CN105330967A - Polypropylene material modified by magnesium hydroxide crystal whiskers and preparation method of polypropylene material - Google Patents
Polypropylene material modified by magnesium hydroxide crystal whiskers and preparation method of polypropylene material Download PDFInfo
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- CN105330967A CN105330967A CN201510851925.1A CN201510851925A CN105330967A CN 105330967 A CN105330967 A CN 105330967A CN 201510851925 A CN201510851925 A CN 201510851925A CN 105330967 A CN105330967 A CN 105330967A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/08—Oxygen-containing compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5808—Measuring, controlling or regulating pressure or compressing force
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/58—Measuring, controlling or regulating
- B29C2043/5816—Measuring, controlling or regulating temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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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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Abstract
The invention provides a polypropylene material modified by magnesium hydroxide crystal whiskers and a preparation method of the polypropylene material. The material is mainly prepared from the following components in parts by weight: 100 parts of polypropylene resin, 0 to 40 parts (not including 0) of the magnesium hydroxide crystal whiskers, 0 to 3 parts (not including 0) of a lubricant and 0 to 3 parts (not including 0) of a stabilizer. The polypropylene material provided by the invention takes the polypropylene resin as a base material and takes the magnesium hydroxide crystal whiskers as a modifying agent; under specific technological conditions, the base material, the modifying agent and additives are mixed to prepare the polypropylene material modified by the magnesium hydroxide crystal whiskers; compared with a composite material prepared from common magnesium hydroxide and polypropylene, the breaking strength and elongation at break of the material are remarkably improved, and the flame retardant property of the material is better than that of the composite material prepared from the common magnesium hydroxide and the polypropylene.
Description
Technical field
The invention belongs to matrix material to receive, relate to a kind of polypropylene material and preparation method thereof, particularly relate to polypropylene material of a kind of magnesium hydroxide crystal whisker modification and preparation method thereof.
Background technology
Polypropylene (PP) is one of five large general-purpose plastics, and it has many premium propertiess, as high in fusing point (167 DEG C), heat-resisting, and goods used vapour is sterilized, density 0.90g/cm
3deng, be the lightest general-purpose plastics; It is corrosion-resistant, and intensity, rigidity and the transparency are all good etc. than polyethylene.Because its production cost is low, comprehensive mechanical property is good, and polypropylene is widely used in the fields such as chemical industry, chemical fibre, building, light industry and packaging.But polypropylene oxygen index is between 16 ~ 19, and melting zone is narrow, produces molten drop in combustion test, do not reach FV-O level, belong to inflammable material, this makes its application in the field such as electronics and electrical equipment be restricted.For this reason, in polypropylene material, fire retardant is usually added to improve its flame retardant properties.Research and development Halogen, low cigarette and nontoxic fire-retardant PP system are the problems that an existing great social benefit has again distinct economic.
21 century people particularly pay close attention to the research and development of multifunctional material and using, and to material, multi-functional and environmental-protecting performance requires more and more higher, and therefore many and high end materials of environmental protection of quality better, function is one of the research and development of current material circle and Main way of producing.
Magnesium hydroxide is used as the fire retardant of macromolecular material, have nontoxic, press down the feature such as cigarette and good flame retardation effect, present stage is widely used in PP goods, with obtained halogen-free flameproof product.And ordinary hydrogen magnesium oxide product adds in polymkeric substance as fire retardant and mainly contains two shortcomings: one is to play flame retardant effect, just the addition of magnesium hydroxide needs to play very much good flame retardant effect; Two is poor with the consistency of polymeric matrix.To obtain good flame retardant effect, the addition of magnesium hydroxide often needs to reach more than 50 parts (whisker quality/substrate qualities), and this can reduce mechanical property and the processing characteristics of matrix material greatly, is difficult to the specification of quality reaching actual use.So not change while strengthening magnesium hydroxide flame retardant effect or the mechanical property of not obvious reduction body material itself is one of the problem of solution of being eager at present.
