CN1318495C - Process for preparing polyolefine/montmorillonite nano non-halogen flame-resisting material - Google Patents
Process for preparing polyolefine/montmorillonite nano non-halogen flame-resisting material Download PDFInfo
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- CN1318495C CN1318495C CNB200410050993XA CN200410050993A CN1318495C CN 1318495 C CN1318495 C CN 1318495C CN B200410050993X A CNB200410050993X A CN B200410050993XA CN 200410050993 A CN200410050993 A CN 200410050993A CN 1318495 C CN1318495 C CN 1318495C
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Abstract
The present invention relates to a process for preparing a nanometer fire-retardant halogen-free polyolefin/montmorillonite material. In the process, unmodified montmorillonite and a polar-group contained vinyl monomer are used for an in-situ reaction under processing conditions of the fire-retardant halogen-free polyolefin material to form the nanometer fire-retardant halogen-free polyolefin/montmorillonite material with intercalation structure, wherein the barrier effect and the nanometer effect of the intercalation structure of the montmorillonite synergize the fire retardance of the existing fire-retardant halogen-free polyolefin material as well as compensate the loss of the mechanical properties and the processing properties of the existing fire-retardant halogen-free polyolefin material, and the in-situ reaction process can structurally improve the compatibility between a halogen-free fire retardant, and the montmorillonite and polyolefin resin. The present invention overcomes the defects that organic montmorillonite modified by an organic intercalation agent is needed for the preparation of the existing nanometer composite material of polyolefin/montmorillonite and the mechanical properties and the processing properties of polyolefin are perished by the addition of the halogen-free fire retardant for the preparation of the fire-retardant halogen-free polyolefin material.
Description
Technical field
The present invention relates to technical field of nano material, be specifically related to a kind of polyolefin/montmorillonite non-halogen fire-retardant preparation methods.
Background technology
Existing polyolefine non-halogen fire-retardant material generally all is to give the polyolefine flame retardant properties by direct interpolation non-halogen fire retardant; Nano composite polymer-montmorillonoid material generally is by adding through the organic intercalation agent montmorillonite modified, makes organo montmorillonite form intercalation under certain condition in polymkeric substance or lift-off structure prepares nano composite polymer-montmorillonoid material.At present, the preparation method of polyolefine non-halogen fire-retardant material and nano composite polymer-montmorillonoid material relative merits separately are as follows:
1, existing polyolefine non-halogen fire-retardant material is to obtain flame retardant properties by direct interpolation non-halogen fire retardant, but, no matter be the higher phosphor-nitrogen expansion type non-halogen fire-retardant system of flame retarding efficiency, or the lower mineral-type non-halogen fire-retardant system of flame retarding efficiency, consistency between non-halogen fire retardant and polyolefin resin is all relatively poor, when obtaining flame retardant properties, infringement in various degree polyolefinic mechanical property and processing characteristics.
2, the polynite of using when existing nano composite polymer-montmorillonoid material prepares all is the organo montmorillonite through the organic intercalation agent modification, although organo montmorillonite can form intercalation or lift-off structure prepares nano composite polymer-montmorillonoid material in polymkeric substance under certain condition, every performance of polymkeric substance is significantly increased, but, technological line was long when existing organo montmorillonite prepared, technology is loaded down with trivial details, (price of polynite is about about 1000 yuan/ton to cause the price of organo montmorillonite very expensive, and the price of organo montmorillonite is up to more than 20000 yuan/ton), have a strong impact on the practical application of polynite, and in the production process of organo montmorillonite, have a large amount of waste water to produce, pollute surrounding enviroment.
3, the organic intercalation agent of existing organo montmorillonite use is generally inert substance, do not exist can with the functional group of polymer reaction, therefore, when adding in polymkeric substance as properties-correcting agent organo montmorillonite, there is poor, the difficult dispersive shortcoming of consistency with polyolefin resin, is difficult to reach the nano modification effect of expection.
