, then put the mould on a hot press for tabletting, and the tabletting size is as follows: the length, the width and the thickness are 100mm, 100mm and 0.2mm, the mould pressing pressure is 10MPa, the mould pressing temperature is 180 ℃, and then whether the surface has agglomeration points or not is observed;
and (3) shading condition: and (3) irradiating one surface of the square plate by using a light source, and observing whether light penetrates through the other surface, wherein the distance between the light source and the square plate is 5mm, and the length and the width of the square plate are 60 x 60 mm.
The results of the performance test of the white shading halogen-free flame-retardant polypropylene materials of examples 1-6 and comparative examples 1-6 are shown in tables 1-2:
TABLE 1 Performance test results of the white shading halogen-free flame retardant polypropylene materials of examples 1-6
Figure BDA0003627589470000101
TABLE 2 Performance test results of the white shading halogen-free flame-retardant polypropylene materials of comparative examples 1 to 6
Figure BDA0003627589470000102
Figure BDA0003627589470000111
And (3) analyzing a test result:
as can be seen from the test data of the examples 1-6 and the comparative examples 1-6, the components in the formula are matched with each other, and the halogen-free flame-retardant polypropylene material prepared by the method of blending the halogen-free flame-retardant master batch and the titanium white master batch realizes the flame retardance V0 and the shading effect of 0.75mm thickness. Meanwhile, the zinc oxide is added in the formula, so that the use amount of the flame retardant and the titanium dioxide is reduced; in addition, the addition of the compatilizer not only improves the flame retardant grade, but also improves the mechanical property of the material; on the other hand, the titanium dioxide is firstly subjected to surface treatment in the titanium dioxide master batch, so that the shading efficiency of the titanium dioxide can be greatly improved, and meanwhile, the special polar lubricant is added, so that the dispersion of the titanium dioxide in a halogen-free flame-retardant system is greatly improved, and the shading efficiency is improved. Specifically, the method comprises the following steps:
(1) from the test results of examples 1 to 6 and comparative example 1, it can be seen that: when the one-step method is adopted for production, the flame retardant grade of the material is greatly reduced, and the material cannot pass the V-2 grade, which shows that the titanium dioxide has very serious negative influence on the flame retardant, and the reason is that the flame retardant is degraded in advance due to strong shearing heat and complexing action.
(2) From the test results of examples 1 to 6 and comparative example 2, it can be seen that: when the zinc oxide is not used, the flame retardant grade of the material can only pass the V-1 grade, and meanwhile, the shading effect is reduced because the zinc oxide has a certain shading effect and is also a flame retardant synergist, and when the nano zinc oxide is adopted, the flame retardant efficiency and the shading effect are more obvious than those of common zinc oxide.
(3) From the test results of examples 1 to 6 and comparative example 3, it can be seen that: the shading effect is reduced when the mica powder is not used because the mica powder has an obvious lamellar structure and has a certain shading effect. The invention selects proper filler, so that the prepared material can pass a shading test.
(4) From the test results of examples 1 to 6 and comparative example 4, it can be seen that: when no compatilizer is used, the compatibility of the filler and the flame retardant with PP is poor, and various mechanical properties are obviously reduced. The invention selects proper compatilizers, particularly PP-g-MAH and POE-g-MAH, can endow the alloy material with excellent mechanical property, improves the dispersion effect of the flame retardant, and further improves the flame retardant efficiency.
(5) From the test results of examples 1 to 6 and comparative example 5, it can be seen that: when the titanium dioxide is not subjected to surface treatment, the shading effect of the material is reduced because the dispersing effect of the untreated titanium dioxide is reduced, especially in a halogen-free system with high viscosity. The invention selects the proper coupling agent, which not only can improve the dispersion of the titanium dioxide, but also can improve the compatibility of the titanium dioxide and the halogen-free flame retardant, so that the prepared material can achieve the shading effect of 0.75mm and can pass the flame retardant V0 grade.