CN102604230A discloses a kind of composite modified magnesium hydroxide/polypropylene high-impact resistant halogen-free flame-proof composite material, be made up of polypropylene, magnesium hydroxide, ethylene-vinyl acetate copolymer and vulcanizing agent and cocuring agent, this matrix material needs to add a large amount of magnesium hydroxides in preparation process just can reach flame retardant effect.
CN104987598A discloses a kind of polypropylene flame redardant modified plastics, and this polypropylene flame redardant modified plastics comprises the material of following weight part: polypropylene 100 ~ 120 parts, 1 ~ 10 part, calcium carbonate, glyceryl monostearate 0.8 ~ 3 part, three butoxyethyl phosphate 1 ~ 3 part, nano-aluminum hydroxide 1 ~ 2 part, nano-sized magnesium hydroxide 1 ~ 5 part, polyoxyethylene glycol 0.1 ~ 0.8 part; Although this material fire retardant addition is few, the consistency of its oxyhydroxide added and matrix is poor, result in the decline of material mechanical performance.
Research shows, magnesium hydroxide is remarkable to the Effect on Mechanical Properties of matrix material with the adhesive ability of polymeric matrix and the reunion degree of magnesium hydroxide, and magnesium hydroxide crystal pattern is one of key factor of these influence factors.Ordinary hydrogen magnesium oxide is hexagonal flake crystal, and crystal grain trends towards secondary aggregation, is a kind of strong polar compound, has hydrophilic and oleophobic, poor with the consistency of polymer molecule.When magnesium hydroxide is added in polymer materials, space can be produced at material interface, cause the mechanical mechanics property (mainly tensile strength and elongation at break) of material to decline.The special mechanical property of magnesium hydroxide crystal to body material of pattern has good reinforcing effect, but the different reinforcing effect of pattern is different.
For this reason, working out a kind of PP material having good flame-retardance energy and mechanical property concurrently is the problem needing solution badly.
Summary of the invention
For above-mentioned problems of the prior art, the invention provides polypropylene material of a kind of magnesium hydroxide crystal whisker modification and preparation method thereof, present invention incorporates the performances such as good heat-resisting, heat insulation, the adiabatic and enhancing of magnesium hydroxide crystal whisker, and the widespread use of PP material and inflammable feature, adopt magnesium hydroxide crystal whisker to carry out modification to polypropylene base-material, prepare tensile strength, shock strength and flame retardant properties all apparently higher than the polypropylene material of the magnesium hydroxide crystal whisker modification of ordinary hydrogen magnesium oxide/polypropylene composite material.
The present invention for base-material, take magnesium hydroxide crystal whisker as properties-correcting agent with common commercial polypropylene (PP) material, carries out mixing in proportion, make the polypropylene material of magnesium hydroxide crystal whisker modification under specific processing condition by base-material and properties-correcting agent.Obtained matrix material is compared with ordinary hydrogen magnesium oxide and the obtained matrix material of PP, and breaking tenacity and elongation at break are significantly improved, and flame retardant properties is also better than the matrix material that ordinary hydrogen magnesium oxide and PP obtain.
For reaching this object, the present invention by the following technical solutions:
First aspect, the invention provides a kind of polypropylene material of magnesium hydroxide crystal whisker modification, described material forms by weight primarily of following raw material:
Wherein, the weight part of magnesium hydroxide crystal whisker can be 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts or 40 parts etc.; The weight part of lubricant can be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts etc.; The weight part of stablizer can be 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts or 3 parts etc.
Wherein, described acrylic resin is the plain polypropylene granular feedstock that market is sold.
As preferred version of the present invention, described material forms by weight primarily of following raw material:
More preferably, described material forms by weight primarily of following raw material:
Wherein, of the present invention " primarily of " mean, except described component, other components can also be comprised, such as coupling agent etc., in addition, of the present invention " primarily of " can also replace with enclosed " by ... composition ".
