CN106700376A - High-weather-resistance high-flowability halogen-free flame-retardant HIPS/PPO alloy material and preparation method thereof - Google Patents

High-weather-resistance high-flowability halogen-free flame-retardant HIPS/PPO alloy material and preparation method thereof Download PDF

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Publication number
CN106700376A
CN106700376A CN201611212413.1A CN201611212413A CN106700376A CN 106700376 A CN106700376 A CN 106700376A CN 201611212413 A CN201611212413 A CN 201611212413A CN 106700376 A CN106700376 A CN 106700376A
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Prior art keywords
parts
free flame
hips
ppo
alloy materials
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CN201611212413.1A
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Inventor
黄骎
李荣群
姚为忠
魏子芳
邵禹通
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HEFEI ORINKO PLASTICS GROUP CO Ltd
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HEFEI ORINKO PLASTICS GROUP CO Ltd
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Publication of CN106700376A publication Critical patent/CN106700376A/en
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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
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • 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
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The invention discloses a high-weather-resistance high-flowability halogen-free flame-retardant HIPS/PPO alloy material and a preparation method thereof, and belongs to the technical field of macromolecular materials. The alloy material consists of the following components in parts by weight: 40 to 50 parts of HIPS resin, 25 to 40 parts of PPO resin, 2 to 5 parts of a toughening agent, 15 to 20 parts of a flame retardant, 0.3 to 0.5 part of an antioxidant, 1 to 2 parts of a lubricating agent and 1 to 2 parts of a compound weather-resistant agent. The preparation method provided by the invention is simple and reasonable in formula; the prepared high-weather-resistance high-flowability halogen-free flame-retardant HIPS/PPO alloy material has the advantages of high impact and flame retardance, excellent flowability, hydrolysis resistance, excellent weather resistance, heat resistance and the like. The alloy material has great advantages when being used for forming large workpieces and thin-walled appearance products with heat-resistant and hydrolysis-resistant requirements, and has wide application prospect.

