CN114921024B - 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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CN114921024B
CN114921024B CN202210480609.8A CN202210480609A CN114921024B CN 114921024 B CN114921024 B CN 114921024B CN 202210480609 A CN202210480609 A CN 202210480609A CN 114921024 B CN114921024 B CN 114921024B
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flame retardant
halogen
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titanium dioxide
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CN114921024A (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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    • 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
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    • 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
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition

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Abstract

The invention discloses a white shading halogen-free flame retardant polypropylene material and a preparation method thereof. The white shading halogen-free flame retardant polypropylene material is prepared from 40-90wt% of flame retardant master batch and the balance of titanium dioxide master batch; the preparation raw materials of the flame-retardant master batch comprise 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 realize light-tightness with the thickness of 0.75mm, achieves the V0 level of flame retardance and has excellent mechanical property.

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 appliances and lighting industries, faults such as short circuit, spark and the like may occur in a circuit in photoelectric equipment, so that fire disaster is caused, and in order to ensure use safety, light transmission is often required to be reduced or prevented, and certain requirements are provided for light shielding performance and flame retardance of materials.
The polypropylene has the characteristics of low cost and no moisture absorption, and has good electrical property, corrosion resistance and high insulation property, 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 V2 level, and in recent years, along with the continuous occurrence of fire accidents, the requirements on the polypropylene material are more and more strict, and on the premise of shading, the flame retardance also reaches the white shading level of V0 level or higher.
Patent application CN109438764a discloses a highly lightproof white or light colored flame retardant polypropylene composition with flame retardant rating only up to V2 grade, and with addition of a large amount of filler. For V0-level shading polypropylene materials, brominated flame retardants are the most used in the market, because titanium dioxide and fillers have no influence on the flame retardant efficiency, but because brominated flame retardants are expensive, toxic gas and dense smoke can be generated by combustion, and in many fields, the brominated flame retardants do not meet halogen-free requirements, and are limited in application.
For the halogen-free P-N type flame-retardant polypropylene material, the complete shading of 1.5mm is realized, and the titanium dioxide is added to more than 12%, but the negative effect is that the flame retardance cannot pass through V0 or even cannot reach V2 level. The influence of titanium dioxide on flame retardance mainly has two aspects: firstly, titanium dioxide has very high rigidity, and if the titanium dioxide is granulated by double screws, the titanium dioxide has very strong shearing action on the halogen-free flame retardant, and a large amount of shearing heat is generated to degrade the halogen-free flame retardant, so that the flame retardant efficiency is reduced. Secondly, the main component of the titanium dioxide is titanium dioxide, the titanium belongs to transition metal elements, and-OH and NH 4 + The group has stronger complexing capability and better catalysis in 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, thereby being mismatched with the degradation temperature of polypropylene and greatly reducing the flame retardant efficiency.
Disclosure of Invention
In order to solve the problem that the polypropylene material in the prior art cannot meet the requirements of good shading and flame retardance simultaneously, one of the purposes 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 above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a white shading halogen-free flame retardant polypropylene material, wherein the preparation raw material consists of 40-90wt% of flame retardant master batch and the balance of titanium dioxide master batch;
the preparation raw materials of the flame-retardant master batch comprise 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 white shading halogen-free flame retardant polypropylene material is prepared from 50-85 wt% of flame retardant master batch and the balance of titanium dioxide master batch; further preferably, the preparation raw materials comprise 60-85 wt% of flame-retardant master batch and the balance of titanium dioxide master batch.
Preferably, the white shading halogen-free flame retardant polypropylene material comprises 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 white shading halogen-free flame retardant polypropylene material is prepared from 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 melt index of the white shading halogen-free flame retardant polypropylene material is 5-30g/10min under the condition of 2.16kg at 230 ℃; it is further preferred that the polypropylene has a melt index of 10-30g/10min at 230℃and 2.16 kg.