As preferred version of the present invention, the diameter of described magnesium hydroxide crystal whisker is 0.1 ~ 3 μm, such as 0.1 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm or 3 μm etc.; Length-to-diameter ratio > 15, such as 20,25,30,35,40,45,50,55,60,65,70,75,80,85 or 90 and larger length-to-diameter ratio.
Preferably, the length-to-diameter ratio of described magnesium hydroxide crystal whisker is 80 ~ 100, such as 80,85,90,95 or 100 etc.
Preferably, purity >=95% of described magnesium hydroxide crystal whisker.
Preferably, the heat decomposition temperature of described magnesium hydroxide crystal whisker is 330 ~ 350 DEG C, such as 330 DEG C, 335 DEG C, 340 DEG C, 345 DEG C or 350 DEG C etc., specific surface area < 20m
2/ g, such as 18m
2/ g, 15m
2/ g, 13m
2/ g, 10m
2/ g, 7m
2/ g, 5m
2/ g or 3m
2/ g etc.
In the present invention, magnesium hydroxide crystal whisker carries out modification to polypropylene material, can play fire-retardant, to press down cigarette and enhancing mechanical property effect.This is because can be evenly distributed in PP material matrix compared with the whisker of big L/D ratio, when material is heated and reaches more than 330 ~ 350 DEG C, magnesium hydroxide crystal whisker just can decompose, and can avoid material combustion, and then serves fire retardation.
Further, the mechanism of magnesium hydroxide crystal whisker strongthener performance is:
The polypropylene material of magnesium hydroxide crystal whisker modification, in its Tensile Fracture Process, experienced by the process of a viscous deformation, interface debonding and brittle failure.Because magnesium hydroxide crystal whisker is single crystal, there is higher Young's modulus, after matrix material experienced by certain viscous deformation under external force, whisker starts to bear and absorb the external reactive force of major part, by whisker conduction its reactive force for matrix is greatly weakened, in certain scope, the whisker in matrix more and distribution more even, the reactive force that whisker bore and consumed is larger, and therefore the breaking tenacity of matrix material also will progressively strengthen.When tensile stress reaches enough large, composite material surface and inside thereof there will be many fine cracks and expand to multiple directions, when crack propagation is to the position at whisker place, because the Young's modulus of whisker is high, crackle is generally difficult to continue by original Directional Extension through whisker, crackle deflects and causes by-local forces to change direction, further consumption effect energy.Crackle after deflection needs to consume more energy because of the growth of extensions path, and these factors all cause the increase of Materials Fracture intensity.
As preferred version of the present invention, described lubricant is the combination of any one or at least two kinds in polyethylene wax, ethylene bis stearamide or stearic acid, described combination typical case but limiting examples have: the combined system of polyethylene wax and ethylene bis stearamide, ethylene bis stearamide and stearic combined system, polyethylene wax system, ethylene bis stearamide system and stearic acid system, more preferably polyethylene wax.
Preferably, described stablizer is Metallic stearates.
Preferably, described Metallic stearates is the combination of any one or at least two kinds in calcium stearate, Zinic stearas, Magnesium Stearate or sodium stearate, described combination typical case but limiting examples have: the combination of calcium stearate and Zinic stearas, the combination of Zinic stearas and Magnesium Stearate, the combination of Magnesium Stearate and sodium stearate, the combination of calcium stearate, Zinic stearas and Magnesium Stearate, the combination etc. of calcium stearate, Zinic stearas, Magnesium Stearate and sodium stearate, more preferably calcium stearate.
Second aspect, the invention provides the preparation method of the polypropylene material of above-mentioned magnesium hydroxide crystal whisker modification, and described method comprises banburying and compression moulding two processes.
As preferred version of the present invention, described internal mixing pass is as follows:
Take acrylic resin, magnesium hydroxide crystal whisker, lubricant and stablizer by formula ratio to add in Banbury mixer and mix, then extrude, be cooled to room temperature and obtain; Wherein, setting banburying temperature is 160 ~ 180 DEG C, and the banburying time is 10 ~ 20min, and rotor speed is 20 ~ 40r/min.