Description

A kind of high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials and its preparation Method
Technical field
The invention belongs to technical field of polymer materials, specifically a kind of high durable high fluidity halogen-free flame-retarding HIPS/PPO Alloy material and preparation method thereof.
Background technology
Polyphenylene oxide (PPO) is after polycarbonate, polyformaldehyde POM, polyamide PA, thermoplastic polyester PBT, after PET Five large-engineering plastics, have the advantages that big rigidity, heat resistance high, fire retardant, wear-resisting, anti-pollution, intensity are excellent compared with high electrical performance.City The PPO overwhelming majority is used by modified on field, it can be common that with HIPS, PA is modified, in the majority with HIPS, after being modified Polyphenylene oxide, is referred to as MPPO, is the minimum kind of relative density in general engineering plastic, with linear expansion coefficient is small, good electrical property, Many advantages, such as heat-resisting, fire retardant and hydrolysis, it is widely used in office equipment, electronics, electrical equipment, auto parts and components, discharge water dispenser Tool parts etc..
The melt fluidity of conventional fire-retardant MPPO is poor, difficult forming, it is impossible to prepare large-scale product, due to HIPS and PPO weather resistances in itself are poor, its application is very limited；Concern with people to environmental protection simultaneously, in the world to nothing The requirement of halogen fire proofing, reduce or do not use halogen containing flame-retardant will necessarily turn into industry trend.Ensureing that MPPO is excellent in itself On the basis of different mechanical performance, while improving the mobility and weather resistance of material, high durable is developed using halogen-free flame retardants High fluidity halogen-free flame-retarding HIPS/PPO alloy materials, has broad application prospects, and can be widely applied to appearance requirement high Big product and thin-walled property product.
The content of the invention
It is an object of the invention to provide a kind of high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials and its system Preparation Method.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials, it is by weight, composed of the following components：
Further scheme, the melt flow rate (MFR) of the HIPS resins is 10-15g/10min.
Further scheme, the melt flow rate (MFR) that the PPO resins are is 9-14g/10min.
Further scheme, the toughener is one or two the mixture in SBS, SEBS.
Further scheme, the fire retardant is bisphenol-A double (diphenyl phosphoester), 1,3- phenylenes phosphoric acid four (2,6- bis- Aminomethyl phenyl) ester, the mixture of one or more in triphenyl phosphate.
Further scheme, the antioxidant is in Hinered phenols antioxidant, phosphorous acid lipid and suffocated amine antioxidant The mixture of one or more.
Further scheme, the lubricant is pentaerythritol stearate, N, and N- has supportted bis-stearamides, amide-type, silicon The mixture of one or more in ketone.
Further scheme, the compounding weather resisting agent is hindered amines and benzotriazole by weight 7:The mixing of 3 compoundings Thing.
It is another object of the present invention to provide a kind of high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials Preparation method, comprise the following steps：
(1) fire retardant, toughener, lubricant, antioxidant, weather resisting agent are weighed by proportioning, is added to together in high mixer and mixes Close uniform；
(2) by HIPS resins, PPO resins and step (1) mixed powder, twin-screw extrusion is accurately added to by weighing balance In machine, at 240-250 DEG C, screw slenderness ratio is 25-40 for extruder temperature control, and screw speed is controlled in 400r/min, material After being melted in screw rod, high durable high fluidity halogen-free flame-retarding HIPS/PPO alloys are obtained by extrusion, cooling, air-dried, pelletizing Material.
Beneficial effects of the present invention：
1st, the present invention is resistance to by adding halogen-free flame retardants, toughener and compounding during HIPS/PPO alloy materials are prepared Agent is waited, obtained alloy material has mechanical strength higher compared with HIPS resins, and heat resistance compared with PPO resins, has More preferable mobility, it is easier to be molded, and flame-retardant V 0-stage can be arrived not, with excellent weather resistance, anti-hydrolytic performance extensively should Used in the big product of shaping and thin-walled property product；
2nd, high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials prepared by the present invention, according to the detection of the industry Standard, notch impact strength is more than 8KJ/m2, bending modulus be more than 2000MPa, show good toughness, melt flow rate (MFR) More than 5g/10min, while flame-retardant V 0-stage is not, with good mobility, weatherability and fire resistance；
3rd, high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials of the present invention are using HIPS resins and PPO resins It is matrix, addition toughener, fire retardant, antioxidant, lubricant and compounding weather resisting agent, its raw material are easy to get and can be directly used for work Industry metaplasia is produced.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
PPO resins of the present invention are bought from blue star chemical industry.
Embodiment 1
High durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials in the present embodiment be by following raw materials according by weight Part composition：
Specific preparation method is comprised the following steps：
(1) 15 parts of combustion inhibitor bisphenol A bis double (diphenyl phosphoester), 2 parts of toughener SBS, 1 part of lubricant pentaerythrite are weighed Stearate, 0.3 part of antioxidant 1010,0.7 part of light stabilizer, 944,0.3 part of ultraviolet absorber UV-P, are added to high mixed together It is well mixed in machine；
