CN102604226A - Special halogen-free flame-retardant master batch for polypropylene and preparation method for halogen-free flame retardant master batch - Google Patents
Special halogen-free flame-retardant master batch for polypropylene and preparation method for halogen-free flame retardant master batch Download PDFInfo
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- CN102604226A CN102604226A CN2012100742286A CN201210074228A CN102604226A CN 102604226 A CN102604226 A CN 102604226A CN 2012100742286 A CN2012100742286 A CN 2012100742286A CN 201210074228 A CN201210074228 A CN 201210074228A CN 102604226 A CN102604226 A CN 102604226A
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Abstract
The invention discloses a special halogen-free flame-retardant master batch for polypropylene and a preparation method for the halogen-free flame retardant master batch. Components of the master batch comprise, in mass percent, 75-90% of phosphorus-nitrogen halogen-free flame retardant, 8-22% of carrier and 0.1-5% of modified ethylene bis-fatty acid amide. By the aid of the master batch, quality instability of materials due to non-uniform mixing of powder and granules is effectively avoided, easiness in generation of chippings or powder during granule cutting is avoided, production efficiency is improved, and production cost is lowered. Adopting a continuous banburying-extrusion production process leads production efficiency to be high. The master batch effectively solves the problems of easiness in moisture absorption, degradation and foaming of halogen-free flame retardant, so that storage time of the phosphorus-nitrogen halogen-free flame retardant is prolonged, and processability of the phosphorus-nitrogen halogen-free flame retardant is improved. Besides, the special halogen-free flame-retardant master batch for the polypropylene has the advantages of easiness in dispersion, high flame-retardant efficiency and low production cost, and has less influence on physical and mechanical properties, heat resistance, processability and surface color of composite materials than a special traditional halogen-free flame-retardant master batch for polypropylene.
Description
Technical field
The invention discloses the preparation method of the special-purpose halogen-free flameproof master batch of a kind of Vestolen PP 7052.
Background technology
Fire-retardant master granule is also claimed flame-retardant master batch, fire prevention master batch.Be called " enriched material " abroad, the concentrating of the fire retardant of meaning.Fire-retardant master granule produces has had decades historical; It mainly is to solve in the use of fire retardant powder to disperse inequality at first; The problem that dust pollution is serious; Through years of development, the application of a large amount of scientific methods and new technique, people not only limit to and disperse, prevented to pollute on these general issues the research of fire-retardant master granule.It has formed an independent educational project and has developed into an independently industry.A large amount of technical study makes fire-retardant master granule become the product of high-tech, hi-tech type with using.
Existing flame-retarded technology all is to give the polyolefine flame retardant properties through direct interpolation fire retardant.At present; Halogen-free flame retardants commonly used mainly contains inorganic combustion inhibitor and phosphorus-nitrogen expansion type fire retardant; And inorganic combustion inhibitor is because poor with the consistency of polyolefin resin; Flame retarding efficiency is low, only when a large amount of the filling, just has certain flame retardant effect, and understands polyolefinic mechanical property of heavy damage and processing characteristics like this.In order to overcome too low this shortcoming of mineral-type fire retardant efficient, in polyolefin resin, adopt the higher P-N type halogen-free flame retardants of flame retarding efficiency usually, this based flame retardant surface energy when being heated forms one deck dense charcoal layer; Play heat insulation, oxygen barrier, press down cigarette; Can prevent molten drop again, have good flame retardancy, and when burning Halogen, low toxicity and non-corrosiveness gas produce; The flame-retardant system that belongs to environment-friendly type is so development very rapidly.
Because this P-N type fire retardant generally all is a powder; And its fineness is easy to generate amounts of dust and pollutes generally more than 400 orders in weighing, mixing, granulation process, worsens production environment; HUMAN HEALTH is caused very big harm, and can cause wearing and tearing to a certain degree processing units.And the P-N type fire retardant all has that water absorbability is strong, thermostability is not high, with the relatively poor problem of consistency of polyolefin resin, cause that fire retardant material is responsive to moisture, to be prone to foaming and degraded, fire retardant dispersed relatively poor and damage the shortcoming of Drawing abillity and physical and mechanical properties to a certain extent in resin.
