CN117700915A - Matte environment-friendly PP composite material and processing technology thereof - Google Patents
Matte environment-friendly PP composite material and processing technology thereof Download PDFInfo
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- CN117700915A CN117700915A CN202311445475.7A CN202311445475A CN117700915A CN 117700915 A CN117700915 A CN 117700915A CN 202311445475 A CN202311445475 A CN 202311445475A CN 117700915 A CN117700915 A CN 117700915A
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000012545 processing Methods 0.000 title claims abstract description 25
- 238000005516 engineering process Methods 0.000 title claims abstract description 14
- 239000004743 Polypropylene Substances 0.000 claims abstract description 86
- 229920001155 polypropylene Polymers 0.000 claims abstract description 65
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 55
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 55
- -1 aminosiloxane Chemical class 0.000 claims abstract description 40
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 30
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 30
- 241000208202 Linaceae Species 0.000 claims abstract description 29
- 235000004431 Linum usitatissimum Nutrition 0.000 claims abstract description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 27
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 17
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 20
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000005047 Allyltrichlorosilane Substances 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 7
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000001746 injection moulding Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 30
- 239000003063 flame retardant Substances 0.000 abstract description 30
- 239000000463 material Substances 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 11
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 abstract description 5
- 238000005507 spraying Methods 0.000 abstract description 5
- 239000004254 Ammonium phosphate Substances 0.000 abstract description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract description 3
- 235000019289 ammonium phosphates Nutrition 0.000 abstract description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 241000196324 Embryophyta Species 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 9
- 238000005452 bending Methods 0.000 description 7
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 229920013822 aminosilicone Polymers 0.000 description 4
- 239000011151 fibre-reinforced plastic Substances 0.000 description 4
- 239000006224 matting agent Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical group [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of PP composite materials, and discloses a matte environment-friendly PP composite material and a processing technology thereof, wherein flax fibers are natural plant fibers, can be naturally degraded, and can not only protect the environment but also enhance the mechanical properties of PP after being blended with PP; the aminosiloxane grafted PP has a stable cage structure, is combined with the phosphoric acid functionalized carbon nano tube with large specific surface area to form a nitrogen-phosphorus-silicon-containing ammonium phosphate flame-retardant system, and the interface of the two is tightly combined, so that not only can the dispersibility in the PP be improved, but also the thermal stability of the expanded carbon layer at high temperature can be improved, and the synergistic flame-retardant effect is obvious; the matte agent basic magnesium sulfate whisker increases micro convex-concave formed on the surface of the PP material, increases diffuse reflection of light rays, and gradually reduces surface glossiness, so that a matte effect is achieved, a spraying process of the material is avoided, environmental pollution is reduced, and the prepared polypropylene composite material has excellent comprehensive performance.
Description
Technical Field
The invention relates to the technical field of PP composite materials, in particular to a matte environment-friendly PP composite material and a processing technology thereof.
Background
Polypropylene (PP) is a crystalline polymer with regular structure and easy processing and forming, and is widely applied to the fields of construction, machinery, automobiles and the like, and is the thermoplastic plastic with the most application and the most wide application at present due to good processing property, high strength and high wear resistance; however, polypropylene is extremely easy to burn, and after burning, molten drops are generated, so that flame spread can not be realized, and the application field with high requirements on flame retardance cannot be met.
In the prior art, flame retardant is generally added to improve the flame retardant property of polypropylene, but the conventional flame retardant has larger polarity and poor compatibility with polypropylene, is easy to separate out and migrate to the surface of the material in the process of storing or using the flame retardant polymer material, and can only play a flame retardant effect when a large amount of flame retardant is added, so that the flame retardant property is required to be further improved; there are also many techniques to flame-retardant polypropylene using intumescent flame retardant systems compounded of polyphosphoric acid amine, pentaerythritol and melamine, but because of the opposite polarity between polypropylene and intumescent flame retardant particles, the intumescent flame retardant has poor compatibility and uneven dispersion in polypropylene, thus causing the intumescent flame retardant to easily agglomerate and reducing the flame retardant and mechanical properties of the composite material.