Wherein, banburying temperature can be 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C or 180 DEG C etc.; The banburying time can be 10min, 12min, 14min, 16min, 18min or 20min etc.; Rotor speed can be 20r/min, 22r/min, 24r/min, 26r/min, 28r/min, 30r/min, 32r/min, 34r/min, 36r/min, 38r/min or 40r/min etc.
Preferably, described banburying is carried out in rheometer, such as Haake torque rheometer.
Preferably, described banburying temperature is 170 DEG C, and the banburying time is 15min, and rotor speed is 30r/min.
As preferred version of the present invention, described compression moulding process comprises precompressed and hydraulic pressure.
Preferably, described compression moulding process is carried out in vulcanizing press.
Preferably, the temperature of described precompressed is 160 ~ 180 DEG C, such as 160 DEG C, 165 DEG C, 170 DEG C, 175 DEG C or 180 DEG C etc., more preferably 170 DEG C.
Preferably, described squeeze time is 20 ~ 40min, such as 20min, 25min, 30min, 35min or 40min etc., more preferably 30min.
Preferably, described hydraulic temperature is 170 ~ 190 DEG C, such as 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C or 190 DEG C etc., more preferably 180 DEG C.
Preferably, the described hydraulic pressure time is 0.5 ~ 2h, such as 0.5h, 1h, 1.5h or 2h etc., more preferably 1h;
Preferably, described hydraulic pressure is 5 ~ 15MPa, such as 5MPa, 7MPa, 10MP, 13MPa or 15MPa etc., more preferably 5 ~ 10Mpa.
The third aspect, the invention provides the another kind of preparation method of the polypropylene material of above-mentioned magnesium hydroxide crystal whisker modification, and namely adopt twin screw extruder to carry out the preparation of polypropylene material, preparation method is:
Take acrylic resin, magnesium hydroxide crystal whisker, lubricant and stablizer by formula ratio to mix, then join and carry out mixing in twin screw extruder, granulation obtains product.
As preferred version of the present invention, the processing temperature of described twin screw extruder is:
Head temperature: 190 ~ 210 DEG C, such as 190 DEG C, 195 DEG C, 200 DEG C, 205 DEG C or 210 DEG C etc.;
First district's temperature: 35 ~ 45 DEG C, such as 35 DEG C, 37 DEG C, 40 DEG C, 43 DEG C or 45 DEG C etc.;
Second district's temperature: 85 ~ 95 DEG C, such as 85 DEG C, 87 DEG C, 90 DEG C, 93 DEG C or 95 DEG C etc.;
3rd district's temperature: 130 ~ 140 DEG C, such as 130 DEG C, 133 DEG C, 135 DEG C, 137 DEG C or 140 DEG C etc.;
4th district's temperature: 150 ~ 160 DEG C, such as 150 DEG C, 153 DEG C, 155 DEG C, 157 DEG C or 160 DEG C etc.;
5th district's temperature: 165 ~ 175 DEG C, such as 165 DEG C, 167 DEG C, 170 DEG C, 173 DEG C or 175 DEG C etc.;
6th district's temperature: 185 ~ 195 DEG C, such as 185 DEG C, 187 DEG C, 190 DEG C, 193 DEG C or 195 DEG C etc.;
SECTOR-SEVEN temperature: 195 ~ 205 DEG C, such as 195 DEG C, 197 DEG C, 200 DEG C, 203 DEG C or 205 DEG C etc.;
Section Eight temperature: 205 ~ 215 DEG C, such as 205 DEG C, 207 DEG C, 210 DEG C, 213 DEG C or 215 DEG C etc.;
9th district's temperature: 205 ~ 215 DEG C, such as 205 DEG C, 207 DEG C, 210 DEG C, 213 DEG C or 215 DEG C etc.