Domestic research about the halogen-free flameproof master batch at present mainly contains: Chinese patent CN101643649 discloses a kind of expanding halide-free fire-retardant and has adopted the fire-retardant master granule of this fire retardant; This fire-retardant master granule has adopted low molecular MDA, phosphide etc.; In polyolefin resin, move easily; And the fire-retardant master granule content of preparation is lower, has only 50-65%.Patent CN102212228A has prepared a kind of halogen-free polypropylene flame redardant masterbatch, and the master batch content of preparation is lower, has only 40-60%, and adopts the working method of twin screw, can cause bigger dust pollution.Patent CN1159355C discloses a kind of preparation method who prepares polyolefine non-halogen fire-retardant master granule; This method is to adopt the method for chemistry on flame retardant molecule, to introduce polar group; Thereby structurally improve the consistency of fire retardant and polyolefin resin; Adopt the method for chemistry to be difficult to control reaction conditions, quality product is difficult to stablize.
Summary of the invention
The objective of the invention is to overcome the defective and the deficiency of prior art, special-purpose halogen-free flameproof master batch of a kind of Vestolen PP 7052 and preparation method thereof is provided.
To achieve these goals, the present invention adopts following technical scheme:
The special-purpose halogen-free flameproof master batch of a kind of Vestolen PP 7052, process by following component by mass percent:
P-N type halogen-free flame retardants 75～90%
Carrier 8～22%
Modification ethylene bis-fatty acid amides 0.1～5%.
Carrier is the carrier as this fire-retardant master granule, and main effect is to be glued together P-N type halogen-free flame retardants powder, to obtain granular halogen-free flameproof masterbatch; The effect of modification ethylene bis-fatty acid amides is the wearing and tearing that reduce between material and the equipment on the one hand; Be to improve the dispersion effect of halogen-free flame retardants powder in carrier on the other hand; Simultaneously owing to have oleophylic, wetting ability; Can increase the consistency of halogen-free flame retardants powder and carrier, thereby improve its interfacial adhesion, increase the flame retardant properties and the physical and mechanical properties of matrix material.
In the special-purpose halogen-free flameproof master batch of above-mentioned Vestolen PP 7052; Said P-N type halogen-free flame retardants is meant that phosphorus, nitrogen, the carbon of the method preparation of adopting chemosynthesis are main Trinitarian macromolecular cpd; Its polymerization degree is greater than 2000, and the median size of powdery solid is 5～25 μ m, wet method whiteness 70～95; Phosphorus element content 18-25%, nitrogen element content 15-35%.
In the special-purpose halogen-free flameproof master batch of above-mentioned Vestolen PP 7052; Said carrier is a Vestolen PP 7052; Comprise one or both of HOPP (PPH), block copolymerization polypropylene (PPC), atactic copolymerized polypropene (PPR), ternary polymerized polypropylene; Polyacrylic melting index is 20～100g/10min, 230 ℃, and 2.16KG.
In the special-purpose halogen-free flameproof master batch of above-mentioned Vestolen PP 7052, said modification ethylene bis-fatty acid amides is be base-material with ethylene bis-fatty acid amides (EBS), and under the effect of catalyzer, the reactive monomer that contains polar group and EBS react the BAB type multipolymer of formation.
The preparation method of the special-purpose halogen-free flameproof master batch of above-mentioned Vestolen PP 7052 comprises the steps:
(1) P-N type halogen-free flame retardants, carrier, modification ethylene bis-fatty acid amides are pressed the proportion speed weighing;
(2) earlier carrier, modification ethylene bis-fatty acid amides are joined in the adding pressure type upset Banbury mixer; Temperature in the control banburying chamber is 150～190 ℃; Rotor speed is 20～80r/min; The banburying time is 3～15min, treats to divide after the material fusion three times P-N type halogen-free flame retardants powder to be joined in the Banbury mixer, and 2～5min at interval feeds intake at every turn; Banburying 5～15min again after material all adds;
(3) the glue head after the above-mentioned banburying is transported in the hopper of single screw extrusion machine through transport tape; Cutting knife in hopper is cut into fragment; The machine barrel of entering forcing machine under action of gravity is extruded through single screw rod melting mixing then, processes the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 through air-cooled flour milling pelletizing.
In above-mentioned preparation method, the length-to-diameter ratio of said single screw extrusion machine is 20～55; The barrel zone temperature of said single screw extrusion machine is 130～180 ℃; Engine speed 300～the 1000r/min of said single screw extrusion machine.
