CN114213841B - PA6 composite material and preparation method and application thereof - Google Patents
PA6 composite material and preparation method and application thereof Download PDFInfo
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- CN114213841B CN114213841B CN202111592067.5A CN202111592067A CN114213841B CN 114213841 B CN114213841 B CN 114213841B CN 202111592067 A CN202111592067 A CN 202111592067A CN 114213841 B CN114213841 B CN 114213841B
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- 239000002131 composite material Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title description 22
- 229920002748 Basalt fiber Polymers 0.000 claims abstract description 127
- 239000000945 filler Substances 0.000 claims abstract description 68
- 239000011521 glass Substances 0.000 claims abstract description 61
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical class O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000011324 bead Substances 0.000 claims abstract description 53
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 10
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000243 solution Substances 0.000 claims description 53
- 239000008367 deionised water Substances 0.000 claims description 51
- 229910021641 deionized water Inorganic materials 0.000 claims description 51
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 38
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 35
- 150000002910 rare earth metals Chemical class 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000007800 oxidant agent Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- 230000001590 oxidative effect Effects 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 10
- 150000007522 mineralic acids Chemical class 0.000 claims description 9
- -1 rare earth metal salt Chemical class 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 6
- 238000006011 modification reaction Methods 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 3
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 3
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 abstract description 5
- 229920002292 Nylon 6 Polymers 0.000 description 71
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 20
- 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 12
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 10
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 10
- 229910001961 silver nitrate Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K7/10—Silicon-containing compounds
-
- 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
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
- C08K7/20—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The PA6 composite material comprises the following components in parts by weight: 80 to 100 parts of PA6, 8 to 12 parts of modified composite filler, 16 to 20 parts of modified basalt fiber and 0.1 to 0.5 part of antioxidant, wherein the modified composite filler is a composite filler of modified talcum powder and glass beads. The PA6 composite material has excellent physical properties and uniform longitudinal and transverse shrinkage.
Description
Technical Field
The application relates to the technical field of composite materials, in particular to a PA6 composite material, a preparation method and application thereof.
Background
Polyamide 6 (PA 6) is a widely used high molecular polyester resin. PA6 has advantages of good fatigue resistance, good heat resistance, good dimensional stability, etc., but PA6 has general physical properties, uneven shrinkage ratio and aspect ratio, and irregular surface of the product is easy to occur when PA6 is used for producing the product, which limits the application of PA6 in some fields.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the application.
The application provides a PA6 composite material, a preparation method and application thereof, wherein the PA6 composite material has excellent physical properties and uniform longitudinal and transverse shrinkage.
The application provides a PA6 composite material, which comprises the following components in parts by weight:
the modified composite filler is a composite filler of modified talcum powder and glass beads.
In the embodiment of the application, the modified composite filler can be a composite filler of talcum powder and glass beads with the rare earth surface modified.
In the embodiment of the application, the rare earth surface modified talcum powder and glass microsphere composite filler can be obtained by the following method:
s1: dissolving rare earth metal salt in a solvent to obtain rare earth metal salt solution;
s2: mixing talcum powder, glass beads and the rare earth metal salt solution obtained in the step S1 with inorganic acid, carrying out modification reaction on the talcum powder and the glass beads, and cleaning the modified talcum powder and the modified glass beads by deionized water until the pH value of the deionized water for cleaning is neutral, thus obtaining modified composite filler wet material;
s3: and (3) drying the modified composite filler wet material obtained in the step (S2) to obtain the composite filler of the rare earth surface modified talcum powder and the glass beads.
In an embodiment of the present application, the rare earth metal salt may be selected from any one or more of lanthanum chloride, lanthanum nitrate, cerium chloride, cerium nitrate, praseodymium chloride, praseodymium nitrate, yttrium chloride, and yttrium nitrate.
In an embodiment of the present application, in step S1, the solvent may be selected from any one or more of deionized water, acetone, ethanol, and isopropyl alcohol;
in step S2, the inorganic acid may be selected from any one or more of concentrated nitric acid, concentrated sulfuric acid, concentrated hydrochloric acid, and concentrated phosphoric acid.