Preferably, the processing temperature of described twin screw extruder is:
Head temperature: 200 DEG C; First district's temperature: 40 DEG C; Second district's temperature: 90 DEG C; 3rd district's temperature: 135 DEG C; 4th district's temperature: 155 DEG C; 5th district's temperature: 170 DEG C; 6th district's temperature: 190 DEG C; SECTOR-SEVEN temperature: 200 DEG C; Section Eight temperature: 210 DEG C; 9th district's temperature: 210 DEG C.
Compared with prior art, the present invention has following beneficial effect;
The present invention take magnesium hydroxide crystal whisker as properties-correcting agent, under specific processing condition, modification is carried out to polypropylene material, mechanical property and the flame retardant properties of making the polypropylene material of magnesium hydroxide crystal whisker modification are all obviously better than the magnesium oxide modified polypropylene composite materials material of ordinary hydrogen, its tensile strength can reach more than 10MPa, elongation at break can reach more than 2%, oxygen index can reach more than 21%, and the breaking tenacity of the magnesium oxide modified polypropylene composite materials material of ordinary hydrogen is 8.68Mpa, elongation at break is 0.84%, and oxygen index is 21%; The polypropylene material of the magnesium hydroxide crystal whisker modification prepared by the present invention overcomes in prior art the problem that the mechanical property that adopts a large amount of ordinary hydrogen magnesium oxide to cause polypropylene material modification and processing characteristics decline, and has good application prospect.
Embodiment
Below in conjunction with several specific embodiments; exemplary illustration and help understand the present invention further; but embodiment detail is only in order to the present invention is described; do not represent the present invention and conceive lower whole technical scheme; therefore should not be construed as the technical scheme total to the present invention to limit, some are In the view of technician, and the unsubstantiality not departing from inventive concept is changed; such as simply change with the technical characteristic with same or similar technique effect or replace, all belonging to scope.
(1) to carry out the condition that mechanical property (as tensile strength and elongation at break) tests as follows for following embodiment and comparative example products obtained therefrom:
Experimental installation: Instron-5569 universal testing machine
Ambient test conditions: temperature 23 ± 2 DEG C, relative humidity 50 ± 5%
Testing standard: GB1040-79
(2) following embodiment and comparative example products obtained therefrom all adopt oxygen index to carry out the size of evaluating material fire retardancy.
The principle of described oxygen index test is: make sample be in the nitrogen of flowing and the mixed atmosphere of oxygen, measure minimum oxygen concn when just can maintain smooth combustion, in gas mixture, the percent by volume of oxygen level just represents oxygen index.
The described oxygen index test oxygen index measurer that uses, its structure consists of glass combustion barrel, style folder and flow and Measurement and Control System.Wherein, be one deck granulated glass sphere bottom combustion barrel, in order to smooth air; Layer of metal net is arranged at granulated glass sphere top, in order to carry dropping during sample burning.During test, sample is vertically fixed in combustion barrel, oxygen-nitrogen mixture stream is passed through from bottom to top, lights sample top, clock simultaneously and observe sample burning length, then with defined according to compared with.
Embodiment 1: a kind of preparation of polypropylene material of magnesium hydroxide crystal whisker modification
(1) the banburying temperature arranging rheometer is 170 DEG C, the banburying time is 15min, rotor speed is 30r/min, take the acrylic resin of 100 parts by formula ratio, (its diameter is 0.1 ~ 0.3 μm to 30 parts of magnesium hydroxide crystal whiskers, length-to-diameter ratio is 80 ~ 90), 1 part of stearic acid and 1 part of calcium stearate pour in Haake torque rheometer, mix, then extrude, be cooled to room temperature;
(2) first vulcanizing press is carried out precompressed, setting precompressed temperature is 170 DEG C, and squeeze time is 30min, after precompressed, reconcile temperature control knob, setting hydraulic temperature is 180 DEG C, after plate temperature is stable, the sample that step (1) obtains is placed on flat board, starts hydraulic pressure button, flat board is pressed, is forced into 5 ~ 10MPa, pressurize 1h, then heating is stopped, be cooled to room temperature, take out sample by after pressure recovery, with hacksaw, sample is sawn into rectangular product.
