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CN103374225A - Halogen-free flame-retardant heat-resistant HIPS (high impact polystyrene)/PPS (polyphenylene sulfide) composite material and preparation method thereof - Google Patents

Halogen-free flame-retardant heat-resistant HIPS (high impact polystyrene)/PPS (polyphenylene sulfide) composite material and preparation method thereof Download PDF

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Publication number
CN103374225A
CN103374225A CN2012101301736A CN201210130173A CN103374225A CN 103374225 A CN103374225 A CN 103374225A CN 2012101301736 A CN2012101301736 A CN 2012101301736A CN 201210130173 A CN201210130173 A CN 201210130173A CN 103374225 A CN103374225 A CN 103374225A
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Prior art keywords
halogen
hips
heat
resisting
pps
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Inventor
骆意
胡付余
田晋丽
李靓
王传新
臧玉波
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Priority to CN2012101301736A priority Critical patent/CN103374225A/en
Publication of CN103374225A publication Critical patent/CN103374225A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92561Time, e.g. start, termination, duration or interruption
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885Screw or gear
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a halogen-free flame-retardant heat-resistant HIPS (high impact polystyrene)/PPS (polyphenylene sulfide) composite material and a preparation method thereof. The composite material comprises the following components by weight percent: 65-75% of polyphenylene sulfide resin, 10-20% of high impact-resistant polystyrene resin, 7-12% of a toughening agent, 1.5-5% of a halogen-free flame retardant, 0.5-1.5% of a flame-retardant synergist and 2.5-5% of other additives. The preparation method comprises the following steps: firstly, uniformly mixing the raw materials according to the proportion, then adding the raw materials into a double-screw extruder, controlling the temperature to be 250-290 DEG C, and prilling. The composite material with excellent integrated performance is prepared by adopting a composite flame-retardant system and a toughening master batch, the composite material has prominent high temperature resistance performance, high flame retardant performance, high environment protection performance and high impact resistance performance, and the preparation method has the advantages that the technology is simple, the operation is convenient and the cost is low.