The present invention compared with prior art; Have following positively effect: the effective element phosphorus of the P-N type halogen-free flame retardants that (1) the present invention adopts and nitrogen content are high; Thereby can reduce the addition of fire retardant; Reduce the influence of fire retardant, and do not influence the flame retardant properties of material the Material Physics mechanical property; (2) the special-purpose halogen-free flame retardants master batch of the Vestolen PP 7052 of the present invention's preparation so mixing of materials is even, has effectively avoided powder and pellet to mix the inhomogeneous unsettled situation of quality of materials that causes owing to be the particle size basically identical of particulate state and base resin; (3) the master batch carrier selected for use of the present invention mainly is the higher Vestolen PP 7052 of melting index; Because it is mobile better, and is very good to the covered effect of powder, thereby be prone to produce the phenomenon of chip or powder when having avoided pelletizing; Also improve production efficiency on the other hand, reduced production cost; (4) the present invention adopts the continuous production processes of banburying-extrude; Compare traditional first high-speed stirring; And then compare through the technology that twin screw is extruded and to have following advantage: the one, the production efficiency of Banbury mixer and single screw extrusion machine is high, and under same consumption energy and the output, production cost is low; The 2nd, Banbury mixer melt blending process is carried out in airtight cavity, is difficult for airborne dust, produces cleaning, reduced the harm healthy to the workman, and dispersion effect is better than twin screw; The 3rd, the employing Banbury mixer can improve the loading level of the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 greatly, and good mixing effect.(5) the special-purpose halogen-free flameproof master batch of Vestolen PP 7052 of the present invention efficiently solves the problem that halogen-free flame retardants is prone to the moisture absorption, is prone to degraded and easy foaming, has prolonged the shelf-time of P-N type halogen-free flame retardants, has improved its processing characteristics.(6) the special-purpose halogen-free flame retardants master batch of the Vestolen PP 7052 of the present invention preparation have be prone to disperse, flame retarding efficiency is high, production cost is low characteristics, all little to the influence of physical and mechanical properties, resistance toheat, processing characteristics and the surface color of matrix material than the special-purpose halogen-free flame retardants master batch of conventional polypropylene.
Embodiment
Embodiment 1
Carry out proportioning by following mass percent composition: the P-N type halogen-free flame retardants 75% (trade mark: NP430; Jiangmen high-end chemical industry ltd); HOPP (PPH) 22% (trade mark EP500N; CSPC petro-chemical corporation), modification ethylene bis-fatty acid amides (ethylene bis-fatty acid amides grafted maleic anhydride) 3% (commercial conventional model).After the accurate weighing of above-mentioned material PPH, modification ethylene bis-fatty acid amides being joined adding pressure type rolls in the Banbury mixer; Temperature in the control banburying chamber is 150 ℃; Rotor speed is 40r/min; The banburying time is 4min, treats to divide after the material fusion three times P-N type halogen-free flame retardants powder to be joined in the Banbury mixer, and 3min at interval feeds intake at every turn; Banburying 10min again after material all adds.Glue head after the above-mentioned banburying is transported in the hopper of single screw extrusion machine through transport tape; Cutting knife in hopper is cut into fragment with the glue head; Each section of control machine barrel temperature is 150 ℃; Engine speed 800r/min extrudes through single screw rod melting mixing, processes the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 through air-cooled flour milling pelletizing then.
Embodiment 2
Carry out proportioning by following mass percent composition: the P-N type halogen-free flame retardants 80% (trade mark: NP430; Jiangmen high-end chemical industry ltd); HOPP (PPH) 19% (trade mark EP500N; CSPC petro-chemical corporation), modification ethylene bis-fatty acid amides (ethylene bis-fatty acid amides grafted maleic anhydride) 1% (commercial conventional model).After the accurate weighing of above-mentioned material PPH, modification ethylene bis-fatty acid amides being joined adding pressure type rolls in the Banbury mixer; Temperature in the control banburying chamber is 160 ℃; Rotor speed is 40r/min; The banburying time is 4min, treats to divide after the material fusion three times P-N type halogen-free flame retardants powder to be joined in the Banbury mixer, and 3min at interval feeds intake at every turn; Banburying 5min again after material all adds.Glue head after the above-mentioned banburying is transported in the hopper of single screw extrusion machine through transport tape; Cutting knife in hopper is cut into fragment with the glue head; Each section of control machine barrel temperature is 150 ℃; Engine speed 800r/min extrudes through single screw rod melting mixing, processes the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 through air-cooled flour milling pelletizing then.
