CN109181196A - A kind of HIPS composite and preparation method thereof of high glaze composite flame-proof - Google Patents
A kind of HIPS composite and preparation method thereof of high glaze composite flame-proof Download PDFInfo
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- CN109181196A CN109181196A CN201810852665.3A CN201810852665A CN109181196A CN 109181196 A CN109181196 A CN 109181196A CN 201810852665 A CN201810852665 A CN 201810852665A CN 109181196 A CN109181196 A CN 109181196A
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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
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
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- Compositions Of Macromolecular Compounds (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
Abstract
The invention discloses a kind of HIPS composites and preparation method thereof of high glaze composite flame-proof, the composition of composite material are as follows: HIPS100 parts by weight, 20~40 parts by weight of Flame-retardant PET, 2~8 parts by weight of compatilizer, 5~10 parts by weight of main flame retardant, 0.1~1 parts by weight of auxiliary flame retardant 1-3,0.1~1 parts by weight of antioxidant and lubricant；Glazed flame-retardant HIPS composite of the invention, not only increase the lustrous surface of HIPS composite, and there is excellent anti-flammability, chemical-resistance and high mechanical strength, dimensional stability is good, has widened the application range of HIPS significantly, is widely used in the occasion relatively high for glossiness and flame-retardancy requirements, it has broad application prospects, novel glazed flame-retardant HIPS composite preparation method of the invention, compound process and process are simple, preparation easy to process.
Description
Technical field
The present invention relates to technical field of polymer composite materials, the HIPS composite wood of specifically a kind of high glaze composite flame-proof
Material and preparation method thereof.
Background technique
Polystyrene homopolymer is usually the quite crisp resin with bad impact strength.By being introduced on strand
Rubber components unit obtains the good HIPS resin of toughness.But this also causes the lustrous surface of resin to substantially reduce, limitation
It is having a certain surface gloss requirement occasion such as phone, is widely applied in computer and other electric consumers；And by
It does not require nothing more than relatively good gloss in many electric appliances, and it is also desirable to have anti-flammability, prevent electric appliance from catching fire and generating fire.
The method of the practical continuous bulk polymerization of patent CN1256699A has prepared the modification HIPS with certain gloss, but
Preparation process and the device is complicated, technical requirements are high, and industrialized production difficulty is larger；Patent CN106939112A is using HIPS and returns
PET bottle piece is received, the HIPS composite of high glaze can be prepared, but material does not have anti-flammability.
Using traditional brominated triazine, the anti-flammability of HIPS composite may be implemented, but since its dosage is in 15-20%,
Dosage is big, influences the gloss of material.
Summary of the invention
It is an object of the invention to overcome the deficiencies of existing technologies, the HIPS for providing a kind of high glaze composite flame-proof is compound
Material and preparation method thereof.
To achieve the above object, the invention provides the following technical scheme:
A kind of HIPS composite of high glaze composite flame-proof, the composite material includes following component:
100 parts by weight of hips；
20~40 parts by weight of Flame-retardant PET；
2~8 parts by weight of compatilizer；
5~10 parts by weight of main flame retardant；
1~3 parts by weight of auxiliary flame retardant；
0.1~1 parts by weight of antioxidant；
0.1~1 parts by weight of lubricant；
It is preferred that are as follows:
100 parts by weight of hips；
25~35 parts by weight of Flame-retardant PET；
2~5 parts by weight of compatilizer；
5~8 parts by weight of main flame retardant；
1~2 parts by weight of auxiliary flame retardant；
0.1~0.5 parts by weight of antioxidant；
0.5~1 parts by weight of lubricant.
Preferably, the HIPS relative density is 1.05, and average molecular weight is 6~150,000；The Izod of the HIPS
Notch impact strength is 8.5-9.5 KJ/m2, preferably 9.0-9.5 KJ/m2.
Preferably, the Flame-retardant PET is that the 2- hydroxy phenyl phosphinic acids containing 5%-10% are copolymerized PET, contains 1%- simultaneously
3% antimony glycol (is added in polymerization process, is uniformly dispersed, do not influence the transparency), and appearance color is the slice of white clear,
Intrinsic viscosity is 0.68~0.78dl/g, preferably 0.70~0.75dl/g.
Preferably, the compatilizer is styrene-Bing Xi Celadon-glycidyl methacrylate, and melt index is
The content of 6-9g/10min (200 DEG C/5Kg), GMA are 1.8%-2.2%, and the fire retardant is that brominated triazine is saturating, wherein fusing point
220-230 DEG C, bromine content content is 65-70%, preferably 67-68%.
Preferably, the primary antioxidant is specially antioxidant 1010 or 1076, preferably antioxidant 1010；Auxiliary antioxidant
For irgasfos 168；Major-minor antioxidant is matched by weight 2:1-3:1.