(2) by 40 parts of HIPS resins, 40 parts of PPO resins and step (1) mixed powder, accurately it is added to by weighing balance double In screw extruder, at 240-250 DEG C, screw slenderness ratio is 25-40 for extruder temperature control, and screw speed is controlled in 400r/ Min, after material is melted in the screw rod, by extrusion, cooling, air-dry, pelletizing obtain high durable high fluidity halogen-free flame-retarding HIPS/ PPO alloy materials.
Embodiment 2
High durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials in the present embodiment be by following raw materials according by weight Part composition：
Specific preparation method is comprised the following steps：
(1) weigh 16 parts of fire retardants 1,3- phenylenes phosphoric acid four (2,6- 3,5-dimethylphenyl) ester, 3 parts of toughener SEBS, 1 part Lubricant N, N- have supportted bis-stearamides, 0.1 part of irgasfos 168,0.2 part of antioxidant 1010,0.7 part of light stabilizer 944,0.3 Part ultraviolet absorber UV-P, is added to high-speed mixer and mixing uniform together；
(2) by 45 parts of HIPS resins, 35 parts of PPO resins and step (1) mixed powder, accurately it is added to by weighing balance double In screw extruder, at 240-250 DEG C, screw slenderness ratio is 25-40 for extruder temperature control, and screw speed is controlled in 400r/ Min, after material is melted in the screw rod, by extrusion, cooling, air-dry, pelletizing obtain high durable high fluidity halogen-free flame-retarding HIPS/ PPO alloy materials.
Embodiment 3
High durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials in the present embodiment be by following raw materials according by weight Part composition：
Specific preparation method is comprised the following steps：
(1) 18 portions of fire retardant triphenyl phosphates, 2 parts of toughener SEBS, 2 parts of toughener SBS, 1.5 parts of lubricant silicon are weighed Ketone, 0.1 part of irgasfos 168,0.2 part of antioxidant 1010,0.7 part of light stabilizer, 944,0.3 part of ultraviolet absorber UV-P, add together Enter uniform to high-speed mixer and mixing；
(2) by 47 parts of HIPS resins, 30 parts of PPO resins and step (1) mixed powder, accurately it is added to by weighing balance double In screw extruder, at 240-250 DEG C, screw slenderness ratio is 25-40 for extruder temperature control, and screw speed is controlled in 400r/ Min, after material is melted in the screw rod, by extrusion, cooling, air-dry, pelletizing obtain high durable high fluidity halogen-free flame-retarding HIPS/ PPO alloy materials.
Embodiment 4
High durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials in the present embodiment be by following raw materials according by weight Part composition：
Specific preparation method is comprised the following steps：
(1) 18 portions of fire retardant triphenyl phosphates, 3.5 parts of toughener SEBS, 1 part of lubricant pentaerythrite stearic acid are weighed Ester, 0.5 part of lubricant N, N- have supportted bis-stearamides, 0.2 part of irgasfos 168,0.2 part of antioxidant 1010,1.4 parts of light stabilizers 944th, 0.6 part of ultraviolet absorber UV-P, is added to high-speed mixer and mixing uniform together；
(2) by 46 parts of HIPS resins, 30 parts of PPO resins and step (1) mixed powder, accurately it is added to by weighing balance double In screw extruder, at 240-250 DEG C, screw slenderness ratio is 25-40 for extruder temperature control, and screw speed is controlled in 400r/ Min, after material is melted in the screw rod, by extrusion, cooling, air-dry, pelletizing obtain high durable high fluidity halogen-free flame-retarding HIPS/ PPO alloy materials.
Embodiment 5
High durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials in the present embodiment be by following raw materials according by weight Part composition：
Specific preparation method is comprised the following steps：
(1) 10 parts of combustion inhibitor bisphenol A bis double (diphenyl phosphoester), 10 parts of fire retardants 1 are weighed, 3- phenylenes phosphoric acid four (2, 6- 3,5-dimethylphenyls) ester, 5 parts of toughener SBS, 1 part of lubricant pentaerythritol stearate, 1 part of lubricant silicone, 0.3 part resist 1010,0.2 part of irgasfos 168 of oxygen agent, 1.4 parts of light stabilizers, 944,0.6 part of ultraviolet absorber UV-P, are added to high mixer together In be well mixed；
(2) by 50 parts of HIPS resins, 25 parts of PPO resins and step (1) mixed powder, accurately it is added to by weighing balance double In screw extruder, at 240-250 DEG C, screw slenderness ratio is 25-40 for extruder temperature control, and screw speed is controlled in 400r/ Min, after material is melted in the screw rod, by extrusion, cooling, air-dry, pelletizing obtain high durable high fluidity halogen-free flame-retarding HIPS/ PPO alloy materials.
HIPS/PPO alloy materials prepared by each embodiment are first molded into standard batten by GB standards, then by test Standard is tested, and main performance test data is shown in Table 2.
The high durable high fluidity halogen-free flame-retarding HIPS of table 2/PPO alloy material performance indications
From table 2 it can be seen that HIPS/PPO alloy materials of the invention have good impact and fire resistance, good stream Dynamic property and weather resistance.
The above-mentioned description to embodiment is to be understood that and apply this hair for ease of those skilled in the art It is bright.Person skilled in the art obviously can easily make various modifications to case study on implementation, and described herein one As principle be applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation case here Example, those skilled in the art's announcement of the invention, not departing from improvement that scope made and modification all should be Within protection scope of the present invention.