In an embodiment of the present application, in step S1, the mass ratio of the rare earth metal salt to the solvent may be (30 to 40): (160 to 200);
in the step S2, the mass ratio of the talcum powder, the glass beads, the rare earth metal salt solution and the inorganic acid may be (40 to 50): (6 to 10): (120 to 160): (30 to 40).
In the embodiment of the application, in the step S2, the reaction temperature for the modification reaction of the talcum powder and the glass beads may be 30 ℃ to 50 ℃ and the reaction time may be 10 hours to 12 hours.
In step S3, the drying temperature of the drying may be 50 ℃ to 70 ℃ and the drying time may be 5 hours to 7 hours.
In an embodiment of the present application, the modified basalt fiber may be SiO 2 Coated basalt fiber.
In an embodiment of the application, the SiO 2 The coated basalt fiber can be obtained by the following method:
s10: mixing an oxidant, a catalyst, basalt fibers and deionized water, and carrying out an oxidation reaction of the basalt fibers under a stirring condition to obtain a solution containing oxidized basalt fibers;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: mixing the oxidized basalt fiber obtained in the step S20, tetrabutyl orthosilicate and deionized water, and reacting under the stirring condition to obtain a composite material containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the solution of the coated basalt fiber to obtain the SiO 2 Coated basalt fiber.
In an embodiment of the present application, in step S10, the reaction temperature of the oxidation reaction may be 60 ℃ to 80 ℃ and the reaction time may be 8 hours to 10 hours.
In the embodiment of the present application, in the step S10, the mass ratio of the oxidizing agent, the catalyst, the basalt fiber, and the deionized water may be (2 to 6): (0.6 to 0.8): (40 to 50): (120 to 160).
In an embodiment of the present application, in step S30, the reaction temperature of the reaction may be 40 ℃ to 60 ℃ and the reaction time may be 6 hours to 8 hours.
In the embodiment of the application, in the step S30, the mass ratio of the oxidized basalt fiber to the tetrabutyl orthosilicate to the deionized water can be (30 to 40): 24 to 28): 160 to 200.
The embodiment of the application also provides a preparation method of the PA6 composite material, which comprises the following steps:
s100: weighing 80 to 100 parts by weight of PA6, 8 to 12 parts by weight of talcum powder and glass microsphere composite filler, 16 to 20 parts by weight of basalt fiber and 0.1 to 0.5 part by weight of antioxidant, mixing and stirring uniformly to obtain a mixture;
s200: and (3) extruding and granulating the mixture obtained in the step (S100) to obtain the PA6 composite material.
In an embodiment of the present application, the extrusion granulation of step S200 may be performed in a twin-screw extruder comprising six temperature zones arranged in sequence, in sequence: the temperature of the first area is 200 ℃ to 220 ℃, the temperature of the second area is 240 ℃ to 260 ℃, the temperature of the third area is 240 ℃ to 260 ℃, the temperature of the fourth area is 240 ℃ to 260 ℃, the temperature of the fifth area is 240 ℃ to 260 ℃, the temperature of the sixth area is 240 ℃ to 260 ℃, the temperature of the machine head is 240 ℃ to 260 ℃, and the rotating speed of the screw is 200r/min to 280r/min.
The embodiment of the application also provides the application of the PA6 composite material in the production of automobile outer door handles.
The PA6 composite material provided by the embodiment of the application has excellent mechanical properties and uniform transverse and longitudinal shrinkage, and solves the problems of poor impact strength and nonuniform shrinkage of the PA6 composite material.
In addition, the PA6 composite material provided by the embodiment of the application contains the composite filler of talcum powder and glass beads, and can generate a synergistic effect after the talcum powder and the glass beads are compounded, so that the mechanical property of the PA6 composite material can be improved.