Carry out mechanical property (tensile strength and elongation at break) test and oxygen index test to products obtained therefrom, test result is listed in table 1.
Embodiment 2: a kind of preparation of polypropylene material of magnesium hydroxide crystal whisker modification
(1) the banburying temperature arranging rheometer is 160 DEG C, the banburying time is 20min, rotor speed is 40r/min, take the acrylic resin of 100 parts by formula ratio, (its diameter is 2.5 ~ 3 μm to 10 parts of magnesium hydroxide crystal whiskers, length-to-diameter ratio is 90 ~ 100), 2 parts of ethylene bis stearamides and 2 parts of Zinic stearass pour in Haake torque rheometer, mix, then extrude, be cooled to room temperature;
(2) first vulcanizing press is carried out precompressed, setting precompressed temperature is 160 DEG C, and squeeze time is 40min, after precompressed, reconcile temperature control knob, setting hydraulic temperature is 170 DEG C, after plate temperature is stable, the sample that step (1) obtains is placed on flat board, starts hydraulic pressure button, flat board is pressed, is forced into 10 ~ 15MPa, pressurize 2h, then heating is stopped, be cooled to room temperature, take out sample by after pressure recovery, with hacksaw, sample is sawn into rectangular product.
Carry out mechanical property (tensile strength and elongation at break) test and oxygen index test to products obtained therefrom, test result is listed in table 1.
Embodiment 3: a kind of preparation of polypropylene material of magnesium hydroxide crystal whisker modification
Except the banburying temperature arranging rheometer in step (1) is 180 DEG C, the banburying time is 10min, rotor speed is 20r/min, acrylic resin, 20 parts of magnesium hydroxide crystal whiskers (its diameter is 1.5 ~ 2.0 μm, and length-to-diameter ratio is 85 ~ 90), 3 parts of polyethylene waxs and 3 parts of Magnesium Stearates of 100 parts are taken by formula ratio; In step (2), precompressed temperature is 180 DEG C, and squeeze time is 20min, and hydraulic temperature is 190 DEG C, and outside pressurize 0.5h, other steps are all in the same manner as in Example 1, obtained desired product.
Carry out mechanical property (tensile strength and elongation at break) test and oxygen index test to products obtained therefrom, test result is listed in table 1.
Embodiment 4: a kind of preparation of polypropylene material of magnesium hydroxide crystal whisker modification
Twin screw extruder is adopted to carry out the preparation of polypropylene material:
Take 100 parts of acrylic resins by formula ratio, 40 parts of magnesium hydroxide crystal whiskers, 1 part of stearic acid, 1 part of sodium stearate and 1 part of coupling agent mix, then join carry out in twin screw extruder mixing, granulation obtains product, and wherein the processing temperature of twin screw extruder is: head temperature: 200 DEG C; First district's temperature: 40 DEG C; Second district's temperature: 90 DEG C; 3rd district's temperature: 135 DEG C; 4th district's temperature: 155 DEG C; 5th district's temperature: 170 DEG C; 6th district's temperature: 190 DEG C; SECTOR-SEVEN temperature: 200 DEG C; Section Eight temperature: 210 DEG C; 9th district's temperature: 210 DEG C.
Carry out mechanical property (tensile strength and elongation at break) test and oxygen index test to products obtained therefrom, test result is listed in table 1.
Embodiment 5:
Except the processing temperature of twin screw extruder is: head temperature: 190 DEG C; First district's temperature: 35 DEG C; Second district's temperature: 85 DEG C; 3rd district's temperature: 130 DEG C; 4th district's temperature: 150 DEG C; 5th district's temperature: 165 DEG C; 6th district's temperature: 185 DEG C; SECTOR-SEVEN temperature: 195 DEG C; Section Eight temperature: 205 DEG C; 9th district's temperature: outside 205 DEG C, unclassified stores consumption and operation steps are all identical with embodiment 4.