Claims (9)

1. a kind of high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials, it is characterised in that by weight, by following Component is constituted：
40-50 parts of HIPS resins
25-40 parts of PPO resins
Toughener 2-5 parts
Fire retardant 15-20 parts
Antioxidant 0.3-0.5 parts
Lubricant 1-2 parts
1-2 parts of weather resisting agent of compounding.
2. high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials according to claim 1, it is characterised in that institute The melt flow rate (MFR) for stating HIPS resins is 10-15g/10min.
3. high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials according to claim 1, it is characterised in that institute It is 9-14g/10min to state the melt flow rate (MFR) that PPO resins are.
4. high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials according to claim 1, it is characterised in that institute It is one or two the mixture in SBS, SEBS to state toughener.
5. high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials according to claim 1, it is characterised in that institute It is bisphenol-A double (diphenyl phosphoester), 1,3- phenylenes phosphoric acid four to state fire retardant（2,6- 3,5-dimethylphenyls）Ester, triphenyl phosphate In the mixture of one or more.
6. high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials according to claim 1, it is characterised in that institute It is the mixture of one or more in Hinered phenols antioxidant, phosphorous acid lipid and suffocated amine antioxidant to state antioxidant.
7. high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials according to claim 1, it is characterised in that institute Lubricant is stated for pentaerythritol stearate, N, N- has supportted the mixed of one or more in bis-stearamides, amide-type, silicone Compound.
8. high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials according to claim 1, it is characterised in that institute It is hindered amines and benzotriazole by weight 7 to state compounding weather resisting agent:The mixture of 3 compoundings.
9. the preparation side of the high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials as described in claim any one of 1-8 Method, it is characterised in that comprise the following steps：
（1）Fire retardant, toughener, lubricant, antioxidant, weather resisting agent are weighed by proportioning, high-speed mixer and mixing is added to together equal It is even；
（2）By HIPS resins, PPO resins and step（1）Mixed powder, double screw extruder is accurately added to by weighing balance In, at 240-250 DEG C, screw slenderness ratio is 25-40 for extruder temperature control, and screw speed is controlled in 400r/min, and material exists After being melted in screw rod, high durable high fluidity halogen-free flame-retarding HIPS/PPO alloy materials are obtained by extrusion, cooling, air-dried, pelletizing Material.
CN201611212413.1A 2016-12-25 2016-12-25 High-weather-resistance high-flowability halogen-free flame-retardant HIPS/PPO alloy material and preparation method thereof Pending CN106700376A (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN109370137A (en) * 2018-07-27 2019-02-22 会通新材料股份有限公司 A kind of high intensity high TV Mobile rear shell flame-retarding HIPS/PPO alloy material and preparation method thereof
CN111087738A (en) * 2019-12-27 2020-05-01 会通新材料股份有限公司 MPPO material for carbon fiber reinforced flame-retardant television rear shell and preparation method thereof
JP7280133B2 (en) 2019-07-17 2023-05-23 旭化成株式会社 Polyphenylene ether resin composition

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109370137A (en) * 2018-07-27 2019-02-22 会通新材料股份有限公司 A kind of high intensity high TV Mobile rear shell flame-retarding HIPS/PPO alloy material and preparation method thereof
JP7280133B2 (en) 2019-07-17 2023-05-23 旭化成株式会社 Polyphenylene ether resin composition
CN111087738A (en) * 2019-12-27 2020-05-01 会通新材料股份有限公司 MPPO material for carbon fiber reinforced flame-retardant television rear shell and preparation method thereof

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Application publication date: 20170524