The allyl silicate trimethylol methylamine cage-shaped ester prepared by the invention has a stable cage-shaped structure, is melt-grafted with PP, avoids the problem of uneven dispersion, and is mixed and extruded with phosphoric acid functionalized carbon nano-tubes, matt agent basic magnesium sulfate whisker and modified flax fiber to obtain the polypropylene composite material with strong flame retardant property, matt and environmental protection.
Disclosure of Invention
The invention solves the technical problems that:
aiming at the defects of the prior art, the invention provides a matte environment-friendly PP composite material and a processing technology thereof, which solve the problem that the PP material is extremely easy to burn in the use process.
Aiming at the problems, the technical scheme of the invention is as follows:
a processing technology of a matte environment-friendly PP composite material, which comprises the following steps:
(1) Polypropylene is structured intoAdding allyl silicate trimethylol methylamine cage ester and initiator dicumyl peroxide into a double screw extruder for melt grafting, extruding, cooling, drying and granulating to obtain aminosiloxane grafted PP.
(2) Adding the hydroxylated carbon nano tube and triethylamine into tetrahydrofuran, dispersing for 0.5-1.5h under ice water bath, dripping phosphorus trichloride and tetrahydrofuran, refluxing for 16-32h at 70-90 ℃, cooling, adding sodium hydroxide aqueous solution, adjusting pH to 7-8, hydrolyzing for 2-6h at 55-70 ℃, filtering, then deionized water, and drying to obtain the phosphoric acid functionalized carbon nano tube.
(3) Adding aminosiloxane grafted PP, phosphoric acid functionalized carbon nano tube, matt agent basic magnesium sulfate whisker, modified flax fiber and antioxidant into a high-speed mixer, mixing at high speed, adding into a double-screw extruder, carrying out blending extrusion, and then carrying out injection molding under the pressure of 50-60MPa and the temperature of 190-220 ℃ to obtain the matt environment-friendly PP composite material.
Preferably, the mass ratio of each substance in the step (1) is as follows: PP, allyl silicate tris (hydroxymethyl) methylamine cage ester, dicumyl peroxide=100 (5-25) and (2-6).
Preferably, the temperature of the first region to the fifth region of the extruder in the step (1) is 170-180 ℃, 180-190 ℃, 190-200 ℃, 195-205 ℃, 190-200 ℃ and 5-10min of melt grafting time, and the screw rotating speed is 150-170r/min.
Preferably, the mass ratio of each substance in the step (2) is as follows: hydroxylated carbon nanotube, triethylamine, phosphorus trichloride=1, (30-40) and (12-18).
Preferably, the mass ratio of each substance in the step (3) is as follows: the aminosiloxane grafted PP is phosphoric acid functionalized carbon nano tube, the matte agent basic magnesium sulfate whisker is modified flax fiber=100 (0.5-5), 2-8 and 15-35.
Preferably, in the step (3), the extrusion processing temperature is 195-205 ℃, 220-230 ℃, 215-225 ℃, 200-210 ℃ and the temperature of the machine head is 200-220 ℃, the screw rotating speed is 210-230r/min, and the feeding speed is 60-75r/min.
Preferably, the processing technology of the allyl silicate trimethylol methylamine cage-like ester in the step (1) comprises the following steps: adding tris (hydroxymethyl) aminomethane, triethylamine and dioxane into a reaction flask carrying a dropping funnel and a reflux condenser, uniformly stirring, protecting by nitrogen, dropwise adding allyl trichlorosilane at 25-40 ℃, stirring for reaction after the dropwise adding is finished, filtering while the reaction is finished, and washing a filter cake by acetone to obtain the allyl silicate tris (hydroxymethyl) methylamine cage-shaped ester. The preparation process comprises the following steps:
preferably, the mass ratio of the substances is as follows: tris (hydroxymethyl) aminomethane: triethylamine: allyl trichlorosilane = 100 (80-96): 140-170).
Preferably, the reaction temperature is 60-80 ℃ and the reaction time is 6-10h.