Embodiment 6:
Except the processing temperature of twin screw extruder is: head temperature: 210 DEG C; First district's temperature: 45 DEG C; Second district's temperature: 95 DEG C; 3rd district's temperature: 140 DEG C; 4th district's temperature: 160 DEG C; 5th district's temperature: 175 DEG C; 6th district's temperature: 195 DEG C; SECTOR-SEVEN temperature: 205 DEG C; Section Eight temperature: 215 DEG C; 9th district's temperature: outside 215 DEG C, unclassified stores consumption and operation steps are all identical with embodiment 4.
Comparative example 1:
Except magnesium hydroxide crystal whisker being replaced to except the common magnesium hydroxide of equivalent, the consumption of unclassified stores and preparation process are all in the same manner as in Example 1, obtained carries out mechanical property (tensile strength and elongation at break) test and oxygen index test, and test result is listed in table 1.
Comparative example 2:
Except not adding except magnesium hydroxide crystal whisker, the consumption of unclassified stores and preparation process are all in the same manner as in Example 1, and obtained carries out mechanical property (tensile strength and elongation at break) test and oxygen index test, and test result is listed in table 1.
Table 1: embodiment 1-4 and comparative example 1-2 performance test table
Fracture rapidly after the polypropylene material of gained magnesium hydroxide crystal whisker modification in embodiment 1-4 is cooled at-40 DEG C, S-3400N type high resolution scanning electron microscope is utilized to observe matrix material fracture, can see when magnesium hydroxide crystal whisker weight part is below 40 parts, magnesium hydroxide crystal whisker can be scattered in PP base-material more uniformly and length-to-diameter ratio keeps better.Be understood that, just because of magnesium hydroxide crystal whisker being uniformly distributed in body material, just make the mechanical property of matrix material obtain obvious improvement.
The result of integrated embodiment 1-4 and comparative example 1-2 can be found out, the present invention take magnesium hydroxide crystal whisker as properties-correcting agent, under specific processing condition, modification is carried out to polypropylene material, mechanical property and the flame retardant properties of making the polypropylene material of magnesium hydroxide crystal whisker modification are all obviously better than the magnesium oxide modified polypropylene composite materials material of ordinary hydrogen, its tensile strength can reach more than 10MPa, elongation at break can reach more than 2%, oxygen index can reach more than 21%, and the breaking tenacity of the magnesium oxide modified polypropylene composite materials material of ordinary hydrogen is 8.68Mpa, elongation at break is 0.84%, oxygen index is 21%, therefore, the polypropylene material of the magnesium hydroxide crystal whisker modification prepared by the present invention overcomes in prior art the problem that the mechanical property that adopts a large amount of ordinary hydrogen magnesium oxide to cause polypropylene material modification and processing characteristics decline, and has good application prospect.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a polypropylene material for magnesium hydroxide crystal whisker modification, is characterized in that, described material forms by weight primarily of following raw material:
2. polypropylene material according to claim 1, is characterized in that, described material forms by weight primarily of following raw material:
3. polypropylene material according to claim 1 and 2, is characterized in that, described material forms by weight primarily of following raw material:
4. the polypropylene material according to any one of claim 1-3, is characterized in that, the diameter of described magnesium hydroxide crystal whisker is 0.1 ~ 3 μm, length-to-diameter ratio > 15;
Preferably, the length-to-diameter ratio of described magnesium hydroxide crystal whisker is 80 ~ 100;
Preferably, purity >=95% of described magnesium hydroxide crystal whisker;
Preferably, the heat decomposition temperature of described magnesium hydroxide crystal whisker is 330 ~ 350 DEG C, specific surface area < 20m
2/ g.
