CN101333298B - Method for preparing halogen-free fire retardant plastic mastre batch and special resin by compounding hyperbranched polyesteramides and misch metal oxide - Google Patents
Method for preparing halogen-free fire retardant plastic mastre batch and special resin by compounding hyperbranched polyesteramides and misch metal oxide Download PDFInfo
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- CN101333298B CN101333298B CN2008100715028A CN200810071502A CN101333298B CN 101333298 B CN101333298 B CN 101333298B CN 2008100715028 A CN2008100715028 A CN 2008100715028A CN 200810071502 A CN200810071502 A CN 200810071502A CN 101333298 B CN101333298 B CN 101333298B
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- retardant plastic
- earth oxide
- fire retardant
- mixed rare
- halogen
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Abstract
The invention relates to a method for preparing a flame retardant plastic master batch and a special resin thereof. When preparing the composite halogen-less flame retardant plastic master batch of branched polyesteramide and mixed rare earth oxide, taking 100 portions of matrix resin as reference, the proportion of the ingredients is as follow: 100 potions of matrix resin, 150-200 portions of BPEA/RE2O3, 2-10portions of processing flow aid and 80-160portions of calcium carbonate; putting above ingredients into a high speed mixer under 110-130 DEG C and blending for 10mins, in this way, composite halogen-less flame retardant plastic master batch of branched polyesteramide and mixed rare earth oxide can be prepared; adding resin PE, PP, ABS or PVC, 8-15 times the weight of the original matrix resin, into the master batch, blending thoroughly and then extruding the granulas, in this way, the special resin for the composite halogen-less flame retardant plastic master batch of branched polyesteramide and mixed rare earth oxide can be prepared. The material prepared through the method of the invention is of high-temperature resistance and flame retardance and can be used for manufacturing automobile parts, electric appliance shells, electric appliance elements, building materials and indoor decorations.
Description
Technical field
The present invention relates to fire retardant plastic mastre batch and resin dedicated preparation method, the resin dedicated preparation method of halogen-free fire retardant plastic who particularly relates to super-branched polyesteramide/mixed rare-earth oxide composite halogen-free fire retardant plastic mastre batch and utilize this masterbatch to prepare.
Background technology
" green " chemistry and chemical industry revolution, just facilitating the continuous development of fire-retardantization of high polymer material treatment technology, requirement to the over-all properties of flame retardant uprises day by day, should reach the fire-retardant rank of regulation, good physical and mechanical property, erosion resistance, low cigarette, nontoxicity and thermostability etc. also will be arranged.
The Halogen flame-retarded technology adopts Polybrominated biphenyl (hexabromobiphenyl, octabromo-diphenyl, nine bromo biphenyls etc.) and polybromodiphenyl ether (decabromodiphynly oxide, eight bromo ether, tetrabromo-bisphenol, pentabromodiphenyl oxide, hexabromocyclododecane etc.) class material to make fire retardant usually, and technical maturity, effect are pretty good.Yet the halogen containing flame-retardant that these are traditional has its inherent defective: if separate out from product human body is had potential harm, can not press down cigarette when fire-retardant and can discharge deleterious hydrogen halide, be faced with superseded destiny.In February, 2003, " ROHS " that parliament of European Union and EU Council put into effect (ROHS) and " make " (WEEE) two ban about waste electronic andelectrical equipment, explicit order limits the use of Polybrominated biphenyl and polybromodiphenyl ether aspect fire retardant.