The beneficial technical effects of the invention are as follows:
firstly, carrying out a reaction between trimethylol aminomethane and allyl trichlorosilane to obtain allyl silicate trimethylol methylamine cage-shaped ester, then carrying out melt grafting on allyl and PP to obtain aminosiloxane grafted PP, then carrying out a reaction between a hydroxylated carbon nano tube and phosphorus trichloride, then carrying out hydrolysis in a sodium hydroxide aqueous solution to obtain a phosphoric acid functionalized carbon nano tube, utilizing the amino group of the allyl silicate trimethylol methylamine cage-shaped ester and the phosphate group of the phosphoric acid functionalized carbon nano tube to form a nitrogen-phosphorus-silicon expansion flame-retardant ammonium phosphate system, and then blending with a matte agent basic magnesium sulfate whisker and modified flax fiber to obtain the matte environment-friendly PP composite material.
The hydroxylated carbon nano tube has larger specific surface area, can be uniformly dispersed in a polypropylene matrix after phosphoric acid functionalization, has tight interface combination, not only can improve the dispersibility in PP, but also can improve the thermal stability of the expanded carbon layer at high temperature and increase the amount of residues at high temperature; the amino groups of the phosphorylated carbon nano tube and the aminosilicone grafted PP form an ammonium phosphate structure, so that the interfacial force between the carbon nano tube and the polypropylene is enhanced, the dispersibility of the carbon nano tube between the polypropylene matrixes is better, the interfacial strength is higher, and the tensile modulus and the bending strength of the composite material are improved.
The allyl silicate trimethylol methylamine cage-shaped ester has a stable cage-shaped structure, and after being combined with the PP melt grafting and phosphoric acid functionalized carbon nano tube, the allyl silicate trimethylol methylamine cage-shaped ester forms an expansion flame-retardant system containing nitrogen, phosphorus and silicon, has high content of effective flame-retardant elements, can effectively exert the synergistic flame-retardant effect of each element, and achieves the purposes of reducing the consumption of flame retardant and improving the flame-retardant effect.
The addition of the basic magnesium sulfate whisker serving as a matte agent increases micro convex-concave formed on the surface of the PP material, increases diffuse reflection of light rays and gradually reduces the surface glossiness, so that the matte effect is achieved, the spraying process of the material is avoided, the cost can be greatly reduced, the environmental pollution and the harm to human bodies caused by the spraying process can be reduced, and the prepared polypropylene composite material has excellent comprehensive performance.
The flax fiber is natural plant fiber, volatile matters harmful to human bodies can not be emitted during processing, the natural degradation can be realized, the attachments on the surface of the flax fiber treated by NaOH are obviously reduced, the fiber becomes easy to separate, the modified flax fiber is overlapped into a net structure in the composite material, the PP is supported, the plastic deformation generated by the PP is limited, and the rigidity and the hardness of the composite material are improved.
Drawings
FIG. 1 is a reaction mechanism for the preparation of phosphoric acid functionalized carbon nanotubes.
Detailed Description
Hereinafter, preferred examples of the invention will be described in detail. The examples are presented for better illustration of the invention and are not intended to be limiting. Insubstantial modifications and adaptations of the embodiments in accordance with the summary of the invention remain within the scope of the invention.
Preparation of hydroxylated carbon nanotubes: 500mg of carbon nanotubes and 20mL of concentrated sulfuric acid were added to the reaction flask, stirred at room temperature for 24 hours, then 20mL of concentrated nitric acid was added to the flask, stirred at 140℃under reflux for 30 minutes, washed with deionized water, and dried to obtain hydroxylated carbon nanotubes.
Preparing modified flax fibers: immersing the flax fibers in 5% sodium hydroxide aqueous solution for 30min, washing with deionized water, adding 1% acetic acid for neutralization, washing with deionized water again, and drying to obtain the modified flax fibers.
Preparation of a matte environment-friendly PP composite material:
(1) 100g of tris (hydroxymethyl) aminomethane, 80-96g of triethylamine and dioxane are added into a reaction flask carrying a dropping funnel and a reflux condenser, the mixture is stirred uniformly, 140-170g of allyl trichlorosilane is dripped under the protection of nitrogen at the temperature of 25-40 ℃, after the dripping is finished, the mixture is reacted for 6-10 hours at the temperature of 60-80 ℃, the mixture is filtered when the mixture is hot, and a filter cake is washed by acetone to obtain the allyl silicate tris (hydroxymethyl) methylamine cage.