5. the polypropylene material according to any one of claim 1-4, is characterized in that, described lubricant is the combination of any one or at least two kinds in polyethylene wax, ethylene bis stearamide or stearic acid, more preferably polyethylene wax;
Preferably, described stablizer is Metallic stearates;
Preferably, described Metallic stearates is the combination of any one or at least two kinds in calcium stearate, Zinic stearas, Magnesium Stearate or sodium stearate, more preferably calcium stearate.
6. the preparation method of the polypropylene material according to any one of claim 1-5, is characterized in that, described method comprises banburying and compression moulding two processes.
7. preparation method according to claim 6, is characterized in that, described internal mixing pass is as follows:
Take acrylic resin, magnesium hydroxide crystal whisker, lubricant and stablizer by formula ratio to add in Banbury mixer and mix, then extrude, be cooled to room temperature and obtain; Wherein, setting banburying temperature is 160 ~ 180 DEG C, and the banburying time is 10 ~ 20min, and rotor speed is 20 ~ 40r/min;
Preferably, described banburying is carried out in rheometer;
Preferably, described banburying temperature is 170 DEG C, and the banburying time is 15min, and rotor speed is 30r/min.
8. the preparation method according to claim 6 or 7, is characterized in that, described compression moulding process comprises precompressed and hydraulic pressure;
Preferably, described compression moulding process is carried out in vulcanizing press;
Preferably, the temperature of described precompressed is 160 ~ 180 DEG C, more preferably 170 DEG C;
Preferably, described squeeze time is 20 ~ 40min, more preferably 30min;
Preferably, described hydraulic temperature is 170 ~ 190 DEG C, more preferably 180 DEG C;
Preferably, the described hydraulic pressure time is 0.5 ~ 2h, more preferably 1h;
Preferably, described hydraulic pressure is 5 ~ 15MPa, more preferably 5 ~ 10Mpa.
9. the preparation method of the polypropylene material according to any one of claim 1-5, is characterized in that, adopt twin screw extruder to carry out the preparation of polypropylene material, preparation method is:
Take acrylic resin, magnesium hydroxide crystal whisker, lubricant and stablizer by formula ratio to mix, then join and carry out mixing in twin screw extruder, granulation obtains product.
10. preparation method according to claim 9, is characterized in that, the processing temperature of described twin screw extruder is:
Head temperature: 190 ~ 210 DEG C; First district's temperature: 35 ~ 45 DEG C; Second district's temperature: 85 ~ 95 DEG C; 3rd district's temperature: 130 ~ 140 DEG C; 4th district's temperature: 150 ~ 160 DEG C; 5th district's temperature: 165 ~ 175 DEG C; 6th district's temperature: 185 ~ 195 DEG C; SECTOR-SEVEN temperature: 195 ~ 205 DEG C; Section Eight temperature: 205 ~ 215 DEG C; 9th district's temperature: 205 ~ 215 DEG C;
Preferably, the processing temperature of described twin screw extruder is:
Head temperature: 200 DEG C; First district's temperature: 40 DEG C; Second district's temperature: 90 DEG C; 3rd district's temperature: 135 DEG C; 4th district's temperature: 155 DEG C; 5th district's temperature: 170 DEG C; 6th district's temperature: 190 DEG C; SECTOR-SEVEN temperature: 200 DEG C; Section Eight temperature: 210 DEG C; 9th district's temperature: 210 DEG C.
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| CN108440833A (en) * | 2018-02-24 | 2018-08-24 | 河南长兴实业有限公司 | High temperature resistant container bag |
| CN111423657A (en) * | 2020-04-01 | 2020-07-17 | 苏州新华美塑料有限公司 | Low-halogen flame-retardant polypropylene composition and preparation method thereof |
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| CN111423657A (en) * | 2020-04-01 | 2020-07-17 | 苏州新华美塑料有限公司 | Low-halogen flame-retardant polypropylene composition and preparation method thereof |
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