Description

Heat-resisting HIPS/PPS matrix material of a kind of halogen-free flameproof and preparation method thereof
Technical field
The present invention relates to the Modification of High-impact Polystyrene technical field, be specifically related to heat-resisting HIPS/PPS matrix material of a kind of halogen-free flameproof and preparation method thereof.
Background technology
Polystyrene (PS) is one of five large general-purpose plastics, and it has, and formability is good, matter is hard, transparent, electrical insulating property, agent of low hygroscopicity and the advantage such as cheap.Generate high-impact polystyrene resin (HIPS) mixes a small amount of elastomerics in PS after, it has overcome the crisp shortcoming of polystyrene, thereby is widely used in the industries such as electronics, automobile, household electrical appliances, instrument, daily necessities, toy.But HIPS burns easily, and weathering resistance is poor, and easily initiation fire two causes unnecessary financial loss, even loss of life and personal injury.Therefore, all the requirements such as fire-retardant, weather-proof have been proposed high-impact polystyrene resin in many Application Areass.
When guaranteeing fire safety, along with the International Environmental Protection legislation is increasingly strict, people more and more pay close attention to some fire retardants to the harmful effect of environment and human body generation.The RoHS of the European Union environmental protection instruction of putting into effect in 2003 is listed polybromodiphenyl ether in electronic and electrical equipment and is limited the use of the objectionable impurities list, from 1 day July in 2006, forbids using Polybrominated biphenyl (PBB) and Poly Brominated Diphenyl Ethers (PBDE) in electronic electric equipment.The numerous famous enterprise of the U.S., Europe, Japan---Microsoft, DELL, Philip, THOMSON, Sony, Panasonics etc. are all take European environmental protection instruction as limiting the relevant criterion that related substance uses according to having formulated.
There have been the achievement in research of halogen-free flameproof polystyrene correlation technique in more international major companies such as Korea S Samsung, LG-DOW company, but non-environmental-protection flame-retardant PS is high more than 50% for its cost ratio tradition, and there is no at home the ripe the techniques of mass production of grasping this product of producer at present.
Summary of the invention
The object of the invention is to overcome the defective that prior art exists, propose heat-resisting HIPS/PPS matrix material of a kind of halogen-free flameproof and preparation method thereof, to satisfy the needs of electrical equipment industry development.
Technical scheme of the present invention is:
The heat-resisting HIPS/PPS matrix material of a kind of halogen-free flameproof, the weight percentage of its component and each component is:
Figure BDA0000158236050000021
Described polyphenylene sulfide, its crosslinking temperature are 150~350 ℃;
Described high-impact polystyrene, its relative density are 1.04-1.06, and fusing point is 150~180 ℃, and heat decomposition temperature is more than 300 ℃;
Described toughner is one or more the mixture in maleic anhydride stem grafting polyolefin elastomerics, maleic anhydride graft terpolymer EP rubber or the maleic anhydride grafted polyethylene;
Described halogen-free flame retardants is 15-55% by trimeric cyanamide, polyphosphoric acid amine, tetramethylolmethane by weight, 15-55%, and 5-30% is composite;
Described retardant synergist is one or several the mixture in antimonous oxide, borate, molybdenum oxide, the phosphorous acid esters;
Described other auxiliary agent comprises the processing aids such as lubricant, oxidation inhibitor.
The heat-resisting HIPS/PPS composite manufacture of above-mentioned halogen-free flameproof method may further comprise the steps:
(1) with polyphenylene sulfide, high-impact polystyrene resin 70~90 ℃ of drying 4~8h in loft drier respectively;
(2) take by weighing dry good polyphenylene sulfide, high-impact polystyrene resin, toughner, halogen-free flame retardants, retardant synergist and other auxiliary agent by the weight proportion of setting;
(3) raw material in the step (2) is put into be dry mixed 4~5min in the super mixer;
(4) mixed raw material in the step (3) is put into forcing machine, through melting, granulation.
Complete processing is as follows in the step (4): twin screw extruder one district temperature 80-100 ℃, and two district temperature 150-170 ℃, three district temperature 210-230 ℃, four district temperature 210-230 ℃, five district temperature 210-230 ℃, six district temperature 210-230 ℃, seven district temperature 200-220 ℃, eight district temperature 200-220 ℃, nine district temperature 200-220 ℃, ten district temperature 210-230 ℃, head temperature 200-220 ℃, residence time 2-3min, pressure are 10-20Mpa.