(2) 100g of polypropylene and 5 to 25g of polypropylene are structured asAdding allyl silicate trimethylol methylamine cage ester and 2-6g initiator dicumyl peroxide into a double screw extruder for melt grafting, wherein the temperatures from one region to five regions of the extruder are respectively 170-180 ℃, 180-190 ℃, 190-200 ℃, 195-205 ℃, 190-200 ℃, the melt grafting time is 5-10min, the screw rotating speed is 150-170r/min, and obtaining the aminosiloxane grafted PP after extrusion, cooling, drying and granulating.
(3) Adding 1g of hydroxylated carbon nano tube and 30-40g of triethylamine into tetrahydrofuran, performing ultrasonic dispersion for 0.5-1.5h under ice water bath, dropwise adding 12-18g of phosphorus trichloride and tetrahydrofuran, refluxing for 16-32h at 70-90 ℃, cooling, adding sodium hydroxide aqueous solution, adjusting pH to 7-8, hydrolyzing for 2-6h at 55-70 ℃, filtering, then deionized water, and drying to obtain the phosphoric acid functionalized carbon nano tube.
(4) 100g of aminosiloxane grafted PP, 0.5-5g of phosphoric acid functionalized carbon nano tube, 2-8g of matte agent basic magnesium sulfate whisker, 15-35g of modified flax fiber and an antioxidant are added into a high-speed stirrer to be mixed at high speed, then the mixture is added into a double-screw extruder to be blended and extruded, the extrusion processing temperature is 195-205 ℃, 220-230 ℃, 215-225 ℃, 200-210 ℃, the machine head temperature is 200-220 ℃, the screw rotating speed is 210-230r/min, the feeding speed is 60-75r/min, and then the injection molding is carried out under the conditions that the pressure is 50-60MPa and the temperature is 190-220 ℃ to obtain the matte environment-friendly PP composite material.
Example 1
(1) 15g of tris (hydroxymethyl) aminomethane, 14.25g of triethylamine and dioxane are added into a reaction flask carrying a dropping funnel and a reflux condenser, the mixture is stirred uniformly, 24g of allyl trichlorosilane is added dropwise at 35 ℃ under the protection of nitrogen, after the dropwise addition is finished, the reaction is carried out for 9 hours at 70 ℃, the mixture is filtered while the mixture is hot, and a filter cake is washed by acetone to obtain the allyl silicate tris (hydroxymethyl) methylamine cage.
(2) 100g of polypropylene and 5g of structure areAdding allyl silicate trimethylol methylamine cage ester and 2g initiator dicumyl peroxide into a double screw extruder for melt grafting, wherein the temperatures of a first region and a fifth region of the extruder are 15 ℃, 185 ℃, 195 ℃, 205 ℃, 190 ℃ respectively, the melt grafting time is 8min, the screw rotating speed is 160r/min, and obtaining the aminosiloxane grafted PP after extrusion, cooling, drying and granulating.
(3) Adding 5g of hydroxylated carbon nano tube and 175g of triethylamine into tetrahydrofuran, performing ultrasonic dispersion for 1h in an ice water bath, dropwise adding 80g of phosphorus trichloride and tetrahydrofuran, refluxing for 24h at 85 ℃, cooling, adding a sodium hydroxide aqueous solution, adjusting pH to 8, hydrolyzing for 5h at 60 ℃, filtering, then deionized water, and drying to obtain the phosphoric acid functionalized carbon nano tube.
(4) 100g of aminosiloxane grafted PP, 0.5g of phosphoric acid functionalized carbon nano tube, 2g of matte agent basic magnesium sulfate whisker, 15g of modified flax fiber and antioxidant 1010 are added into a high-speed mixer to be mixed at high speed, then the mixture is added into a double-screw extruder to be blended and extruded, the extrusion processing temperature is 200 ℃, 225 ℃, 205 ℃, the machine head temperature is 210 ℃, the screw speed is 220r/min, the feeding speed is 70r/min, and then the injection molding is carried out under the conditions that the pressure is 55MPa and the temperature is 210 ℃ to obtain the matte environment-friendly PP composite material.
Example 2
This embodiment differs from embodiment 1 in that:
in the step (2), the dosage of the allyl silicate trimethylol methylamine caged ester is 12g, and the initiator is 3.5g of dicumyl peroxide.
The dosage of the phosphoric acid functionalized carbon nano tube in the step (4) is 2g, and other conditions are kept consistent.