Preferably, the lubricant is in ethylene bis stearamide, calcium stearate, polyethylene glycol oxide wax or TAF
It is at least one.
A kind of preparation method of the HIPS composite of high glaze composite flame-proof, comprising the following steps:
(1) Flame-retardant PET is dried in vacuum drying oven；
(2) in proportion by Flame-retardant PET dried in step (1) respectively with HIPS, fire retardant, compatilizer, antioxidant and lubrication
Agent etc. mixes 10~15 minutes to obtain mixture to uniformly mixed；
(3) mixture in step (2) is added twin-screw extrude by the main spout of double screw extruder, melting is squeezed
Out, extruded material is after cooling, air-dried, pelletizing, drying to get novel glazed flame-retardant HIPS composite.
Preferably, the Flame-retardant PET drying be dried to be divided into two stages and be dried in vacuum drying oven, wherein
First stage is dry 3~5h, preferably 3.5~4.5h under conditions of 75~80 DEG C of temperature；Second stage be temperature 130~
Dry 7~10h, preferably 8~9h under conditions of 140 DEG C.
Preferably, the temperature setting range of the double screw extruder is 210~250 DEG C, the double screw extruder
Screw speed is 200~500rpm, and the vacuum degree of the double screw extruder is -0.6~1.0Kgf/cm2.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is compounded using synthesis Flame-retardant PET with a small amount of brominated triazine, and compound process and process are simple, is easy to add
Work preparation, not only may be implemented HIPS anti-flammability, but also can substantially improve HIPS appearance gloss, in addition conventionally used auxiliary flame retardant
Antimony oxide be even more the gloss of material is influenced it is very big, therefore, on the basis of the above, using the good antimony glycol of the transparency come
Auxiliary flame retardant is done, it is fire-retardant that synergistic can be played in this way, and do not influence material glossiness, and prepare high glaze, anti-flammability
Good novel HIPS composite, composite mechanical strength high-dimensional stability is good, and anti-flammability is high, and appearance gloss is opened up significantly
The wide application range of HIPS；It is widely used in the occasion (such as some electric appliance casings) for glossiness and flame-retardancy requirements, has
Have broad application prospects.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
In the embodiment of the present invention one, a kind of HIPS composite of high glaze composite flame-proof is formed as shown in table 1:
Table 1: unit (kg)
| HIPS1300 | Flame-retardant PET | Brominated triazine | Compatilizer | Antioxidant | Lubricant |
| 100 | 20 | 8 | 2 | 0.25 | 0.35 |
Wherein, HIPS relative density is 1.05, and number-average molecular weight is 100,000；Izod notch impact strength is 8.5 KJ/m2.
Flame-retardant PET is the 2- hydroxy phenyl phosphinic acids copolymerization PET containing 6%, contains 1% auxiliary flame retardant ethylene glycol simultaneously
Antimony, synthetic method are as follows:
With PTA (terephthaldehyde's acid diacid) and ethylene glycol, 1:1.30,1% antimony glycol of addition urge progress transesterification anti-in molar ratio
It answers, in 250 DEG C of progress esterifications, after esterification yield reaches 92%-98%, adds 6% 2- hydroxy phenyl phosphinic acids copolymerization list
Body, normal pressure carry out polycondensation 40-60 minutes, pumping high vacuum, are warming up to 275 DEG C -280 DEG C, regulation viscosity to be achieved is 0.70 dL/g
Afterwards, it discharges, Flame-retardant PET slice has been prepared in pelletizing.
Compatilizer is styrene-Bing Xi Celadon-glycidyl methacrylate, and melt index is 8g/10min (200
DEG C/5Kg), the content of GMA is the copolymer SAG-02. of the liter new material Co., Ltd of 2.0%. such as Nantong day
Antioxidant is that antioxidant 1010 and irgasfos 168 compound, weight proportion position 1:2.
Lubricant is TAF；
In the embodiment of the present invention two, a kind of HIPS composite of high glaze composite flame-proof is formed as shown in table 2:
Table 2: unit (kg)
| HIPS1300 | Flame-retardant PET | Brominated triazine | Compatilizer | Antioxidant | Lubricant |
| 100 | 30 | 6 | 2 | 0.25 | 0.35 |
Wherein, HIPS relative density is 1.05, and number-average molecular weight is 100,000；Izod notch impact strength is 8.5 KJ/m2.