Embodiment 3
Carry out proportioning by following mass percent composition: the P-N type halogen-free flame retardants 85% (trade mark: FR-202; Shenzhen Hong Taiji chemical industry ltd); Atactic copolymerized polypropene (PPR) 13% (trade mark R370Y; Korea S SK company), modification ethylene bis-fatty acid amides (ethylene bis-fatty acid amides grafting Vinylstyrene) 2% (commercial conventional model).After the accurate weighing of above-mentioned material PPR, modification ethylene bis-fatty acid amides being joined adding pressure type rolls in the Banbury mixer; Temperature in the control banburying chamber is 160 ℃; Rotor speed is 45r/min; The banburying time is 6min, treats to divide after the material fusion three times P-N type halogen-free flame retardants powder to be joined in the Banbury mixer, and 5min at interval feeds intake at every turn; Banburying 10min again after material all adds.Glue head after the above-mentioned banburying is transported in the hopper of single screw extrusion machine through transport tape; Cutting knife in hopper is cut into fragment with the glue head; Each section of control machine barrel temperature is 170 ℃; Engine speed 800r/min extrudes through single screw rod melting mixing, processes the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 through air-cooled flour milling pelletizing then.
Embodiment 4
Carry out proportioning by following mass percent composition: the P-N type halogen-free flame retardants 85% (trade mark: PNP-1D; Hangzhou Jie Ersi chemical industry ltd); Atactic copolymerized polypropene (PPR) 10% (trade mark R370Y; Korea S SK company), modification ethylene bis-fatty acid amides 5% (ethylene bis-fatty acid amides grafting Vinylstyrene) (commercial conventional model).After the accurate weighing of above-mentioned material PPR, modification ethylene bis-fatty acid amides being joined adding pressure type rolls in the Banbury mixer; Temperature in the control banburying chamber is 160 ℃; Rotor speed is 50r/min; The banburying time is 5min, treats to divide after the material fusion three times P-N type halogen-free flame retardants powder to be joined in the Banbury mixer, and 2min at interval feeds intake at every turn; Banburying 10min again after material all adds.Glue head after the above-mentioned banburying is transported in the hopper of single screw extrusion machine through transport tape; Cutting knife in hopper is cut into fragment with the glue head; Each section of control machine barrel temperature is 170 ℃; Engine speed 700r/min extrudes through single screw rod melting mixing, processes the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 through air-cooled flour milling pelletizing then.
Embodiment 5
Carry out proportioning by following mass percent composition: the P-N type halogen-free flame retardants 90% (trade mark: FR-202; Shenzhen Hong Taiji chemical industry ltd); Block copolymerization polypropylene (PPC) 8% (trade mark J842; China Petrochemical Industry's Guangzhou Branch), modification ethylene bis-fatty acid amides (ethylene bis-fatty acid amides grafting Vinylstyrene) 2% (commercial conventional model).After the accurate weighing of above-mentioned material PPC, modification ethylene bis-fatty acid amides being joined adding pressure type rolls in the Banbury mixer; Temperature in the control banburying chamber is 160 ℃; Rotor speed is 50r/min; The banburying time is 5min, treats to divide after the material fusion three times P-N type halogen-free flame retardants powder to be joined in the Banbury mixer, and 5min at interval feeds intake at every turn; Banburying 15min again after material all adds.Glue head after the above-mentioned banburying is transported in the hopper of single screw extrusion machine through transport tape; Cutting knife in hopper is cut into fragment with the glue head; Each section of control machine barrel temperature is 150 ℃; Engine speed 500r/min extrudes through single screw rod melting mixing, processes the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 through air-cooled flour milling pelletizing then.
Effect to the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 of the present invention preparation is carried out following experiment:
Table 1 material prescription
The test result of the fire-retardant PP material property of table 2
Claims (6)
1. the special-purpose halogen-free flameproof master batch of a Vestolen PP 7052 is characterized in that being processed by following component by mass percent:
P-N type halogen-free flame retardants 75～90%
Carrier 8～22%
Modification ethylene bis-fatty acid amides 0.1～5%.
2. the special-purpose halogen-free flameproof master batch of Vestolen PP 7052 as claimed in claim 1; It is characterized in that said P-N type halogen-free flame retardants is meant that phosphorus, nitrogen, the carbon of the method preparation of adopting chemosynthesis are main Trinitarian macromolecular cpd, its polymerization degree is greater than 2000; The median size of powdery solid is 5～25 μ m; Wet method whiteness 70～95, phosphorus element content 18-25%, nitrogen element content 15-35%.
3. the special-purpose halogen-free flameproof master batch of Vestolen PP 7052 as claimed in claim 1 is characterized in that,
Said carrier is a Vestolen PP 7052, comprises one or both of HOPP, block copolymerization polypropylene, atactic copolymerized polypropene, ternary polymerized polypropylene, and polyacrylic melting index is 20～100g/10min, 230 ℃, and 2.16KG.