Example 3
This embodiment differs from embodiment 1 in that:
in the step (2), the dosage of the allyl silicate trimethylol methylamine caged ester is 18g, and the initiator is 4.8g of dicumyl peroxide.
The dosage of the phosphoric acid functionalized carbon nano tube in the step (4) is 3.5g, and other conditions are kept consistent.
Example 4
This embodiment differs from embodiment 1 in that:
in the step (2), the dosage of the allyl silicate trimethylol methylamine caged ester is 25g, and the initiator is 6g of dicumyl peroxide.
The dosage of the phosphoric acid functionalized carbon nano tube in the step (4) is 5g, and other conditions are kept consistent.
Comparative example 1
The comparative example differs from example 1 in that no phosphoric acid functionalized carbon nanotubes were added in step (4), and other conditions were kept consistent.
Comparative example 2
The comparative example differs from example 1 in that steps (1) and (2) are not present, and in step (4) no aminosilicone grafted PP is added, only ordinary polypropylene is added.
100g of polypropylene, 0.5g of phosphoric acid functionalized carbon nano tube, 2g of matte agent basic magnesium sulfate whisker, 15g of modified flax fiber and antioxidant 1010 are added into a high-speed mixer to be mixed at high speed, then are added into a double-screw extruder to be blended and extruded, the extrusion processing temperature is 200 ℃, 225 ℃, 220 ℃, 205 ℃ and the machine head temperature is 210 ℃, the screw speed is 220r/min, the feeding speed is 70r/min, and then the PP composite material is obtained through injection molding under the conditions that the pressure is 55MPa and the temperature is 210 ℃.
Limiting oxygen index (LO I) test: and testing by adopting a digital display oxygen index tester.
Vertical combustion test: the test standard is UL-94, and a horizontal and vertical burning tester is adopted for testing.
Carbon residue test: and testing the carbon residue rate of the sample under the condition of program temperature rise by adopting a thermal analyzer, wherein the testing temperature is 700 ℃ and the nitrogen atmosphere.
Tensile property test: according to the GB/T1447-2005 fiber reinforced plastic tensile property test method, the tensile speed is 100mm/min.
Bending performance test: according to the method for testing the bending property of the fiber reinforced plastic of GB/T1449-2005, the speed is 15mm/min.
Table 1 polypropylene performance test table
As shown in the test data of the table, with the increase of the dosage of the allylsilicate trimethylol methylamine cage-shaped ester and the phosphoric acid functionalized carbon nano tube, the limiting oxygen index reaches 30.8, the UL-94 test grade is V0, and the flame retardant property is obviously improved compared with that of the comparative example 1, because after the phosphoric acid functionalized carbon nano tube is added, the phosphoric acid group on the surface of the carbon nano tube and the amino group of the aminosilicone grafted PP generate ammonium phosphate when being blended, so that a nitrogen-phosphorus-silicon intumescent flame retardant system with a stable cage-shaped structure is formed, the ammonia generated by thermal decomposition and the phosphoric acid accumulated in an intumescent carbon layer generate corresponding pyrophosphates, polyphosphates and the like, the phosphoric acid accumulated in the coking carbon layer is favorable for further carbonization of cokes, the phosphorus accumulated on the surface of a melt can generate an acidic film layer containing water and acid, and the film layer has a certain blocking effect on air, so that the flame retardant property of the material is favorable for improving.
The carbon residue of example 4 was 17.5%, while the carbon residue of comparative example 2 was only 3.9%, indicating that the carbon forming effect of the nitrogen-phosphorus-silicon intumescent flame retardant system on the PP system was better, and the better the carbon forming effect was, the better the flame retardant property was, because the carbon residue of the nitrogen-phosphorus-silicon intumescent flame retardant system contained Si O 2 Inorganic phaseThe stability of the carbon layer and the carbon residue rate of the flame-retardant system can be improved, and the flame-retardant performance of the PP is further improved.
With the increase of the dosage of the phosphoric acid functionalized carbon nano tube, the mechanical property of the composite material is improved to a certain extent, because the amino groups of the phosphorylated carbon nano tube and the aminosilicone grafted PP form an ammonium phosphate structure, the interfacial acting force between the carbon nano tube and the polypropylene is enhanced, the dispersibility between the carbon nano tube and the polypropylene matrix is better, and the interfacial strength is higher, so that the tensile modulus and the bending strength of the composite material are improved.