Halogen-free flameproof comparison operators trend of fashionable generation has become the hot research problem of fire-retardantization treatment technology.The halogen-free flameproof development trend mainly comprises at present: (1) " greenization ", development low toxicity, few cigarette, high-molecular weight green product; (2) " high efficiency " carries out miniaturization to fire retardant, even nanometer handles, and develops efficient surface treatment agent, high-performance synergistic agent, and then develops novel, cooperative flame retardant system efficiently.(3) " simplification ", preparation collection acid source, the gentle fire retardant that comes from " trinity " all over the body in charcoal source are to simplify the compound process of fire retardant.The halogen-free flame-retardant system of having developed mainly contains: (i) inorganic filling is fire-retardant, comprise polynite, magnesium hydroxide, aluminium hydroxide, potential calcium hydroxide and with compound system of materials such as red phosphorus etc.(ii) expansion type flame-retarding is made of char-forming agent (charcoal source), dewatering agent (acid source) and whipping agent (source of the gas); Char-forming agent refers to the polyhydroxy organic compound that carbon content is high, and common have tetramethylolmethane, a nylon 6 (PA6) etc.; Dewatering agent mainly is some inorganic acid salts and inorganic acid ester class, as ammonium phosphate salt, phosphoric acid ester, borate and silicate etc.; Whipping agent commonly used has trimeric cyanamide, Dyhard RU 100, ammonium polyphosphate, amine borate, Dyhard RU 100 formaldehyde resin etc.(iii) organic silicon flame-retardant, the organosilyl flame retardant properties of general independent use is unsatisfactory, and is normal with it and other fire retardant interworking cooperative flame retardants.As, organosilicon/phosphorus cooperative flame retardant effect highly significant.
From the open source literature of the research halogen-free flameproof aspect seen, adopt nitrogenous poly-hydroxy organism of branching and mixed rare-earth oxide (RE
2O
3) compositely carry out fire-retardant research, do not appear in the newspapers at present.Super-branched polyesteramide (hyperbranched polyesteramide, abbreviate HBPEA as), can successfully synthesize by the commercialized raw materials monomer, contain how active terminal hydroxy group (OH) in the molecular linkage chain, and a certain amount of molecule inner chamber carboxyl (COOH), character such as polarity and viscosity has adjustable, the structure of many branching produces the small molecules volatile matter and generates non-combustible materials with the easy cyclisation of catalyzer (as RE203) effect that suits under hot conditions, is the conglomerate of potential char-forming agent, dewatering agent, whipping agent.With HBPEA and RE
2O
3Compound, can make the high molecular halogen-free flame retardants that tool has " greenization ", " simplification " characteristics concurrently, with itself and other flame-retardant system interworking, be hopeful to realize " high efficiency ".HBPEA/RE
2O
3Fire-retardant fire-retardantization of the high polymer material treatment technology that is applied to of composite halogen-free helps simplifying technology, and save energy improves society and economic benefit.
Summary of the invention
The purpose of this invention is to provide a kind of super-branched polyesteramide (HBPEA) and mixed rare-earth oxide (RE
2O
3) composite halogen-free fire retardant plastic mastre batch and utilize the resin dedicated preparation method of halogen-free fire retardant plastic of this masterbatch preparation.Its technical scheme is that patent " a kind of preparation method of misch metal oxide/hyperbranched polyesteramides composite material " will contain how active terminal hydroxy group (OH) HBPEA of functional group and RE earlier
2O
3Carry out physical mixed or chemical coupling processing and make composite high-molecular auxiliary agent (HBPEA/RE
2O
3), add matrix resin, HBPEA/RE by the actual demand formula ratio again
2O
3, processing flow promotor, mineral filler, mix, extruding pelletization makes with HBPEA and RE
2O
3Composite halogen-free is fire-retardant to be the plastic master pellet of feature.According to different service requirementss, continue adding matrix resin PE, PVC, PP or ABS toward masterbatch simultaneously, mediate fully at a high speed and screw rod extrusion mixing, it is resin dedicated that last granulation makes halogen-free flameproof.
The present technique initiative is utilized super-branched polyesteramide (HBPEA) and mixed rare-earth oxide (RE
2O
3) the compound pluronic polymer of making, and be applied to plastic material.When material combustion, high temperature can be facilitated HBPEA and RE
2O
3Continuous reaction and generate the high temperature resistant non-combustible materials of bulk shape, help improving the flame retardant properties of material.The present invention is resin dedicated to can be used for preparing products such as trolley part, electric appliance casing, electric elements, building materials, upholstery.
For realizing purpose of the present invention, adopted following concrete preparation method:
Preparation super-branched polyesteramide and mixed rare-earth oxide composite halogen-free fire retardant plastic mastre batch
Each component is a benchmark with per 100 parts matrix resin amount, and the amount ratio between the component is:
Matrix resin 100
HBPEA/RE
2O
3 150-200
Processing flow promotor 2-10
Lime carbonate 80-160
Described processing flow promotor is meant macromolecule wax, hard ester acid, magnesium stearate or dioctyl phthalate (DOP) (DOP).Described HBPEA/RE
2O
3Be to obtain according to patent " a kind of preparation method of misch metal oxide/hyperbranched polyesteramides composite material ".