Preferably, the white shading halogen-free flame retardant polypropylene material is at least one of ammonium polyphosphate flame retardant and piperazine pyrophosphate flame retardant; further preferably, at least one of the P-N intumescent flame retardants piperazine pyrophosphate based flame retardants; in some preferred embodiments of the present invention, the P-N intumescent flame retardant is at least one of EPFR-110DM, EPFR-110DL, EPFR-110DN of the Protefosine chemistry.
Preferably, the phosphorus content of the P-N intumescent flame retardant of the white shading halogen-free flame retardant polypropylene material is 18 to 22 weight percent.
Preferably, the nitrogen content of the P-N intumescent flame retardant of the white shading halogen-free flame retardant polypropylene material is 20wt% to 25wt%.
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 mu m.
Preferably, the white shading halogen-free flame retardant polypropylene material is 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 compatibilizer 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 white shading halogen-free flame retardant polypropylene material has the zinc oxide produced by an indirect method and the purity of the zinc oxide is more than 99.9 percent; further preferably, the zinc oxide is nano zinc oxide.
Preferably, the white shading halogen-free flame retardant polypropylene material is at least one of talcum powder, mica powder, montmorillonite and barium sulfate; 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 mu m.
Preferably, the white shading halogen-free flame retardant polypropylene material is prepared from polytetrafluoroethylene powder as an anti-dripping agent; further preferably, the anti-dripping agent is coated polytetrafluoroethylene powder.
Preferably, 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 white shading halogen-free flame retardant polypropylene material is at least one of hindered phenol antioxidants and phosphite antioxidants; further 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 further preferably, the antioxidants are antioxidant 1010 and antioxidant 168; still more preferably, the antioxidants are antioxidant 1010 and antioxidant 168 according to a mass ratio of 1: (1-3) compounding; in some preferred embodiments of the present invention, antioxidants are antioxidant 1010 and antioxidant 168 in a mass ratio of 1:2, compounding.
Preferably, the white shading halogen-free flame retardant polypropylene material is titanium white powder.
Preferably, the white shading halogen-free flame retardant polypropylene material is characterized in that the coupling agent 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 rate of 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 PE wax has a grafting yield of 7% of grafted maleic anhydride; the PE wax grafted maleic anhydride with high grafting rate has the effect of improving compatibility, simultaneously provides a particularly good internal and external lubrication effect, and can further reduce shearing 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 thickness of 0.75mm, light impermeability 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 flame-retardant master batches: mixing, extruding and granulating the preparation raw materials of the flame-retardant master batch to obtain the flame-retardant master batch;
2) Preparing titanium dioxide master batch: carrying out 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 in the step 1) with the titanium dioxide master batch 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 flame retardant master batches, titanium white master batches and white shading halogen-free flame retardant polypropylene materials; 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 300-400r/min; the processing temperature of the twin-screw extruder is 180-220 ℃.
Preferably, in the step 2), the temperature of the surface treatment of the titanium pigment by the coupling agent is 90-120 ℃ and the reaction time is 1.5-2.5h.
The beneficial effects of the invention are as follows:
1. the white shading halogen-free flame retardant polypropylene material can realize light-tightness with the thickness of 0.75mm, achieves the V0 level of flame retardance and has excellent mechanical property.
2. The white shading halogen-free flame retardant polypropylene material is added with zinc oxide, and the addition of the zinc oxide can play a certain shading effect while endowing the material with high flame retardant efficiency, so that the consumption of titanium dioxide can be reduced.
3. The white shading halogen-free flame retardant polypropylene material is added with a proper filler, so that the shading effect of the material can be further improved, and the consumption of titanium pigment can be reduced.
4. The white shading halogen-free flame retardant polypropylene material provided by the invention is added with a proper compatilizer, so that the alloy material can be endowed with excellent mechanical property and flame retardant property.
5. The invention adopts the coupling agent to carry out surface treatment on the titanium white powder, can improve the compatibility of the titanium white powder and the polypropylene resin, and can improve the shading effect of the titanium white powder.