Example 5
The difference between this example and example 1 is that the amount of basic magnesium sulfate whisker as a matting agent in step (4) was 4g, and the other conditions were kept the same.
Example 6
The difference between this example and example 1 is that the amount of basic magnesium sulfate whisker as a matting agent in step (4) was 6g, and the other conditions were kept the same.
Example 7
The difference between this example and example 1 is that the amount of basic magnesium sulfate whisker as a matting agent in step (4) was 8g, and the other conditions were kept the same.
Comparative example 3
This example differs from example 1 in that no basic magnesium sulfate whisker of matting agent is added in step (4), and other conditions remain the same.
Gloss test: and adopting a color difference meter to perform glossiness test, wherein the test angle is 60 degrees.
Table 2 polypropylene gloss test table
The principle of extinction of the surface of the plastic product is that the surface of the product is formed with tiny concave-convex or tiny wrinkles by using a physical or chemical method, and the concave-convex or the wrinkles can generate diffuse reflection and scattering effects on light rays, thereby reducing the glossiness of the surface of the product. As shown by the test results of the table, with the increase of the consumption of the basic magnesium sulfate whisker of the matte agent, the micro convex-concave formed on the surface of the polypropylene material is increased, the diffuse reflection of light is also increased, and the surface glossiness is gradually reduced, so that the matte effect is achieved, the spraying process of the material is avoided by adding the basic magnesium sulfate whisker of the matte agent, the cost is greatly reduced, and the environmental pollution and the harm to human bodies caused by the spraying process are reduced.
Example 8
The difference between this embodiment and example 1 is that the amount of modified flax fiber used in step (4) is 20g, with other conditions being consistent.
Example 9
The difference between this embodiment and example 1 is that the amount of modified flax fiber used in step (4) is 25g, with other conditions being consistent.
Example 10
The difference between this embodiment and example 1 is that the amount of modified flax fiber used in step (4) is 30g, with other conditions being consistent.
Example 11
The difference between this embodiment and example 1 is that the amount of modified flax fiber used in step (4) is 35g, with other conditions being consistent.
Comparative example 4
The difference between this comparative example and example 1 is that the flax fiber is not modified in step (4), i.e., normal flax fiber is added, with other conditions remaining the same.
Comparative example 5
The difference between this comparative example and example 1 is that no modified flax fiber was added in step (4), the other conditions remaining the same.
Tensile property test: according to the GB/T1447-2005 fiber reinforced plastic tensile property test method, the tensile speed is 100mm/min.
Bending performance test: according to the method for testing the bending property of the fiber reinforced plastic of GB/T1449-2005, the speed is 15mm/min.
TABLE 3 Polypropylene tensile Property test Table
| Tensile modulus (GPa) | Flexural Strength (MPa) | |
| Example 1 | 2.34 | 51.7 |
| Example 8 | 2.87 | 55.3 |
| Example 9 | 2.84 | 59.6 |
| Example 10 | 2.81 | 65.4 |
| Example 11 | 2.78 | 60.8 |
| Comparative example 4 | 2.27 | 45.6 |
| Comparative example 5 | 2.14 | 40.3 |
As shown by the test results of the table, with the increase of the dosage of the modified flax fiber in the polypropylene composite material, the tensile modulus and the bending strength of the material are obviously improved, when the dosage of the modified flax fiber in the embodiment 8 is 20g, the tensile modulus of the composite material is improved to 2.87GPa and is higher than that of the comparative example 5 without the modified flax fiber, because the attachments on the surface of the modified flax fiber treated by NaOH are obviously reduced, the fiber becomes easy to separate, the modified flax fiber is overlapped in the composite material to form a net structure, the PP is supported by the net structure, the plastic deformation generated by the PP is limited, and the rigidity and the hardness of the material are improved; the flax fiber of comparative example 4 is not modified, has more attachments on the surface, is relatively coarse, has longitudinal stripes and nodes, is bonded into bundles, and is easy to form aggregation in the polypropylene material, thereby affecting the mechanical property of the material.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (9)
1. The processing technology of the matte environment-friendly PP composite material is characterized by comprising the following steps of:
(1) Polypropylene is structured intoAdding allyl silicate trimethylol methylamine cage ester and initiator dicumyl peroxide into a double-screw extruder for melt grafting, extruding, cooling, drying and granulating to obtain aminosiloxane grafted PP;
(2) Adding the hydroxylated carbon nano tube and triethylamine into tetrahydrofuran, performing ultrasonic dispersion for 0.5-1.5h in ice water bath, dropwise adding phosphorus trichloride and tetrahydrofuran, refluxing for 16-32h at 70-90 ℃, cooling, adding sodium hydroxide aqueous solution, adjusting pH to 7-8, hydrolyzing for 2-6h at 55-70 ℃, filtering, then deionized water, and drying to obtain the phosphoric acid functionalized carbon nano tube;
(3) Adding aminosiloxane grafted PP, phosphoric acid functionalized carbon nano tube, matt agent basic magnesium sulfate whisker, modified flax fiber and antioxidant into a high-speed mixer, mixing at high speed, adding into a double-screw extruder, carrying out blending extrusion, and then carrying out injection molding under the pressure of 50-60MPa and the temperature of 190-220 ℃ to obtain the matt environment-friendly PP composite material.