Flame-retardant PET is the 2- hydroxy phenyl phosphinic acids copolymerization PET containing 6%, contains 1% auxiliary flame retardant ethylene glycol simultaneously
Antimony, synthetic method are as follows:
With PTA (terephthaldehyde's acid diacid) and ethylene glycol, 1:1.30,1% antimony glycol of addition urge progress transesterification anti-in molar ratio
It answers, in 250 DEG C of progress esterifications, after esterification yield reaches 92%-98%, adds 6% 2- hydroxy phenyl phosphinic acids copolymerization list
Body, normal pressure carry out polycondensation 40-60 minutes, pumping high vacuum, are warming up to 275 DEG C -280 DEG C, regulation viscosity to be achieved is 0.70 dL/g
Afterwards, it discharges, Flame-retardant PET slice has been prepared in pelletizing.
Compatilizer is styrene-Bing Xi Celadon-glycidyl methacrylate, and melt index is 8g/10min (200
DEG C/5Kg), the content of GMA is the copolymer SAG-02. of the liter new material Co., Ltd of 2.0%. such as Nantong day
Antioxidant is that antioxidant 1010 and irgasfos 168 compound, weight proportion position 1:2.
Lubricant is TAF；
The preparation method of the HIPS composite of one of above-described embodiment high glaze composite flame-proof, comprising the following steps:
(1) Flame-retardant PET is dried；The drying is dried in vacuum drying oven, is divided into two stages and is done
Dry, the first stage is dry 3h under conditions of 80 DEG C of temperature；Second stage is dry 7h under conditions of 140 DEG C of temperature；
(2) it is uniformly mixed by various component ratios, incorporation time is mixing 10 minutes；
(3) added twin-screw extrude by the main spout of double screw extruder, melting extrusion, extruded material through cooling,
To get white glazed flame-retardant HIPS composite after air-dried, pelletizing, drying.
The temperature setting range of double screw extruder is 65~185 DEG C, and screw speed is 200~500rpm, extruder end
End vacuum degree is -0.08~0.09MPa, the temperature in each area of double screw extruder are as follows:
One area's temperature: 210~215 DEG C, two area's temperature: 215~220 DEG C, three area's temperature: 220~225 DEG C, four area's temperature: 225
~230 DEG C, five area's temperature: 230~235 DEG C, six area's temperature: 235~240 DEG C, seven area's temperature: 233~235 DEG C.
Screw speed is 400rpm, and vacuum degree is -0.6Kgf/cm2.
Its performance of the HIPS composite of a kind of high glaze composite flame-proof such as 3 institute of table being prepared in above embodiments
Show:
Table 3: performance test table
Mechanical performance index is tested according to corresponding ASTM standard, and anti-flammability measures glossiness and use according to UL94 standard testing
Glossiness measuring apparatus.Selected incidence angle angle is 60 degree when measurement.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie
In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, nothing
By from the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by institute
Attached claim rather than above description limit, it is intended that will fall within the meaning and scope of the equivalent elements of the claims
All changes be included within the present invention.
Claims (9)
1. a kind of HIPS composite of high glaze composite flame-proof, which is characterized in that the composite material includes following component:
100 parts by weight of hips；
20~40 parts by weight of Flame-retardant PET；
2~8 parts by weight of compatilizer；
5~10 parts by weight of main flame retardant；
1~3 parts by weight of auxiliary flame retardant；
0.1~1 parts by weight of antioxidant；
0.1~1 parts by weight of lubricant；
It is preferred that are as follows:
100 parts by weight of hips；
25~35 parts by weight of Flame-retardant PET；
2~5 parts by weight of compatilizer；
5~8 parts by weight of main flame retardant；
1~2 parts by weight of auxiliary flame retardant；
0.1~0.5 parts by weight of antioxidant；
0.5~1 parts by weight of lubricant.
2. a kind of HIPS composite of high glaze composite flame-proof described in claim 1, which is characterized in that the HIPS is opposite
Density is 1.05, and average molecular weight is 6~150,000；The Izod notch impact strength of the HIPS is 8.5-9.5 KJ/m2, excellent
Select 9.0-9.5 KJ/m2.
3. a kind of HIPS composite of high glaze composite flame-proof according to claim 1, which is characterized in that described fire-retardant
PET is that the 2- hydroxy phenyl phosphinic acids containing 5%-10% are copolymerized PET, (is added in polymerization process containing 1%-3% antimony glycol simultaneously
Enter, be uniformly dispersed, do not influence the transparency), appearance color is the slice of white clear, and intrinsic viscosity is 0.68~0.78dl/
G, preferably 0.70~0.75dl/g.
4. a kind of HIPS composite of high glaze composite flame-proof according to claim 1, which is characterized in that described is compatible
Agent is styrene-Bing Xi Celadon-glycidyl methacrylate, and melt index is 6-9g/10min (200 DEG C/5Kg), GMA
Content be 1.8%-2.2%, the fire retardant is that brominated triazine is saturating, and wherein 220-230 DEG C of fusing point, bromine content content is 65-
70%, preferably 67-68%.