Summary of the invention
The objective of the invention is to above-mentioned shortcoming at existing polyolefine non-halogen fire-retardant material and nano composite polymer-montmorillonoid material preparation method, a kind of polyolefin/montmorillonite non-halogen fire-retardant preparation methods is provided, this method adopts the polynite of non-modified and contains the vinyl monomer of polar group, by reaction in, form polyolefin/montmorillonite non-halogen fire-retardant material with intercalation configuration.Improve the consistency of fire retardant and polynite and polyolefin resin from structure.The blocking effect and the nano effect of montmorillonite intercalation structure both had synergism to the flame retardant properties that has the polyolefine non-halogen fire-retardant material now simultaneously, again existing polyolefine non-halogen fire-retardant material mechanical performance and processibility loss of energy were had compensating action.
Polyolefin/montmorillonite non-halogen fire-retardant preparation methods of the present invention is to use the vinyl monomer of polynite and polar functionalities, reaction in takes place under the processing conditions of polyolefine non-halogen fire-retardant material, the two key parts and the polyolefin resin generation graft reaction of the vinyl monomer of polar functionalities, polar group partly inserts the interlayer of polynite, obtains having the polyolefin/montmorillonite non-halogen fire-retardant material of intercalation configuration.
Not described polynite is the polynite of non-modified.
The non-halogen fire-retardant of polyolefin/montmorillonite more specifically preparation methods of the present invention comprises:---vinyl monomer of polypropylene, polynite, non-halogen fire retardant, initiator and polar functionalities etc. is mixed;
---said mixture under 150～200 ℃ of molten states mixing 5～40 minutes makes polyolefin/montmorillonite non-halogen fire-retardant material;
Above-mentioned non-halogen fire-retardant material prescription (weight part) is:
Polypropylene 100
Polynite 5～80
The vinyl monomer 5～40 of polar functionalities
Non-halogen fire retardant 0～100
Initiator 0.02～0.6
The optimum range of above-mentioned prescription is as follows:
Polypropylene 100
Polynite 10～50
The vinyl monomer 10～25 of polar functionalities
Non-halogen fire retardant 0～60
Initiator 0.1～0.3;
Wherein: 1. polyolefine is selected from polypropylene, high density polyethylene(HDPE), new LDPE (film grade), linear low density polyethylene, ultrahigh molecular weight polyethylene(UHMWPE), ethylene-propylene rubber(EPR), ethylene-vinyl acetate;
2. the vinyl monomer of polar functionalities is selected from one or more in vinylsiloxane class, vinylformic acid and ester thereof, methacrylic acid and ester thereof, dimethacrylate, Phthalic acid, diallyl ester, maleic anhydride and derivative thereof, fumaric acid anhydride and derivative thereof, vinyl acetate, vinyl cyanide, unsaturated fatty acids and ester thereof, the acrylamide isopolarity monomer;
3. non-halogen fire retardant is selected from inorganic aluminium hydroxide, magnesium hydroxide, magnesium oxide, zinc borate, red phosphorus, antimonous oxide, silicon-dioxide, molybdic oxide, ferric oxide, Yangization , cupric oxide etc. and organic one or more in the non-halogen fire retardants such as ammonium polyphosphate, trimeric cyanamide, terpolycyantoamino-formaldehyde resin, pentaerythritol bis (dihydrogen phosphate) melamine salt, tetramethylolmethane, tritolyl phosphate, trioctyl phosphate, triphenylphosphate;
4. initiator is selected from Diisopropyl azodicarboxylate, peroxidation phenyl-diformyl, ditertiary butyl peroxide, dicumyl peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2, a kind of in 5-two tert-butyl peroxy base hexanes, peroxidation two (2-toluyl) and the dilauroyl peroxide;
The vinyl monomer of polyolefine, polynite, non-halogen fire retardant, polar functionalities and initiator etc. can mix with kneader.
Mixture can use plastic industries such as twin-roll plastic mixing mill, single screw rod or twin screw extruder equipment commonly used mixing under molten state, makes polyolefin/montmorillonite non-halogen fire-retardant material.
