CN102585347A - Halogen-free intumescent flame-retardant polypropylene mixture and preparation method thereof - Google Patents
Halogen-free intumescent flame-retardant polypropylene mixture and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a halogen-free intumescent flame-retardant polypropylene mixture and a preparation method thereof and relates to the field of resin flamer-retardant modification. The mixture comprises the following components: polypropylene, a phosphorus-nitrogen intumescent flame retardant, a silicon-containing triazine macromolecule charring agent, an organic ceramic precursor, phosphorus-containing nano montmorillonite and an antioxidant; and the polypropylene mixture is prepared by carrying out melt blending on the components. Compared with the prior art, the mixture prepared by the invention has the characteristics of outstanding water resistance, good flame retardance, excellent mechanical property and the like and can be widely applied to the fields of the automobile industry, wires and cables, building materials and the like.
Description
Technical field
The invention belongs to the flame-retardant modified field of resin, especially relate to a kind of halogen-free expansion type flame-proof polypropylene miser and preparation method thereof.
Background technology
Vestolen PP 7052 (PP) is as one of maximum macromolecular material of output, is widely used in automotive industry, house decoraton, field such as electric.Yet PP belongs to inflammable material, and its limiting oxygen index(LOI) (LOI) is merely 17.0～17.5, and PP is difficult for into charcoal in combustion processes, and is accompanied by a large amount of molten drops, and its further Application and Development receives serious restriction.Therefore, be necessary PP is carried out fire-retardant research.The flame-retardant modified main of conventional P P realized through adding halogen containing flame-retardant, though this based flame retardant is remarkably productive, when burning, can discharge a large amount of smog and toxic gas, and be totally unfavorable to withdrawing of scene of fire personnel and rescue work.In recent years, along with the progress of society and the enhancing of people's environmental consciousness, begin to limit or forbid the use of Halogen fire retardant material both at home and abroad.Therefore, the fire retardant of exploitation LSZH, environment-friendly high-efficiency is extremely urgent.
At present, the halogen-free flame retardants that fire-retardant PP is commonly used mainly contains metal hydroxides, red phosphorus, organic silicon fibre retardant and expansion type flame retardant (IFR) etc.Wherein, IFR is owing to have advantages such as low-smoke low-toxicity, no etchant gas release, is one of halogen-free flame retardants of tool development prospect.Yet though existing IFR system has the advantage that other flame-retardant system hardly matches, also there are many deficiencies in himself, like poor water resistance, flame retarding efficiency is lower, addition is big, it is serious etc. that material mechanical performance is worsened.Therefore, development of new is the halogen-free expanded flame-retardant system efficiently, and its objective necessity is not only arranged, and also has important social meaning and economic benefit.
To the problems referred to above; Wu Kun is the capsule material with melamine formaldehyde resin etc., through the In-situ polymerization microcapsule technology, has prepared the microcapsule ammonium polyphosphate with higher water resistance; And with itself and composite polypropylene flame redardant mixture (the Micro encapsulated ammonium polyphosphate with urea-melamine-formaldehyde shell:preparation that prepared of tetramethylolmethane; Characterization, and its flame retardance in polypropylene, Polymers for Advanced Technologies; 2008,19 (8): 1118-1125).Yet therefore tetramethylolmethane water-soluble more much bigger than ammonium polyphosphate only carry out the water resistance that coating modification can not effectively improve system to ammonium polyphosphate.Patent CN101225187A discloses a kind of novel triazines char-forming agent; And with itself and ammonium polyphosphate composite prepared have good flame-retardance can and the polypropylene miser of mechanical property; But employed char-forming agent Semi-polarity group is more, and the water resistance and the flame retarding efficiency of system are not ideal.Marosi has reported a kind of polyborosiloxane fire retardant with good water resistance ability and synergistic effect; And with itself and ammonium polyphosphate, tetramethylolmethane etc. composite prepared have excellent flame retardancy can expansion type flame-retarding PP material (Ceramic precursor in flame retardant systems.Polymer Degradation and Stability; 2002; 77 (2): 259-265), but because tetramethylolmethane is water-soluble bigger, the water resistance of prepared mixture is still undesirable.