6. According to the invention, the titanium dioxide is firstly prepared into the master batch, and then the master batch is mixed with the halogen-free flame-retardant master batch for injection molding, so that the problem of high shear heat caused in the process of granulating the titanium dioxide and the halogen-free flame-retardant master batch together is effectively avoided, and meanwhile, as the halogen-free flame retardant and the titanium dioxide are not granulated together by the double screw, the catalysis effect of the titanium dioxide is greatly weakened, and the flame retardant efficiency of the flame retardant can be effectively maintained.
7. The white shading halogen-free flame retardant polypropylene material is added with the renewable P-N intumescent flame retardant, and compared with a brominated 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 is presented herein for purposes of illustration only and is not intended to limit the invention. The specific process parameters and the like described below are also merely examples of suitable ranges, i.e., one skilled in the art can make a selection within the suitable ranges by the description herein and are not intended to be limited to the specific data described below. The starting materials used in the examples were all commercially available from conventional sources unless otherwise specified.
The raw materials used in the examples and comparative examples are as follows:
polypropylene: SZ30S, luxuriant petrochemical; EP548R, middle sea shell;
ammonium polyphosphate system flame retardant: EPFR-100D/EPFR-100C, probefur chemical Co., ltd;
piperazine pyrophosphate system flame retardant: EPFR-110DL/EPFR-110DM/EPFR-110DN, probefur chemical Co., ltd;
titanium white powder: r103, duPont;
titanate coupling agent: KR-38S, kennecky, U.S.;
aluminate coupling agent: DL-411, mountain-I plasticization;
silane coupling agent: KH550, daokanning;
PE wax grafted maleic anhydride: PE-4430, a new material easy to use;
talc powder: BHS-718A (1250 mesh), BHS-934071 (4000 mesh), xuefeng;
mica powder: HY-PM2 (400 meshes), HY-PM3 (2500 meshes), and sea weed powder;
anti-drip agent: SN3308, guangzhou entropy energy;
and (3) a lubricant: PE wax BN500, ponny chemical industry; calcium stearate CV500, zinc stearate AV-300, hanwei;
an antioxidant: antioxidant 1010, antioxidant 168, basf;
example 1
Preparing flame-retardant master batches: 49 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 38 parts of ammonium polyphosphate flame retardant (EPFR-100D) 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 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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 with the example 1 is that the flame retardant master batch uses piperazine pyrophosphate system flame retardant, and the addition amount is reduced by 2%.
Preparing flame-retardant master batches: 51 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) 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 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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 flame-retardant master batches: 51 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) and 5 parts of mica powder (HY-PM 3) are added from a side feed, and the halogen-free flame retardant master batch is obtained through extrusion and granulation.
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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 copolyPP (EP 548R) and the compatibilizer is SEBS-g-MAH.
Preparing flame-retardant master batches: 51 parts of PP (EP 548R), 5 parts of SEBS-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) 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 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; 38.2 parts of PP (EP 548R), 60 parts of titanium dioxide processed by a titanate coupling agent, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride are put into a double screw extruder for granulation, thus obtaining a titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 example 2 is that the titanium pigment master batch uses a silane coupling agent.
Preparing flame-retardant master batches: 51 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) 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 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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 example 2 is that the titanium pigment master batch uses an aluminate coupling agent.
Preparing flame-retardant master batches: 51 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) 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 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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 formulation of example 1, the only difference is the use of a one-step process for production.
39.2 parts of PP (SZ 30S), 7.64 parts of PP (EP 548R), 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 titanium dioxide (2 parts of titanate coupling agent (KR-38S) subjected to surface treatment are subjected to surface treatment on 100 parts of titanium dioxide (R103), the reaction temperature is 105 ℃, the reaction time is 2 hours), 0.3 part of PE wax grafted maleic anhydride, 0.24 part of anti-dripping agent (SN 3308), 0.32 part of PE wax (BN 500) and 0.3 part of antioxidant, and the mixture is fed into a double-screw extruder to be extruded and granulated 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 does not use zinc oxide.
Preparing flame-retardant master batches: 53 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) 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-110 DN) and 5 parts of mica powder (HY-PM 3) 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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 free of added filler.