The modified basalt fiber in the PA6 composite material of the embodiment of the application can adopt SiO 2 Coated basalt fiber, thereby improving the mechanical property and the longitudinal and transverse shrinkage of the PA6 composite materialUniformity.
Additional features and advantages of the application will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the application. Other advantages of the application may be realized and attained by means of the instrumentalities and combinations particularly pointed out in the specification.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, embodiments of the present application will be described in detail hereinafter. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be arbitrarily combined with each other.
The embodiment of the application provides a PA6 composite material, which comprises the following components in parts by weight:
the modified composite filler is a composite filler of modified talcum powder and glass beads.
The PA6 composite material provided by the embodiment of the application has excellent mechanical properties and uniform transverse and longitudinal shrinkage, and solves the problems of poor impact strength and nonuniform shrinkage of the PA6 composite material.
In addition, the PA6 composite material provided by the embodiment of the application contains the composite filler of talcum powder and glass beads, and can generate a synergistic effect after the talcum powder and the glass beads are compounded, so that the mechanical property of the PA6 composite material can be improved.
The PA6 composite material provided by the embodiment of the application also contains modified basalt fiber, so that the mechanical property of the PA6 composite material can be further improved.
In an embodiment of the application, the PA6 composite material may be composed of the following components in parts by weight:
the modified composite filler is a composite filler of modified talcum powder and glass beads.
In the embodiment of the application, the modified composite filler can be a composite filler of talcum powder and glass beads with the rare earth surface modified.
In the embodiment of the application, the rare earth surface modified talcum powder and glass microsphere composite filler can be obtained by the following method:
s1: dissolving rare earth metal salt in a solvent to obtain rare earth metal salt solution;
s2: mixing talcum powder, glass beads and the rare earth metal salt solution obtained in the step S1 with inorganic acid, carrying out modification reaction on the talcum powder and the glass beads, and cleaning the modified talcum powder and the modified glass beads by deionized water until the pH value of the deionized water for cleaning is neutral, thus obtaining modified composite filler wet material;
s3: and (3) drying the modified composite filler wet material obtained in the step (S2) to obtain the composite filler of the rare earth surface modified talcum powder and the glass beads.
In the description of the present application, "pH neutral" means a pH of 7 at 25 ℃.
In an embodiment of the present application, the rare earth metal salt may be selected from any one or more of lanthanum chloride, lanthanum nitrate, cerium chloride, cerium nitrate, praseodymium chloride, praseodymium nitrate, yttrium chloride, and yttrium nitrate.
In an embodiment of the present application, in step S1, the solvent may be selected from any one or more of deionized water, acetone, ethanol, and isopropyl alcohol.
In an embodiment of the present application, in step S2, the inorganic acid may be selected from any one or more of concentrated nitric acid, concentrated sulfuric acid, concentrated hydrochloric acid, and concentrated phosphoric acid.
In embodiments of the present application, the "concentrated nitric acid" may be commercially available concentrated nitric acid having a mass fraction of about 68%; the concentrated sulfuric acid can be commercially available concentrated sulfuric acid with a mass fraction of about 98%; the "concentrated hydrochloric acid" may be commercially available concentrated hydrochloric acid having a mass fraction of about 36% to 38%; the "concentrated phosphoric acid" may be commercially available concentrated phosphoric acid having a mass fraction of about 85%.
In an embodiment of the present application, in step S1, the mass ratio of the rare earth metal salt to the solvent may be (30 to 40): (160 to 200).
In the embodiment of the present application, in the step S2, the mass ratio of the talc powder, the glass beads, the rare earth metal salt solution, and the inorganic acid may be (40 to 50): 6 to 10): 120 to 160): 30 to 40.
In the embodiment of the application, in the step S2, the reaction temperature for the modification reaction of the talcum powder and the glass beads may be 30 ℃ to 50 ℃ and the reaction time may be 10 hours to 12 hours.
In an embodiment of the present application, in step S3, the drying temperature of the drying may be 50 ℃ to 70 ℃ and the drying time may be 5 hours to 7 hours.