Summary of the invention
The object of the invention is exactly in order to overcome the defective that existing expansion type flame-retarding system exists; A kind of halogen-free expansion type flame-proof polypropylene miser is provided; Advantages such as it has, and water resistance is outstanding, flame retardant properties is good, and the fire retardant consumption is few when reaching identical fire-retardant rank.
The object of the invention can be realized through following technical scheme:
A kind of halogen-free expansion type flame-proof polypropylene miser, the parts by weight of main ingredient are following:
Said siliceous triazine macromolecular carbon forming agent (Si-TBM) is to be made through polycondensation by cyanuric chloride, quadrol and γ-An Bingjisanyiyangjiguiwan, and its molecular structure is following:
Said phosphorus nitrogen expansion type combustion inhibitor is wherein a kind of in polyphosphoric acid melamine (MPP), melamine pyrophosphate (MPy), melamine phosphate (MP) and the ammonium polyphosphate (APP).
The preparation method of said organic ceramic precursor is the mixture that in boric acid, slowly drips octamethylcyclotetrasiloxane and tetraethoxy; Wherein, The mol ratio of octamethylcyclotetrasiloxane, boric acid and tetraethoxy is 15: 1: 1, reacts 6h down at 108 ℃, with zero(ppm) water and washing with alcohol product; Suction filtration, the dry organic ceramic precursor that gets.
The preparation method of said phosphorous nano imvite adds 40.0g sodium-based montmorillonite and 200mL ethanol in the four-hole boiling flask of 500mL, stirs down until forming homogeneous solution at 70 ℃; Subsequently, will be dissolved in 50mL alcoholic acid 10.0g Resorcinol (phenylbenzene) SULPHOSUCCINIC ACID ESTER and slowly drop in the montmorillonite suspension liquid, and be added dropwise to complete the back and react 10h down at 75 ℃; With reaction soln deposition, filtration, in 100 ℃ of vacuum drying ovens, dry to constant weight then, grinding is sieved, and obtains phosphorous nano imvite.
The preferred oxidation inhibitor B215 of said oxidation inhibitor, a kind of in antioxidant 1010 and the oxidation inhibitor 168.
The preparation method of described a kind of halogen-free expansion type flame-proof polypropylene miser; This method is: be to add Vestolen PP 7052 on 170～190 ℃ the open warm-up mill at two roll temperatures; After treating its fusion bag roller; Add oxidation inhibitor, phosphorus nitrogen expansion type combustion inhibitor, siliceous triazine macromolecular carbon forming agent, organic ceramic precursor and phosphorous nano imvite successively, mixing 10～15min can make the halogen-free expansion type flame-proof polypropylene miser.
Compared with prior art; The prepared halogen-free polypropylene flame redardant mixture of the present invention has that water resistance is outstanding, flame retardant properties is good, good mechanical performance, when reaching identical fire-retardant rank the few characteristics of fire retardant consumption, can be widely used in fields such as automotive industry, electric wire and material of construction.
Embodiment
To combine specific embodiment that the present invention is elaborated below.It is important to point out the embodiment that lifts just further specify of the present invention, be not restriction to protection domain of the present invention.
Embodiment 1
Present embodiment is the preparation of siliceous triazine macromolecular carbon forming agent and organic ceramic precursor.
, the 500mL four-hole boiling flask of reflux condensing tube, TM, whisking appliance and constant pressure funnel adds 36.8g cyanuric chloride and 50mL acetone in being housed; Reaction flask is put into abundant stirring of ice-water bath is uniformly dispersed cyanuric chloride; Controlled temperature is 0～2 ℃; Slowly drip 44.2g γ-An Bingjisanyiyangjiguiwan and sodium hydroxide solution (the 8g dissolution of sodium hydroxide is in 30mL zero(ppm) water) then while stirring, the temperature of control reaction system is 0～2 ℃ in the reaction process, and the pH value is 6; The dropping time is 2h, is added dropwise to complete continued reaction 5h.Be warming up to 50 ℃ then, slowly drip 12g quadrol and sodium hydroxide solution (the 10g dissolution of sodium hydroxide is in 40mL zero(ppm) water) again, pH value is 6, and the dropping time is 2h, is added dropwise to complete continued reaction 1h.The temperature of reaction that raises then, reaction 6h under reflux state, when pH value >=7, stopped reaction.After reaction finishes respectively with ethanol and acetone to product wash, suction filtration, obtaining white powder after the vacuum-drying is siliceous triazine macromolecular carbon forming agent (Si-TBM).