Owing to taked technique scheme, matrix material of the present invention has been obtained following beneficial effect: 1) the present invention adopts the organonitrogen series composite flame retardant, cooperates inorganic fire-retarded synergistic agent to obtain excellent flame retardant effect, and flame retardant properties reaches the V-0 level; 2) prepared matrix material has resistance to elevated temperatures, and heat-drawn wire is higher than 170 ℃; 3) good fluidity, melting index reaches 48g/10min; 4) excellent insulation performance.Simultaneously, preparation method proposed by the invention has the advantage that technique is simple, easy to operate, cost is low.
Embodiment
In following examples, polyphenylene sulfide is the 1140A6 of Polyplastics; High-impact polystyrene is the HG-1760S of Korea S Cheil Industries Inc.; The maleic anhydride stem grafting polyolefin elastomerics is the AG-P300 that Nanjing friendly auxiliary agent chemical industry limited liability company sells; Trimeric cyanamide is that Sichuan fine chemistry industry research institute produces; Polyphosphoric acid amine and tetramethylolmethane are that the Jinan gold is full of safe chemical industry company limited; Antimonous oxide is that Shanghai Wuization chemical industry company limited produces; The lubricant trade mark is P-130, and Indonesia CMS produces; Oxidation inhibitor is selected four [β-(3,5-di-tert-butyl-4-hydroxy phenyl) propionic acid] pentaerythritol ester, and the trade mark is Irganox1010, Ciba fine chemicals production.
Embodiment 1
Prescription:
Halogen-free flame retardants is by trimeric cyanamide 25%, and polyphosphoric acid amine 50% and tetramethylolmethane 25% are composite.
Polyphenylene sulfide 68 weight parts, high-impact polystyrene 15 weight parts, maleic anhydride stem grafting polyolefin elasticity 7.7 weight parts, halogen-free flame retardants 5 weight parts, antimonous oxide 1.3 weight parts, lubricant 1 weight part, oxidation inhibitor 2 weight parts.
The preparation method:
(1) at first with polyphenylene sulfide, polystyrene 70~90 ℃ of drying 4~8h in loft drier;
(2) take by weighing raw material by above-mentioned weight proportion;
(3) raw material in the step (2) is put into be dry mixed 4~5min in the super mixer;
(4) mixed raw material in the step (3) is put into forcing machine, through melting, granulation; Complete processing is as follows: twin screw extruder one district temperature 80-100 ℃, and two district temperature 150-170 ℃, three district temperature 210-230 ℃, four district temperature 210-230 ℃, five district temperature 210-230 ℃, six district temperature 210-230 ℃, seven district temperature 200-220 ℃, eight district temperature 200-220 ℃, nine district temperature 200-220 ℃, ten district temperature 210-230 ℃, head temperature 200-220 ℃, residence time 2-3min, pressure are 10-20Mpa.
Embodiment 2
Prescription:
Halogen-free flame retardants is by trimeric cyanamide 55%, and polyphosphoric acid amine 40% and tetramethylolmethane 5% are composite.
Polyphenylene sulfide (PPS) 70 weight parts, high-impact polystyrene (HIPS) 15 weight parts, maleic anhydride stem grafting polyolefin elastomerics 7.7 weight parts, halogen-free flame retardants 3 weight parts, antimonous oxide 1.3 weight parts, lubricant 1 weight part, oxidation inhibitor 2 weight parts.
Preparation does not repeat them here with embodiment 1.
Embodiment 3
Prescription:
Halogen-free flame retardants is by trimeric cyanamide 45%, and polyphosphoric acid amine 45% and tetramethylolmethane 10% are composite.
Polyphenylene sulfide (PPS) 70.5 weight parts, high-impact polystyrene (HIPS) 15 weight parts, maleic anhydride stem grafting polyolefin elastomerics 7.7 weight parts, halogen-free flame retardants 2.5 weight parts, antimonous oxide 1.3 weight parts, lubricant 1 weight part, oxidation inhibitor 2 weight parts.
Preparation does not repeat them here with embodiment 1.
Embodiment 4
Prescription:
Halogen-free flame retardants is by trimeric cyanamide 25%, and polyphosphoric acid amine 45% and tetramethylolmethane 30% are composite.
Polyphenylene sulfide (PPS) 71 weight parts, high-impact polystyrene (HIPS) 15 weight parts, maleic anhydride stem grafting polyolefin elastomerics 7.7 weight parts, halogen-free flame retardants 2 weight parts, antimonous oxide 1.3 weight parts, lubricant 1 weight part, oxidation inhibitor 2 weight parts.
Preparation does not repeat them here with embodiment 1.
Embodiment 5
Prescription:
Halogen-free flame retardants is by trimeric cyanamide 55%, and polyphosphoric acid amine 20% and tetramethylolmethane 25% are composite.
Polyphenylene sulfide (PPS) 71.5 weight parts, high-impact polystyrene (HIPS) 15 weight parts, maleic anhydride stem grafting polyolefin elastomerics 7.7 weight parts, halogen-free flame retardants 1.5 weight parts, antimonous oxide 1.3 weight parts, lubricant 1 weight part, oxidation inhibitor 2 weight parts.
Preparation does not repeat them here with embodiment 1.
Embodiment 1-5 material property sees Table 1.
Table 1
Performance index Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Tensile strength 69 66 68 65 68
Elongation at break (%) 14 12 17 16 13
Modulus in flexure (Mpa) 2490 2530 2575 2520 2580
Notched Izod impact strength (KJ/m 2) 18 20 19 21 20
Heat-drawn wire (1.82Mpa, ℃) 140 175 186 185 180
Melting index (g/10min) 32 42 48 55 50
Flame retardant resistance (3.2mm) V-0 V-0 V-0 V-0 V-0
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment.So everyly do not break away from the equivalence of finishing under the spirit disclosed in this invention or revise, all fall into the scope of protection of the invention.