Preparing flame-retardant master batches: 56 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) is 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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 free of added compatibilizing agent.
Preparing flame-retardant master batches: 56 parts of PP (SZ 30S), 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) and 5 parts of mica powder (HY-PM 3) 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; 38.2 parts of PP (EP 548R), 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 are put into a double screw extruder for granulation, so as to obtain the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 pigment has not been treated with a coupling agent.
Preparing flame-retardant master batches: 51 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) and 5 parts of mica powder (HY-PM 3) are added from a side feed, and the halogen-free flame retardant master batch is obtained through extrusion and granulation.
Preparing titanium dioxide master batch: 38.2 parts of PP (EP 548R), 60 parts of titanium dioxide, 0.3 part of antioxidant and 1.5 parts of PE wax grafted maleic anhydride are put into a double screw extruder for granulation, thus obtaining the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 flame-retardant master batches: 51 parts of PP (SZ 30S), 5 parts of PP-g-MAH, 2 parts of zinc oxide, 0.3 part of anti-dripping agent (SN 3308), 0.4 part of PE wax (BN 500) and 0.3 part of antioxidant are fed into a main feed of a double-screw extruder, 36 parts of piperazine pyrophosphate flame retardant (EPFR-110 DN) and 5 parts of mica powder (HY-PM 3) are added from a side feed, and the halogen-free flame retardant master batch is obtained through extrusion and granulation.
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; 39.7 parts of PP (EP 548R), 60 parts of titanium dioxide processed by titanate coupling agent and 0.3 part of antioxidant are put into a double screw to be extruded and granulated, thus obtaining the titanium dioxide master batch.
The preparation of the white shading halogen-free flame retardant polypropylene material comprises the following steps: the halogen-free flame retardant master batch and the titanium dioxide master batch obtained in the previous two steps are mixed 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 respectively weighed according to the raw material compositions of the examples 1-6 and the comparative examples 1-6, and are extruded and granulated, wherein the rotating speed of a screw is 400r/min, the processing temperature is 190-210 ℃, the vacuum degree is 0.08MPa, and the white shading halogen-free flame retardant polypropylene materials of the examples 1-6 and the comparative examples 1-6 are respectively obtained.
And (3) testing material performance:
the white shading halogen-free flame retardant polypropylene materials prepared in examples 1 to 6 and comparative examples 1 to 6 were subjected to the following performance tests:
density: testing according to ASTM D792 standard;
flame retardant properties: testing according to the UL-94 detection standard;
tensile strength and elongation at break: testing according to ASTM D638;
flexural strength, flexural modulus: testing according to ASTM D790;
impact strength: testing according to ASTM D256 standard;
dispersion conditions: and (3) a tabletting method, namely putting the particles on a die, and then putting the particles on a hot press for tabletting, wherein the tabletting size is as follows: the length, width and thickness are 100mm, 100mm and 0.2mm, the molding pressure is 10MPa, the molding temperature is 180 ℃, and then whether agglomeration points exist on the surface is observed;
shading condition: and (3) irradiating one surface of the square plate by adopting a light source, and observing whether light passes 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 mm by 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 results of Performance test of white shading halogen-free flame retardant Polypropylene materials of examples 1-6
Figure BDA0003627589470000101
Table 2 test results of the Performance test of white shading halogen-free flame retardant Polypropylene materials of comparative examples 1 to 6
Figure BDA0003627589470000102
Figure BDA0003627589470000111
Analysis of test results:
as can be seen from the test data of examples 1-6 and comparative examples 1-6, the halogen-free flame retardant polypropylene material prepared by the invention can realize flame retardance V0 and realize the shading effect with the thickness of 0.75mm by mutually matching the components in the formula and utilizing the mode of batch mixing of halogen-free flame retardant master batches and titanium white master batches. Meanwhile, 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 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 further improved. Specifically:
(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 V-2 grade cannot be passed through, so that the titanium pigment 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 complexation.