In the embodiment of the application, the rare earth surface modified talcum powder and glass microsphere composite filler can be obtained by the following method:
s1: weighing a certain amount of LaCl 3 ·6H 2 O, acetone, laCl 3 ·6H 2 O is added into acetone to obtain LaCl 3 A solution;
s2: talcum powder, glass beads and LaCl obtained in the step S1 3 Placing the solution into a beaker containing concentrated nitric acid, placing the beaker into a water bath kettle with the temperature of 30-50 ℃ for 10-12 hours, and then washing the filler with deionized water until the pH value of the deionized water for cleaning is neutral, thus obtaining a modified composite filler wet material;
s3: drying the modified composite filler obtained in the step S2 in a vacuum drying oven at 50-70 ℃ for 5-7 h to obtain the composite filler of the rare earth surface modified talcum powder and the glass beads;
wherein in step S1, laCl 3 ·6H 2 The mass ratio of O to acetone can be (30 to 40): 160 to 200;
in the step S2, the talcum powder,The glass beads and the LaCl 3 The mass ratio of solution to the concentrated nitric acid may be (40 to 50): (6 to 10): (120 to 160): (30 to 40).
In an embodiment of the present application, the modified basalt fiber may be SiO 2 Coated basalt fiber.
In an embodiment of the application, the SiO 2 The coated basalt fiber can be obtained by the following method:
s10: mixing an oxidant, a catalyst, basalt fibers and deionized water, and carrying out an oxidation reaction of the basalt fibers under a stirring condition to obtain a solution containing oxidized basalt fibers;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: mixing the oxidized basalt fiber obtained in the step S20, tetrabutyl orthosilicate and deionized water, and reacting under the stirring condition to obtain a composite material containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the solution of the coated basalt fiber to obtain the SiO 2 Coated basalt fiber.
Preparation of SiO according to the embodiment of the application 2 The reaction mechanism of the coated basalt fiber is as follows:
Si(OC 4 H 9 ) 4 +2H 2 O→SiO 2 +4C 4 H 9 OH
introducing basalt fibers into SiO 2 During the formation of (a) so that SiO is formed 2 And coating basalt fibers.
When basalt fiber selects SiO 2 When the basalt fiber is coated, the mechanical property and the longitudinal and transverse shrinkage uniformity of the PA6 composite material can be further improved; furthermore, siO 2 SiO in coated basalt fiber 2 Can be used as heterogeneous nucleating agent to perfect the crystallinity of PA6 and improve the physical properties of PA6 composite material.
In an embodiment of the present application, in step S10, the reaction temperature of the oxidation reaction may be 60 ℃ to 80 ℃ and the reaction time may be 8 hours to 10 hours.
In an embodiment of the present application, in step S10, the oxidizing agent may be selected from any one or more of potassium persulfate and sodium persulfate.
In an embodiment of the present application, in step S10, the catalyst may be silver nitrate.
In the embodiment of the present application, in the step S10, the mass ratio of the oxidizing agent, the catalyst, the basalt fiber, and the deionized water may be (2 to 6): (0.6 to 0.8): (40 to 50): (120 to 160).
In an embodiment of the present application, in step S30, the reaction temperature of the reaction may be 40 ℃ to 60 ℃ and the reaction time may be 6 hours to 8 hours.
In the embodiment of the application, in the step S30, the mass ratio of the oxidized basalt fiber to the tetrabutyl orthosilicate to the deionized water can be (30 to 40): 24 to 28): 160 to 200.