During preparation, above-mentioned each component is metered in the high-speed mixer, under 110～130 ℃, high-speed stirring 10min obtains super-branched polyesteramide and mixed rare-earth oxide composite halogen-free fire retardant plastic mastre batch.
Preparation super-branched polyesteramide and mixed rare-earth oxide composite halogen-free flame retardant plastics are resin dedicated
Continue parts by weight resin PE, PP, ABS or the PVC of 8～15 times of amounts of adding masterbatch initial substrate resin toward above-mentioned masterbatch, holding temperature, continue high-speed stirring 10min and carry out thorough mixing, last extruding pelletization makes super-branched polyesteramide and mixed rare-earth oxide composite halogen-free flame retardant plastics is resin dedicated.
Embodiment 1
In the high speed kneader, add PE, the 175kg HBPEA/RE of 100kg
2O
3, 10kg macromolecule wax, 160kg 1000-1250 order lime carbonate, 120 ℃ of maintenance system temperature keep high-speed stirring 10min, cooling, discharging, extruding pelletization obtains super-branched polyesteramide and mixed rare-earth oxide composite halogen-free flame retardant plastics master batch material.
In the gained masterbatch, add 800kg PE, holding temperature, behind the continuation high-speed stirring 10min, machine extrusion mixing of immigration multiscrew and traction, cutting, granulation obtain super-branched polyesteramide and mixed rare-earth oxide compound halogen-free fire retardant plastic is resin dedicated.
Embodiment 2
In the high speed kneader, add PP, the 150kg HBPEA/RE of 100kg
2O
3, the hard ester acid of 5kg, 120kg 1000-1250 order lime carbonate, 130 ℃ of maintenance system temperature keep high-speed stirring 10min, cooling, discharging, extruding pelletization obtains super-branched polyesteramide and mixed rare-earth oxide composite halogen-free flame retardant plastics master batch material.
In the gained masterbatch, add 1500kg PP, holding temperature, behind the continuation high-speed stirring 10min, machine extrusion mixing of immigration multiscrew and traction, cutting, granulation obtain super-branched polyesteramide and mixed rare-earth oxide compound halogen-free fire retardant plastic is resin dedicated.
Embodiment 3
In the high speed kneader, add ABS, the 160kgHBPEA/RE of 100kg
2O
3, 2kg Magnesium Stearate, 80kg 1000-1250 order lime carbonate, 110 ℃ of maintenance system temperature keep high-speed stirring 10min, cooling, discharging, extruding pelletization obtains super-branched polyesteramide and mixed rare-earth oxide composite halogen-free flame retardant plastics master batch material.
In the gained masterbatch, add 1200kg ABS, holding temperature, behind the continuation high-speed stirring 10min, machine extrusion mixing of immigration multiscrew and traction, cutting, granulation obtain super-branched polyesteramide and mixed rare-earth oxide compound halogen-free fire retardant plastic is resin dedicated.
Embodiment 4
In the high speed kneader, add PVC, the 180kg HBPEA/RE of 100kg
2O
3, 10kg DOP, 100kg 1000-1250 order lime carbonate, 110 ℃ of maintenance system temperature keep high-speed stirring 10min, cooling, discharging, extruding pelletization obtains super-branched polyesteramide and mixed rare-earth oxide composite halogen-free flame retardant plastics master batch material.
Add 1000kg PVC in the gained masterbatch, behind the high-speed stirring 10min, machine extrusion mixing of immigration multiscrew and traction, cutting, granulation obtain super-branched polyesteramide and mixed rare-earth oxide compound halogen-free fire retardant plastic is resin dedicated.
Claims (3)
1. the preparation method of branched polyamide ester and mixed rare-earth oxide composite halogen-free fire retardant plastic mastre batch, each component is a benchmark with the matrix resin amount of per 100 weight parts when it is characterized in that preparing branched polyamide ester and mixed rare-earth oxide composite halogen-free fire retardant plastic mastre batch, and the amount ratio between the component is:
Matrix resin 100
HBPEA/RE
2O
3 150-200
Processing flow promotor 2-10
Lime carbonate 80-160
Wherein: HBPEA is a super-branched polyesteramide, RE
2O
3Be mixed rare-earth oxide, HBPEA/RE
2O
3Mixture for super-branched polyesteramide/mixed rare-earth oxide;
During preparation, above-mentioned each component is metered in the high-speed mixer, under 110～130 ℃, high-speed stirring 10min obtains halogen-free fire retardant plastic mastre batch.