5. a kind of HIPS composite of high glaze composite flame-proof according to claim 1, which is characterized in that the master is anti-
Oxygen agent is specially antioxidant 1010 or 1076, preferably antioxidant 1010；Auxiliary antioxidant is irgasfos 168；Major-minor antioxidant is pressed
Weight ratio 2:1-3:1 proportion.
6. a kind of HIPS composite of high glaze composite flame-proof according to claim 1, which is characterized in that the lubrication
Agent is selected from least one of ethylene bis stearamide, calcium stearate, polyethylene glycol oxide wax or TAF.
7. according to claim 1-6 it is one of any described in a kind of preparation method of the HIPS composite of high glaze composite flame-proof,
It is characterized in that, the described method comprises the following steps:
Flame-retardant PET is dried in vacuum drying oven；
In proportion by Flame-retardant PET dried in step (1) respectively with HIPS, fire retardant, compatilizer, antioxidant and lubricant etc.
Mixture is obtained to uniformly mixed within mixing 10~15 minutes；
Mixture in step (2) is added twin-screw extrude, melting extrusion by the main spout of double screw extruder, is squeezed
Material is after cooling, air-dried, pelletizing, drying to get novel glazed flame-retardant HIPS composite out.
8. a kind of preparation method of the HIPS composite of high glaze composite flame-proof according to claim 7, which is characterized in that
The Flame-retardant PET drying is to be dried to be divided into two stages and be dried in vacuum drying oven, and wherein the first stage is in temperature
Dry 3~5h, preferably 3.5~4.5h under conditions of 75~80 DEG C of degree；Second stage is under conditions of 130~140 DEG C of temperature
Dry 7~10h, preferably 8~9h.
9. a kind of preparation method of the HIPS composite of high glaze composite flame-proof according to claim 7, which is characterized in that
The temperature setting range of the double screw extruder is 210~250 DEG C, the screw speed of the double screw extruder is 200~
500rpm, the vacuum degree of the double screw extruder are -0.6~1.0Kgf/cm2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810852665.3A CN109181196A (en) | 2018-07-30 | 2018-07-30 | A kind of HIPS composite and preparation method thereof of high glaze composite flame-proof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810852665.3A CN109181196A (en) | 2018-07-30 | 2018-07-30 | A kind of HIPS composite and preparation method thereof of high glaze composite flame-proof |
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| CN201810852665.3A Pending CN109181196A (en) | 2018-07-30 | 2018-07-30 | A kind of HIPS composite and preparation method thereof of high glaze composite flame-proof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111849085A (en) * | 2020-07-28 | 2020-10-30 | 青岛福尔蒂新材料有限公司 | High-impact PS/PET resin composition |
| CN111925622A (en) * | 2020-08-25 | 2020-11-13 | 佳易容聚合物(上海)有限公司 | HIPS (high impact polystyrene) composite material with excellent chemical resistance and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153307A (en) * | 1998-07-30 | 2000-11-28 | Nova Chemicals Inc. | Compatibilizer and laminates containing said compatibilizer |
| CN101412805B (en) * | 2001-01-18 | 2011-10-19 | 东洋纺织株式会社 | Catalyst for polymerization of polyester, polyester and process for preparing polyester |
| CN106939112A (en) * | 2016-01-05 | 2017-07-11 | 上海奇彩塑胶原料有限公司 | A kind of high glaze HIPS/ recycled PET bottles piece composite and preparation method thereof |
-
2018
- 2018-07-30 CN CN201810852665.3A patent/CN109181196A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6153307A (en) * | 1998-07-30 | 2000-11-28 | Nova Chemicals Inc. | Compatibilizer and laminates containing said compatibilizer |
| CN101412805B (en) * | 2001-01-18 | 2011-10-19 | 东洋纺织株式会社 | Catalyst for polymerization of polyester, polyester and process for preparing polyester |
| CN106939112A (en) * | 2016-01-05 | 2017-07-11 | 上海奇彩塑胶原料有限公司 | A kind of high glaze HIPS/ recycled PET bottles piece composite and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 中国有色金属工业协会专家委员会: "《有色金属系列丛书 中国锑业》", 31 December 2014, 冶金工业出版社 * |
| 王忠卫: "羟甲基苯基次磷酸阻燃共聚酯的合成与性能", 《高分子材料科学与工程》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111849085A (en) * | 2020-07-28 | 2020-10-30 | 青岛福尔蒂新材料有限公司 | High-impact PS/PET resin composition |
| CN111925622A (en) * | 2020-08-25 | 2020-11-13 | 佳易容聚合物(上海)有限公司 | HIPS (high impact polystyrene) composite material with excellent chemical resistance and preparation method thereof |
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Application publication date: 20190111 |