4. the special-purpose halogen-free flameproof master batch of Vestolen PP 7052 as claimed in claim 1 is characterized in that,
Said modification ethylene bis-fatty acid amides is to be base-material with the ethylene bis-fatty acid amides, under the effect of catalyzer, contains the reactive monomer of polar group and the BAB type multipolymer that the EBS reaction forms.
5. the preparation method of the special-purpose halogen-free flameproof master batch of the said Vestolen PP 7052 of claim 1 is characterized in that comprising the steps:
(1) P-N type halogen-free flame retardants, carrier, modification ethylene bis-fatty acid amides are pressed the proportion speed weighing;
(2) earlier carrier, modification ethylene bis-fatty acid amides are joined in the adding pressure type upset Banbury mixer; Temperature in the control banburying chamber is 150～190 ℃; Rotor speed is 20～80r/min; The banburying time is 3～15min, treats to divide after the material fusion three times P-N type halogen-free flame retardants powder to be joined in the Banbury mixer, and 2～5min at interval feeds intake at every turn; Banburying 5～15min again after material all adds;
(3) the glue head after the above-mentioned banburying is transported in the hopper of single screw extrusion machine through transport tape; Cutting knife in hopper is cut into fragment; The machine barrel of entering forcing machine under action of gravity is extruded through single screw rod melting mixing then, processes the special-purpose halogen-free flame retardants master batch of Vestolen PP 7052 through air-cooled flour milling pelletizing.
6. the preparation method of the special-purpose halogen-free flameproof master batch of Vestolen PP 7052 according to claim 1 is characterized in that the length-to-diameter ratio of said single screw extrusion machine is 20～55; The barrel zone temperature of said single screw extrusion machine is 130～180 ℃; Engine speed 300～the 1000r/min of said single screw extrusion machine.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113672A (en) * | 2013-03-06 | 2013-05-22 | 苏州井村塑料科技有限公司 | Low-smoke halogen-free flame retardant packed master batch special for polypropylene and preparation method thereof |
| CN106995559A (en) * | 2017-04-18 | 2017-08-01 | 广东圆融新材料有限公司 | UL94 5VA grades a kind of high GWIT RPPs composition and preparation method thereof |
| CN107266786A (en) * | 2017-07-11 | 2017-10-20 | 江苏理工学院 | A kind of polypropylene halogen-free flame-retardant master batch and preparation method thereof |
| CN114031844A (en) * | 2021-10-25 | 2022-02-11 | 浙江旭森非卤消烟阻燃剂有限公司 | Halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and preparation method thereof |
| CN115972426A (en) * | 2023-01-04 | 2023-04-18 | 广州汇富研究院有限公司 | System and method for preparing gas-phase silicon dioxide plastic concentrate |
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| CN101469096A (en) * | 2007-12-25 | 2009-07-01 | 上海普利特复合材料股份有限公司 | Flame-retardant polypropylene film material |
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- 2012-03-20 CN CN2012100742286A patent/CN102604226A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101469096A (en) * | 2007-12-25 | 2009-07-01 | 上海普利特复合材料股份有限公司 | Flame-retardant polypropylene film material |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103113672A (en) * | 2013-03-06 | 2013-05-22 | 苏州井村塑料科技有限公司 | Low-smoke halogen-free flame retardant packed master batch special for polypropylene and preparation method thereof |
| CN103113672B (en) * | 2013-03-06 | 2015-09-02 | 苏州井村塑料科技有限公司 | Low-smoke non-halogen flame-retardant filler parent granule that a kind of polypropylene is special and preparation method thereof |
| CN106995559A (en) * | 2017-04-18 | 2017-08-01 | 广东圆融新材料有限公司 | UL94 5VA grades a kind of high GWIT RPPs composition and preparation method thereof |
| CN107266786A (en) * | 2017-07-11 | 2017-10-20 | 江苏理工学院 | A kind of polypropylene halogen-free flame-retardant master batch and preparation method thereof |
| CN114031844A (en) * | 2021-10-25 | 2022-02-11 | 浙江旭森非卤消烟阻燃剂有限公司 | Halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and preparation method thereof |
| CN114031844B (en) * | 2021-10-25 | 2023-10-03 | 浙江旭森阻燃剂股份有限公司 | Halogen-free flame-retardant master batch for continuous long glass fiber reinforced polypropylene and preparation method thereof |
| CN115972426A (en) * | 2023-01-04 | 2023-04-18 | 广州汇富研究院有限公司 | System and method for preparing gas-phase silicon dioxide plastic concentrate |
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Application publication date: 20120725 |