The present invention compared with prior art has following advantage: the polynite that the present invention selects for use is the polynite of non-modified, utilize the response characteristic of polar functionalities vinyl monomer, reaction in takes place in the course of processing of polyolefine non-halogen fire-retardant material, and " on the spot " forms the non-halogen fire-retardant material with intercalation configuration, the blocking effect of montmorillonite intercalation structure and nano effect, both the flame retardant properties to existing polyolefine non-halogen fire-retardant material had synergism, again existing polyolefine non-halogen fire-retardant material mechanical performance and processibility loss of energy are had compensating action, and the reaction in process also can be improved consistency between non-halogen fire retardant and polynite and polyolefin resin from structure.The present invention had both overcome the shortcoming that must use when existing nano composite polymer-montmorillonoid material prepares through the organo montmorillonite of organic intercalation agent modification, had overcome again to add the shortcoming of damaging polyolefine mechanical property and processing characteristics when non-halogen fire retardant prepares the polyolefine non-halogen fire-retardant material.When containing the fire retardant of identical weight part, add polynite, the oxygen index that adopts the polyolefine non-halogen fire-retardant material that the present invention makes is higher by 3～5% than the non-halogen fire-retardant material of montmorillonoid-containing not, and flexural strength and notched Izod impact strength improve more than 20% than the non-halogen fire-retardant material of montmorillonoid-containing not.
Embodiment
Below by embodiment optimum implementation of the present invention is described.
Embodiment 1
1, polyolefin/montmorillonite non-halogen fire-retardant material prescription one:
Polypropylene (CF-501): 100 grams
Polynite: 75 grams
Methyl propenoic acid glycidyl ether-ether: 5 grams
Dicumyl peroxide (DCP): 0.03 gram
After various materials in the above-mentioned prescription are mixed with kneader, under 170～190 ℃ of molten states in twin-roll plastic mixing mill mixing 35 minutes, make level polypropylene/montmorillonoid non-halogen fire-retardant material, the content of polynite is 41.7% in this non-halogen fire-retardant material, the interlamellar spacing of polynite increases to 14.5 by 9.7 , increased by 4.8 , showing has intercalation configuration to form.The oxygen index of this non-halogen fire-retardant material is 27.4, and flexural strength is 48.8MPa, and notched Izod impact strength is 2.6KJ/m
2If adopt same procedure to be all the composite flame-retardant agent replacement polynite of 41.7% aluminium hydroxide and magnesium hydroxide with content, the polyacrylic oxygen index of prepared non-halogen fire-retardant has only 24.3, and flexural strength has only 38.2MPa, and notched Izod impact strength is 2.0KJ/m
2, illustrate that the level polypropylene/montmorillonoid non-halogen fire-retardant material that the present invention makes has better flame retardant effect and mechanical property.
2, polyolefin/montmorillonite non-halogen fire-retardant material prescription two:
Polypropylene (CF-501): 100 grams
Polynite: 9 grams
γ-methacryloyl propyl trimethoxy silicane: 25 grams
Methacrylic acid: 10 grams
Magnesium hydroxide: 25 grams
Aluminium hydroxide: 60 grams
Dicumyl peroxide (DCP): 0.5 gram
After various materials in the above-mentioned prescription are mixed with kneader, under 160～185 ℃ of molten states in twin-roll plastic mixing mill mixing 20 minutes, make level polypropylene/montmorillonoid non-halogen fire-retardant material, the content of aluminium hydroxide and magnesium hydroxide composite fire retardant is 37% in this non-halogen fire-retardant material, the content of polynite is 4%, the interlamellar spacing of polynite increases to 17.6 by 9.7 , has increased by 7.9 , and showing has intercalation configuration to form.The oxygen index of this non-halogen fire-retardant material is 27.8, and flexural strength reaches 49.6MPa, and notched Izod impact strength is 2.7KJ/m
2Be all 37% the aluminium hydroxide and the composite flame-retardant agent of magnesium hydroxide if adopt same procedure only to add content, do not add polynite, the polyacrylic oxygen index of prepared non-halogen fire-retardant has only 23.2, and flexural strength has only 39.4MPa, and notched Izod impact strength is 2.2KJ/m
2, as seen, the level polypropylene/montmorillonoid non-halogen fire-retardant material that the present invention makes is 4% o'clock at polynite content, and oxygen index has improved 4.6%, and flexural strength has improved 25%, and notched Izod impact strength has improved 20%, demonstrates better flame retardant effect and mechanical property.