2. The processing technology of the matte environment-friendly PP composite material according to claim 1, wherein the mass ratio of each substance in the step (1) is as follows: PP, allyl silicate tris (hydroxymethyl) methylamine cage ester, dicumyl peroxide=100 (5-25) and (2-6).
3. The process for processing the matte environment-friendly PP composite material according to claim 1, wherein the temperatures of the first region to the fifth region of the extruder in the step (1) are 170-180 ℃, 180-190 ℃, 190-200 ℃, 195-205 ℃, 190-200 ℃, the melt grafting time is 5-10min, and the screw rotation speed is 150-170r/min.
4. The processing technology of the matte environment-friendly PP composite material according to claim 1, wherein the mass ratio of each substance in the step (2) is as follows: hydroxylated carbon nanotube, triethylamine, phosphorus trichloride=1, (30-40) and (12-18).
5. The processing technology of the matte environment-friendly PP composite material according to claim 1, wherein the mass ratio of each substance in the step (3) is as follows: the aminosiloxane grafted PP is phosphoric acid functionalized carbon nano tube, the matte agent basic magnesium sulfate whisker is modified flax fiber=100 (0.5-5), 2-8 and 15-35.
6. The process for processing the matte environment-friendly PP composite material according to claim 1, wherein the extrusion processing temperature in the step (3) is 195-205 ℃, 220-230 ℃, 215-225 ℃, 200-210 ℃, the temperature of a machine head is 200-220 ℃, the rotating speed of a screw is 210-230r/min, and the feeding speed is 60-75r/min.
7. The processing technology of the matte environment-friendly PP composite material according to claim 1, wherein the processing technology of the allylsilicate trimethylol methylamine cage ester in the step (1) comprises the following steps: adding tris (hydroxymethyl) aminomethane, triethylamine and dioxane into a reaction flask carrying a dropping funnel and a reflux condenser, uniformly stirring, protecting by nitrogen, dropwise adding allyl trichlorosilane at 25-40 ℃, stirring for reaction after the dropwise adding is finished, filtering while the reaction is finished, and washing a filter cake by acetone to obtain the allyl silicate tris (hydroxymethyl) methylamine cage-shaped ester.
8. The processing technology of the matte environment-friendly PP composite material according to claim 7, wherein the mass ratio of the substances is as follows: tris (hydroxymethyl) aminomethane: triethylamine: allyl trichlorosilane = 100 (80-96): 140-170).
9. The process for processing the matte environment-friendly PP composite material according to claim 7, wherein the reaction temperature is 60-80 ℃ and the reaction time is 6-10h.
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| CN106674741A (en) * | 2016-12-26 | 2017-05-17 | 重庆普利特新材料有限公司 | High heat-resistant, halogen-free and flame-retardant type jute fiber-reinforced polypropylene composite material and preparation method thereof |
| CN111349189A (en) * | 2020-04-26 | 2020-06-30 | 杨光云 | Flame-retardant nitrogen-phosphorus synergistic carbon nanotube modified acrylic resin material and preparation method thereof |
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