In the four-hole boiling flask that reflux condensing tube, TM, whisking appliance and constant pressure funnel 500mL are housed, add a certain amount of boric acid; Slowly drip octamethylcyclotetrasiloxane and tetraethoxy mixture again; Wherein, The mol ratio of octamethylcyclotetrasiloxane, boric acid and tetraethoxy is 15: 1: 1, reacts 6h down at 108 ℃.Reaction is washed product with zero(ppm) water and ethanol respectively after finishing, suction filtration, and final drying gets white solid particle organic ceramic precursor (pBSil).
The preparation method of said phosphorous nano imvite adds 40.0g sodium-based montmorillonite and 200mL ethanol in the four-hole boiling flask of 500mL, stirs down until forming homogeneous solution at 70 ℃; Subsequently, will be dissolved in 50mL alcoholic acid 10.0g Resorcinol (phenylbenzene) SULPHOSUCCINIC ACID ESTER and slowly drop in the montmorillonite suspension liquid, and be added dropwise to complete the back and react 10h down at 75 ℃; With reaction soln deposition, filtration, in 100 ℃ of vacuum drying ovens, dry to constant weight then, grinding is sieved, and obtains phosphorous nano imvite (P-MMT).
Embodiment 2～10 and Comparative Examples 1～3
This group embodiment is the preparation of halogen-free expansion type flame-proof polypropylene miser of the present invention.
According to prescription shown in the table 1; Be to add Vestolen PP 7052 (PP) earlier on 175 ℃ the open type dual-roller warm-up mill in the roller temperature; Treat to add oxidation inhibitor B215, phosphorus nitrogen expansion type combustion inhibitor, siliceous triazine macromolecular carbon forming agent (Si-TBM), tetramethylolmethane (PER), organic ceramic precursor (pBSil), phosphorous nano imvite (PMMT) successively behind its fusion bag roller; Slice behind the mixing 15min; Then on vulcanizing press in 180 ℃ of following hot pressing, room temperatures cold pressing, slice, on omnipotent sampling machine, make the fire-retardant PP sample that is used to test mechanical property and flame retardant properties again, test result is as shown in table 2.
Testing method
1, Mechanics Performance Testing: measure tensile strength and elongation at break according to GB/T 1840-1992; Measure the notched izod shock strength according to GB/T 1843-1996.
2, flame retardant properties test: limiting oxygen index(LOI) (LOI) is carried out test according to GB/T 2406-1993 standard, and specimen size is 120mm * 6.5mm * 3mm; Vertical combustion (UL-94) is carried out test according to ASTM D635 standard, and specimen size is 127mm * 12.7mm * 3.2mm.
3, water resistance test: place the standard test specimen that is used for the test of oxygen index and vertical combustion 70 ℃ zero(ppm) water to soak 168 hours, dry to constant weight with 100 ℃ at baking oven then, be used for the test of oxygen index and vertical combustion after the oven dry.