3, polyolefin/montmorillonite non-halogen fire-retardant material prescription three:
Polypropylene (CF-501): 100 grams
Polynite: 16 grams
γ-methacryloyl propyl trimethoxy silicane: 12 grams
Maleic anhydride: 10 grams
Ammonium polyphosphate: 27 grams
Melamine: 6 grams
Tetramethylolmethane: 2.5 grams
Zinc borate: 2.5 grams
Peroxidation phenyl-diformyl (BPO): 0.2 gram
After various materials in the above-mentioned prescription are mixed with kneader, under 155～175 ℃ of molten states in twin-roll plastic mixing mill mixing 8 minutes, make level polypropylene/montmorillonoid non-halogen fire-retardant material, the expansion type flame-retarding system comprises that the total content of ammonium polyphosphate, melamine, tetramethylolmethane, zinc borate etc. is 21.6% in this non-halogen fire-retardant material, the content of polynite is 9%, the interlamellar spacing of polynite increases to 15.4 by 9.7 , has increased by 5.7 , and showing has intercalation configuration to form.The oxygen index of this non-halogen fire-retardant material is 31.8, and flexural strength reaches 48.6MPa, and notched Izod impact strength is 2.6KJ/m
2Be all 21.6% expansion type flame-retarding system if adopt same procedure only to add content, do not add polynite, the polyacrylic oxygen index of prepared non-halogen fire-retardant has only 28.6, and flexural strength has only 40.2MPa, and notched Izod impact strength is 2.1KJ/m
2, as seen, the level polypropylene/montmorillonoid non-halogen fire-retardant material that the present invention makes is 9% o'clock at the content of polynite, and oxygen index has improved 3.2%, and flexural strength and notched Izod impact strength have all improved 20%, demonstrate better flame retardant effect and mechanical property.
Claims (2)
1, a kind of polyolefin/montmorillonite non-halogen fire-retardant preparation methods is characterized in that comprising the steps:
---the vinyl monomer of polypropylene, polynite, non-halogen fire retardant, initiator and polar functionalities is mixed;
---said mixture under 150～200 ℃ of molten states mixing 5～40 minutes makes polyolefin/montmorillonite non-halogen fire-retardant material;
The weight part consumption of said components is:
Polypropylene 100
Polynite 5～80
The vinyl monomer 5～40 of polar functionalities
Non-halogen fire retardant 0～100
Initiator 0.02～0.6;
Wherein: the vinyl monomer of polar functionalities is selected from one or more in vinylsiloxane class, vinylformic acid and ester thereof, methacrylic acid and ester thereof, dimethacrylate, Phthalic acid, diallyl ester, maleic anhydride and derivative thereof, fumaric acid anhydride and derivative thereof, vinyl acetate, vinyl cyanide, unsaturated fatty acids and ester thereof, the acrylamide;
Non-halogen fire retardant is selected from one or more in aluminium hydroxide, magnesium hydroxide, magnesium oxide, zinc borate, red phosphorus, antimonous oxide, silicon-dioxide, molybdic oxide, ferric oxide, bismuth oxide, cupric oxide, ammonium polyphosphate, trimeric cyanamide, terpolycyantoamino-formaldehyde resin, pentaerythritol bis (dihydrogen phosphate) melamine salt, tetramethylolmethane, tritolyl phosphate, trioctyl phosphate, the triphenylphosphate;
Initiator is selected from Diisopropyl azodicarboxylate, peroxidation phenyl-diformyl, ditertiary butyl peroxide, dicumyl peroxide, di-isopropylbenzene hydroperoxide, 2,5-dimethyl-2,5-two tert-butyl peroxy base hexanes, peroxidation two (2-toluyl) or dilauroyl peroxide.
2, polyolefin/montmorillonite non-halogen fire-retardant preparation methods according to claim 1 is characterized in that the weight part consumption of described component is:
Polypropylene 100
Polynite 10～50
The vinyl monomer 10～25 of polar functionalities
Non-halogen fire retardant 0～60
Initiator 0.10～0.3.
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