In an embodiment of the application, the SiO 2 The coated basalt fiber can be obtained by the following method:
s10: weighing a certain amount of oxidant potassium persulfate, catalyst silver nitrate, basalt fiber and deionized water, adding the oxidant potassium persulfate, the catalyst silver nitrate, the basalt fiber and the deionized water into a reaction vessel, and stirring at 60-80 ℃ to perform an oxidation reaction of the basalt fiber for 8-10 hours to obtain a solution containing oxidized basalt fiber;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: weighing a certain amount of oxidized basalt fiber, tetrabutyl orthosilicate and deionized water obtained in the step S20, adding the basalt fiber, the tetrabutyl orthosilicate and the deionized water into a reaction vessel, and stirring and reacting for 6 to 8 hours at the temperature of 40 to 60 ℃ to obtain the product containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the solution of the coated basalt fiber to obtain the SiO 2 Coated basalt fibers;
wherein in the step S10, the mass ratio of the oxidant potassium persulfate to the catalyst silver nitrate to the basalt fiber to the deionized water can be (2 to 6): 0.6 to 0.8): 40 to 50): 120 to 160;
in step S30, the mass ratio of the oxidized basalt fiber, the tetrabutyl orthosilicate and the deionized water may be (30 to 40): 24 to 28): 160 to 200.
In an embodiment of the present application, the antioxidant may be selected from any one or more of phenyl tris (2, 4-di-t-butyl) phosphite (abbreviated as antioxidant 168), pentaerythritol tetrakis [ beta- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate (abbreviated as antioxidant 1010), and 1,3, 5-trimethyl-2, 4,6- (3, 5-di-t-butyl-4-hydroxybenzyl) benzene (abbreviated as antioxidant 1330).
In an embodiment of the present application, the antioxidant 168, the antioxidant 1010, the antioxidant 1330 may be a product from basf corporation.
The embodiment of the application also provides a preparation method of the PA6 composite material, which comprises the following steps:
s100: weighing 80 to 100 parts by weight of PA6, 8 to 12 parts by weight of talcum powder and glass microsphere composite filler, 16 to 20 parts by weight of basalt fiber and 0.1 to 0.5 part by weight of antioxidant, mixing and stirring uniformly to obtain a mixture;
s200: and (3) extruding and granulating the mixture obtained in the step (S100) to obtain the PA6 composite material.
In an embodiment of the present application, the extrusion granulation of step S200 may be performed in a twin-screw extruder comprising six temperature zones arranged in sequence, in sequence: the temperature of the first area is 200 ℃ to 220 ℃, the temperature of the second area is 240 ℃ to 260 ℃, the temperature of the third area is 240 ℃ to 260 ℃, the temperature of the fourth area is 240 ℃ to 260 ℃, the temperature of the fifth area is 240 ℃ to 260 ℃, the temperature of the sixth area is 240 ℃ to 260 ℃, the temperature of the machine head is 240 ℃ to 260 ℃, and the rotating speed of the screw is 200r/min to 280r/min.
The embodiment of the application also provides the application of the PA6 composite material in the production of automobile outer door handles.
The automobile outer door handle is not only used as a common functional part of an automobile, but also an appearance part, and has high requirements on appearance. Common exterior door handles may be divided into integral handles and split handles. The integral external handle has high requirements on mechanical properties of materials, and also has uniform transverse and longitudinal shrinkage of the materials, so that the surface of a workpiece is ensured to be regular, and the surface of the workpiece has good appearance. The common material of the integrated handle is PA6+GF30 composite material (namely PA6 and 30% glass fiber composite material), the ratio of the longitudinal shrinkage rate to the transverse shrinkage rate is generally 1.5-2, the phenomenon of irregular surface of a workpiece is easy to occur, and the surface is regular only through multiple surface treatments, so that the production cost of the external handle is higher.
The PA6 composite material of the embodiment of the application has excellent physical properties, the ratio of the longitudinal shrinkage to the transverse shrinkage is approximately 1, and compared with the ratio of the longitudinal shrinkage to the transverse shrinkage of 1.5 to 2 of the common outer handle composite material, the longitudinal shrinkage and the transverse shrinkage of the PA6 composite material of the embodiment of the application are more uniform.