The experimental formula of table 1 embodiment 2～10 and comparative example 1～3
The test result of table 2 embodiment 2～10 and comparative example 1～3
Can see that from table 1 and table 2 it is good that the prepared halogen-free expansion type flame-proof polypropylene miser of the present invention has the combustion performance, characteristics such as good mechanical performance.Shown in embodiment 9; The fire retardant (12wt% melamine pyrophosphate, the siliceous triazine macromolecular carbon forming agent of 6wt%, 1wt% organic ceramic precursor and the phosphorous nano imvite of 1wt%) that adds 20wt% just can make the oxygen index of mixture reach 30.5; Through the UL94V-0 level; And good mechanical performance, wherein tensile strength is 31.7MPa, shock strength is 3.6kJ/m
2And the expansion type flame-retarding PP mixture (seeing comparative example 3) that adopts traditional method to prepare; The fire retardant oxygen index that adds 20wt% can only reach 26.0, can't test through vertical combustion, and mechanical property worsens serious; The stretching tensile strength has only 24.5MPa, and shock strength is 3.0kJ/m
2
It is worthy of note most that the prepared mixture water resistance of the present invention is given prominence to, immersion still can keep good flame retardant property after 168 hours in 70 ℃ zero(ppm) water, and like embodiment 9, water-fast test back oxygen index still can keep 29.2, through the UL94V-0 level; And the mixture (comparative example 1) that adopts traditional method to prepare, even add the fire retardant of 30wt%, flame retardant properties declines to a great extent after the water-fast test, can't reach the UL94V-0 level.
Claims (7)
1. a halogen-free expansion type flame-proof polypropylene miser is characterized in that, the predominant quantity umber is following:
70 ~ 80 parts of Vestolen PP 7052
12～18 parts of phosphorus nitrogen expansion type combustion inhibitors
5 ~ 15 parts of siliceous triazine macromolecular carbon forming agents
0.5～3 part of organic ceramic precursor
0.5～1.5 part of phosphorous nano imvite
0.05 ~ 0.3 part in oxidation inhibitor.
2. a kind of halogen-free expansion type flame-proof polypropylene miser according to claim 1; It is characterized in that; Said siliceous triazine macromolecular carbon forming agent is to be made through polycondensation by cyanuric chloride, quadrol and γ-An Bingjisanyiyangjiguiwan, and its molecular structure is following:
wherein: n=5 ~ 10.
3. a kind of halogen-free expansion type flame-proof polypropylene miser according to claim 1 is characterized in that said phosphorus nitrogen expansion type combustion inhibitor is a polyphosphoric acid melamine, a kind of in melamine pyrophosphate, melamine phosphate or the ammonium polyphosphate.
4. a kind of halogen-free expansion type flame-proof polypropylene miser according to claim 1 is characterized in that, the preparation method of said organic ceramic precursor is the mixture that in boric acid, slowly drips octamethylcyclotetrasiloxane and tetraethoxy; Wherein, The mol ratio of octamethylcyclotetrasiloxane, boric acid and tetraethoxy is 15:1:1, reacts 6h down at 108 ℃, with zero(ppm) water and washing with alcohol product; Suction filtration, the dry organic ceramic precursor that gets.
5. a kind of halogen-free expansion type flame-proof polypropylene miser according to claim 1; It is characterized in that; The preparation method of said phosphorous nano imvite adds 40.0g sodium-based montmorillonite and 200mL ethanol in the four-hole boiling flask of 500mL, stirs down until forming homogeneous solution at 70 ℃; Subsequently, will be dissolved in 50mL alcoholic acid 10.0g Resorcinol (phenylbenzene) SULPHOSUCCINIC ACID ESTER and slowly drop in the montmorillonite suspension liquid, and be added dropwise to complete the back and react 10h down at 75 ℃; With reaction soln deposition, filtration, in 100 ℃ of vacuum drying ovens, dry to constant weight then, grinding is sieved, and obtains phosphorous nano imvite.
6. a kind of halogen-free expansion type flame-proof polypropylene miser according to claim 1 is characterized in that said oxidation inhibitor is oxidation inhibitor B215, a kind of in antioxidant 1010 and the oxidation inhibitor 168.
7. the preparation method of the described a kind of halogen-free expansion type flame-proof polypropylene miser of claim 1; It is characterized in that; This method is: be to add Vestolen PP 7052 on 170～190 ℃ the open warm-up mill at two roll temperatures, treat its fusion bag roller after, add oxidation inhibitor, phosphorus nitrogen expansion type combustion inhibitor, siliceous triazine macromolecular carbon forming agent, organic ceramic precursor and phosphorous nano imvite successively; Mixing 10～15min can make the halogen-free expansion type flame-proof polypropylene miser.
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