(2) From the test results of examples 1 to 6 and comparative example 2, it can be seen that: when zinc oxide is not used, the flame retardant grade of the material can only pass through V-1 grade, and the shading effect is reduced, because zinc oxide has a certain shading effect, and meanwhile, the flame retardant synergist is more obvious than common zinc oxide in flame retardant efficiency and shading effect when nano zinc oxide is adopted.
(3) From the test results of examples 1 to 6 and comparative example 3, it can be seen that: the light shielding effect is reduced when the mica powder is not used because the mica powder has an obvious lamellar structure and has a certain light shielding effect. The invention selects proper filler to make the prepared material pass the shading test.
(4) From the test results of examples 1 to 6 and comparative example 4, it can be seen that: when the compatilizer is not 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 compatilizer, especially PP-g-MAH and POE-g-MAH, which can endow alloy material with excellent mechanical property, improve the dispersion effect of flame retardant and further improve 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 dispersion effect of untreated titanium dioxide is reduced, and particularly in a halogen-free system with high viscosity. The invention selects proper coupling agent, which not only can improve the dispersion of titanium white powder, but also can improve the compatibility of titanium white powder and halogen-free flame retardant, so that the prepared material can achieve the shading effect of 0.75mm, and can pass through 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 PE wax is not used for grafting the maleic anhydride, the shading effect is reduced, and meanwhile, a conglomeration point exists, so that the PE wax is used for grafting the maleic anhydride, and the PE wax has good dispersing effect on the titanium pigment. The PE wax adopted by the invention is grafted with maleic anhydride, so that the agglomeration problem is solved, the prepared material can achieve the shading effect of 0.75mm, and the V0 grade can be passed through flame retardance.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.

Claims (9)

1. The white shading halogen-free flame retardant polypropylene material is characterized in that the preparation raw material consists of 40-90wt% of flame retardant master batch and the balance of titanium dioxide master batch;
the preparation raw materials of the flame-retardant master batch comprise 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 filler is at least one of talcum powder, mica powder, montmorillonite and barium sulfate;
the white shading halogen-free flame retardant polypropylene material is prepared by a preparation method comprising the following steps:
1) Preparing flame-retardant master batches: mixing, extruding and granulating the preparation raw materials of the flame-retardant master batch to obtain the flame-retardant master batch;
2) Preparing titanium dioxide master batch: carrying out 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 in the step 1) with the titanium dioxide master batch in the step 2), and performing injection molding to obtain the white shading halogen-free flame-retardant polypropylene material.
2. The white shading halogen-free flame retardant polypropylene material according to claim 1, wherein the polypropylene has a melt index of 5-30g/10min at 230 ℃ under 2.16 kg.
3. The white light-shielding halogen-free flame retardant polypropylene material according to claim 1, wherein the P-N intumescent flame retardant is at least one of an ammonium polyphosphate flame retardant and a piperazine pyrophosphate flame retardant.
4. The white light-shielding halogen-free flame retardant polypropylene material according to claim 1, wherein the compatibilizer 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 of claim 4, wherein the compatibilizing agent has a grafting ratio of 0.8% -1.8%.
6. The white light-shielding halogen-free flame retardant polypropylene material according to claim 1, wherein the filler has a particle size of 1.3 to 2.6 μm.
7. The white shading halogen-free flame retardant polypropylene material according to claim 1, wherein the coupling agent is at least one of titanate coupling agent, aluminate coupling agent and silane coupling agent.
8. The white shading halogen-free flame retardant polypropylene material according to claim 1, wherein the grafting rate of the PE wax grafted maleic anhydride is 5% -9%.
9. The method for preparing the white shading halogen-free flame retardant polypropylene material as claimed in any one of claims 1 to 8, comprising the following steps:
1) Preparing flame-retardant master batches: mixing, extruding and granulating the preparation raw materials of the flame-retardant master batch to obtain the flame-retardant master batch;
2) Preparing titanium dioxide master batch: carrying out 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 in the step 1) with the titanium dioxide master batch in the step 2), and performing injection molding to obtain the white shading halogen-free flame-retardant polypropylene material.
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