Claims (9)

1. heat-resisting HIPS/PPS matrix material of halogen-free flameproof is characterized in that the weight percentage of its component and each component is:
Figure FDA0000158236040000011
2. the heat-resisting HIPS/PPS matrix material of halogen-free flameproof according to claim 1, it is characterized in that: the crosslinking temperature of described polyphenylene sulfide is 150~350 ℃.
3. the heat-resisting HIPS/PPS matrix material of halogen-free flameproof according to claim 1, it is characterized in that: its relative density of described high-impact polystyrene resin is 1.04-1.06, and fusing point is 150~180 ℃, and heat decomposition temperature is more than 300 ℃.
4. according to the heat-resisting HIPS/PPS matrix material of claims 1 described halogen-free flameproof, it is characterized in that: described toughner is one or more the mixture in maleic anhydride stem grafting polyolefin elastomerics, maleic anhydride graft terpolymer EP rubber or the maleic anhydride grafted polyethylene.
5. according to the heat-resisting HIPS/PPS matrix material of claims 1 described halogen-free flameproof, it is characterized in that: described halogen-free flame retardants is 15-55% by weight by trimeric cyanamide, polyphosphoric acid amine, tetramethylolmethane, 15-55%, and 5-30% is composite.
6. according to the heat-resisting HIPS/PPS matrix material of claims 1 described halogen-free flameproof, it is characterized in that: described retardant synergist is the one or more kinds of mixtures in antimonous oxide, borate, molybdenum oxide, the phosphorous acid esters.
7. according to the heat-resisting HIPS/PPS matrix material of claims 1 described halogen-free flameproof, it is characterized in that: described other auxiliary agent comprises lubricant, oxidation inhibitor.
8. the heat-resisting HIPS/PPS composite manufacture of halogen-free flameproof method as claimed in claim 1 is characterized in that, may further comprise the steps:
(1) with polyphenylene sulfide, high-impact polystyrene resin 70~90 ℃ of drying 4~8h in loft drier respectively;
(2) take by weighing dry good polyphenylene sulfide, high-impact polystyrene resin, toughner, halogen-free flame retardants, retardant synergist and other auxiliary agent by the weight proportion of setting;
(3) raw material in the step (2) is put into be dry mixed 4~5min in the super mixer;
(4) mixed raw material in the step (3) is put into forcing machine, through melting, granulation.
9. the heat-resisting HIPS/PPS composite manufacture of halogen-free flameproof method as claimed in claim 8, it is characterized in that, complete processing is as follows in the step (4): twin screw extruder one district temperature 80-100 ℃, two district temperature 150-170 ℃, three district temperature 210-230 ℃, four district temperature 210-230 ℃, five district temperature 210-230 ℃, six district temperature 210-230 ℃, seven district temperature 200-220 ℃, eight district temperature 200-220 ℃, nine district temperature 200-220 ℃, ten district temperature 210-230 ℃, head temperature 200-220 ℃, residence time 2-3min, pressure are 10-20Mpa.
CN2012101301736A 2012-04-27 2012-04-27 Halogen-free flame-retardant heat-resistant HIPS (high impact polystyrene)/PPS (polyphenylene sulfide) composite material and preparation method thereof Pending CN103374225A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103665868A (en) * 2013-12-07 2014-03-26 天津市华鑫达投资有限公司 Halogen-free flame retardant thermally conductive and insulating resin composition and preparation method thereof
CN103756320A (en) * 2013-11-28 2014-04-30 芜湖跃飞新型吸音材料股份有限公司 Flexible flame-resistant modified polyphenylene sulfide material for automobile plastic parts
CN103923427A (en) * 2014-04-30 2014-07-16 上海瀚氏模具成型有限公司 Halogen-free flame retardant and heat resistant HIPS (high impact polystyrene) plastic for automotive interior trim parts and preparation method thereof
CN104479323A (en) * 2014-12-08 2015-04-01 苏州新区佳合塑胶有限公司 Flame-retardant plastic for electronic product casing
CN104987719A (en) * 2015-06-30 2015-10-21 苏州博利迈新材料科技有限公司 Method for preparing PPS plastic particles for automotive trim
CN114907696A (en) * 2022-07-01 2022-08-16 四川中物材料股份有限公司 High CTI polyphenylene sulfide composite material and preparation method thereof
CN116575133A (en) * 2023-07-14 2023-08-11 江苏恒力化纤股份有限公司 Preparation method of flame-retardant polyester fiber based on melt reaction extrusion

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103756320A (en) * 2013-11-28 2014-04-30 芜湖跃飞新型吸音材料股份有限公司 Flexible flame-resistant modified polyphenylene sulfide material for automobile plastic parts
CN103665868A (en) * 2013-12-07 2014-03-26 天津市华鑫达投资有限公司 Halogen-free flame retardant thermally conductive and insulating resin composition and preparation method thereof
CN103923427A (en) * 2014-04-30 2014-07-16 上海瀚氏模具成型有限公司 Halogen-free flame retardant and heat resistant HIPS (high impact polystyrene) plastic for automotive interior trim parts and preparation method thereof
CN103923427B (en) * 2014-04-30 2016-02-10 上海瀚氏模具成型有限公司 Heat-resisting HIPS plastic of automotive upholstery halogen-free flameproof and preparation method thereof
CN104479323A (en) * 2014-12-08 2015-04-01 苏州新区佳合塑胶有限公司 Flame-retardant plastic for electronic product casing
CN104479323B (en) * 2014-12-08 2016-01-20 苏州新区佳合塑胶有限公司 A kind of electronic product casing flame retardant plastics
CN104987719A (en) * 2015-06-30 2015-10-21 苏州博利迈新材料科技有限公司 Method for preparing PPS plastic particles for automotive trim
CN114907696A (en) * 2022-07-01 2022-08-16 四川中物材料股份有限公司 High CTI polyphenylene sulfide composite material and preparation method thereof
CN114907696B (en) * 2022-07-01 2024-03-22 四川中物材料股份有限公司 High CTI polyphenylene sulfide composite material and preparation method thereof
CN116575133A (en) * 2023-07-14 2023-08-11 江苏恒力化纤股份有限公司 Preparation method of flame-retardant polyester fiber based on melt reaction extrusion
CN116575133B (en) * 2023-07-14 2023-09-22 江苏恒力化纤股份有限公司 Preparation method of flame-retardant polyester fiber based on melt reaction extrusion

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Application publication date: 20131030