(6) From the test results of examples 1 to 6 and comparative example 6, it can be seen that: the light-shielding effect is reduced without using the PE wax grafted maleic anhydride, and the PE wax grafted maleic anhydride has an agglomeration point, which shows that the PE wax grafted maleic anhydride has a good dispersing effect on titanium dioxide. The PE wax grafted maleic anhydride selected by the invention solves the agglomeration problem, so that the prepared material can achieve the shading effect of 0.75mm, and can pass the flame retardant V0 grade.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. The white shading halogen-free flame-retardant polypropylene material is characterized in that the preparation raw materials consist of 40 wt% -90 wt% of flame-retardant master batch and the balance of titanium dioxide master batch;
the flame-retardant master batch comprises the following raw materials in parts by mass: 40-60 parts of polypropylene, 30-50 parts of P-N intumescent flame retardant, 2-5 parts of compatilizer, 1-5 parts of zinc oxide, 1-10 parts of filler, 0.2-0.5 part of anti-dripping agent, 0.2-0.5 part of lubricant and 0.2-0.4 part of antioxidant;
the preparation raw materials of the titanium dioxide master batch comprise the following raw materials in parts by mass: 35-65 parts of polypropylene, 40-70 parts of titanium dioxide, 1-3 parts of coupling agent, 0.5-1.5 parts of PE wax grafted maleic anhydride and 0.2-0.5 part of antioxidant.
2. The white shading halogen-free flame-retardant polypropylene material as claimed in claim 1, wherein the melt index of the polypropylene at 230 ℃ and 2.16kg is 5-30g/10 min.
3. The white shading halogen-free flame-retardant polypropylene material according to claim 1, wherein the P-N intumescent flame retardant is at least one of ammonium polyphosphate flame retardant and piperazine pyrophosphate flame retardant.
4. The white shading halogen-free flame retardant polypropylene material as claimed in claim 1, wherein the compatilizer is at least one of maleic anhydride grafted polypropylene, maleic anhydride grafted polyethylene, maleic anhydride grafted hydrogenated styrene-butadiene block copolymer, maleic anhydride grafted polyolefin elastomer and maleic anhydride grafted ethylene propylene diene monomer.
5. The white shading halogen-free flame retardant polypropylene material as claimed in claim 4, wherein the grafting ratio of the compatilizer is 0.8-1.8%.
6. The white shading halogen-free flame-retardant polypropylene material according to claim 1, wherein the filler is at least one of talcum powder, mica powder, montmorillonite and barium sulfate.
7. The white shading halogen-free flame retardant polypropylene material according to claim 6, wherein the particle size of the filler is 1.3-2.6 μm.
8. The white shading halogen-free flame retardant polypropylene material as claimed in claim 1, wherein the coupling agent is at least one of titanate coupling agent, aluminate coupling agent and silane coupling agent.
9. The white shading halogen-free flame-retardant polypropylene material as claimed in claim 1, wherein the grafting ratio of the PE wax grafted maleic anhydride is 5-9%.
10. The preparation method of the white shading halogen-free flame retardant polypropylene material of any one of claims 1 to 9, characterized by comprising the following steps:
1) preparing a flame-retardant master batch: mixing, extruding and granulating preparation raw materials of the flame-retardant master batch to obtain the flame-retardant master batch;
2) preparing titanium dioxide master batches: performing surface treatment on titanium dioxide by using a coupling agent in a titanium dioxide master batch preparation raw material; mixing the surface-treated titanium dioxide, polypropylene, PE wax grafted maleic anhydride and an antioxidant, extruding and granulating to obtain titanium dioxide master batches;
3) preparing a white shading halogen-free flame-retardant polypropylene material: mixing the flame-retardant master batch obtained in the step 1) with the titanium dioxide master batch obtained in the step 2), and performing injection molding to obtain the white shading halogen-free flame-retardant polypropylene material.
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