2. the preparation method of branched polyamide ester according to claim 1 and mixed rare-earth oxide composite halogen-free fire retardant plastic mastre batch is characterized in that described processing flow promotor is meant PE, macromolecule wax, stearic acid, Magnesium Stearate or dioctyl phthalate (DOP).
3. the preparation method of branched polyamide ester according to claim 1 and mixed rare-earth oxide composite halogen-free fire retardant plastic mastre batch, resin PE, the PP, ABS or the PVC that it is characterized in that the weight part of 8～15 times of amounts of continuation adding masterbatch initial substrate resin in described masterbatch, high-speed stirring 10min, it is resin dedicated that extruding pelletization makes halogen-free fire retardant plastic.
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|---|---|---|---|
| CN2008100715028A CN101333298B (en) | 2008-07-31 | 2008-07-31 | Method for preparing halogen-free fire retardant plastic mastre batch and special resin by compounding hyperbranched polyesteramides and misch metal oxide |
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| CN2008100715028A CN101333298B (en) | 2008-07-31 | 2008-07-31 | Method for preparing halogen-free fire retardant plastic mastre batch and special resin by compounding hyperbranched polyesteramides and misch metal oxide |
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|---|---|
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| CN101333298B true CN101333298B (en) | 2011-03-30 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101475706B (en) * | 2009-01-22 | 2011-06-08 | 广东华南精细化工研究院有限公司 | Rear earth organic phosphonate flame retardant, synthesizing method and use thereof |
| CN101735452B (en) * | 2009-12-30 | 2011-12-28 | 福建师范大学 | Preparation method of super-branched polyesteramide rare earth complex |
| CN109096502B (en) * | 2018-07-26 | 2020-05-05 | 东华大学 | Flame-retardant antibacterial master batch and preparation method thereof |
| CN113754936A (en) * | 2021-03-23 | 2021-12-07 | 金微纳米新材料(杭州)有限公司 | Polyolefin flame retardant flame-retardant master batch and preparation method thereof |
| CN113388221B (en) * | 2021-05-28 | 2023-02-07 | 珠海格力新材料有限公司 | ABS composite material and preparation method thereof |
| CN115895209A (en) * | 2022-11-24 | 2023-04-04 | 广州华新科智造技术有限公司 | Calcium carbonate master batch and preparation method and application thereof |
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| CN1382739A (en) * | 2001-04-23 | 2002-12-04 | 中国科学技术大学 | Phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation and its preparing process |
| WO2006040066A1 (en) * | 2004-10-08 | 2006-04-20 | Basf Aktiengesellschaft | Flowable thermoplastic materials with halogen-free flame protection |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1382739A (en) * | 2001-04-23 | 2002-12-04 | 中国科学技术大学 | Phosphorus contained ultra-branched polyurethane acrylate as fire retarding agent solidified by radiation and its preparing process |
| WO2006040066A1 (en) * | 2004-10-08 | 2006-04-20 | Basf Aktiengesellschaft | Flowable thermoplastic materials with halogen-free flame protection |
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Assignee: Shanghai Shitian Engineering Plastic Co.,Ltd. Assignor: Fujian Normal University Contract record no.: 2012990000337 Denomination of invention: Method for preparing halogen-free fire retardant plastic mastre batch and special resin by compounding hyperbranched polyesteramides and misch metal oxide Granted publication date: 20110330 License type: Exclusive License Open date: 20081231 Record date: 20120521 |
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Effective date of registration: 20170912 Address after: Jincheng City, Shanxi province 048002 Bagong town of Zezhou County Patentee after: Shanxi energy-saving materials Limited by Share Ltd Address before: 350007 scientific research office, Fujian Normal University, Fuzhou, Cangshan, Fujian province 8 Patentee before: Fujian Normal University |
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Granted publication date: 20110330 Termination date: 20200731 |