The sources of the raw materials used in the following examples and comparative examples are as follows:
PA6 (model CM 1017), eastern japan; acetone, shandong Xu Chemie Co., ltd; talcum powder, guifeng chemical Co., ltd; basalt fiber, shandongsen hong engineering materials limited; glass beads, ming's mineral products Limited in Chengyang county; potassium persulfate, atan's chemical industry limited; silver nitrate, shanghai Zhejiang platinum New Material technologies Co., ltd; deionized water, beijing Bai Oy Lai Bo technology Co., ltd; laCl 3 ·6H 2 O, shandong Desheng New Material Co., ltd; concentrated nitric acid, the mass fraction of the Yangzhou Huafu chemical industry Co., ltd; antioxidant 168, antioxidant 1010, antioxidant 1330, basf company.
In addition, the parts in the following examples and comparative examples refer to parts by weight.
Example 1
(1) Preparation of rare earth surface modified talcum powder and glass bead composite filler
S1: 300g LaCl was weighed out 3 ·6H 2 O, 1.6kg acetone, laCl 3 ·6H 2 Adding O into acetone solution to obtain LaCl 3 A solution;
s2: 400g of talcum powder, 60g of glass beads and 1.2kg of LaCl obtained in the step S1 3 Placing the solution into a beaker containing 300g of concentrated nitric acid, placing the beaker into a water bath kettle at 30 ℃ for 10 hours, and then washing the filler with deionized water until the pH of the deionized water for washing is neutral, thus obtaining a modified composite filler wet material;
s3: and (3) putting the modified composite filler wet material obtained in the step (S2) into a vacuum drying oven at 50 ℃ for drying for 5 hours to obtain the composite filler M1 of the rare earth surface modified talcum powder and the glass beads.
(2)SiO 2 Preparation of coated basalt fiber
S10: weighing 20g of oxidant potassium persulfate, 6g of catalyst silver nitrate, 400g of basalt fiber and 1.2kg of deionized water, adding the materials into a reaction vessel, and stirring and reacting for 8 hours at 60 ℃ to obtain a solution containing oxidized basalt fiber;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: 300g of the oxidized basalt fiber obtained in the step S20, 240g of tetrabutyl orthosilicate and 1.6kg of deionized water are weighed, added into a reaction vessel, stirred and reacted for 6 hours at 40 ℃ to obtain a product containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the coated basalt fiber solution to obtain SiO 2 Coated basalt fiber N1.
(3) Preparation of PA6 composite material
S100: weighing 80 parts of PA6, 8 parts of composite filler M1 prepared in the step (1) and 16 parts of SiO prepared in the step (2) 2 Mixing and uniformly stirring the coated basalt fiber N1 and 0.1 part of antioxidant 1010 to obtain a mixture;
s200: extruding and granulating the mixture obtained in the step S100 from a double-screw extruder to obtain a PA6 composite material P1;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 200 ℃, the temperature of the second area is 240 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 240 ℃, the temperature of the sixth area is 240 ℃, the temperature of the machine head is 240 ℃, and the rotating speed of the screw is 200r/min.
Example 2
(1) Preparation of rare earth surface modified talcum powder and glass bead composite filler
S1: 400g CeCl was weighed 3 ·7H 2 O, 2.0kg ethanol, ceCl 3 ·7H 2 Adding O into ethanol solution to obtain CeCl 3 A solution;
s2: 500g of talcum powder, 100g of glass beads and 1.2kg of CeCl obtained in the step S1 3 Placing the solution into a beaker containing 400g of concentrated nitric acid, placing the beaker into a water bath kettle at 50 ℃ for 12 hours, and then washing the filler with deionized water until the pH value of the deionized water for washing is neutral, thus obtaining a modified composite filler wet material;
s3: and (3) putting the modified composite filler wet material obtained in the step (S2) into a vacuum drying oven at 70 ℃ for drying for 7 hours to obtain the composite filler M2 of the rare earth surface modified talcum powder and the glass beads.
(2)SiO 2 Preparation of coated basalt fiber
S10: weighing 60g of oxidant potassium persulfate, 8g of catalyst silver nitrate, 500g of basalt fiber and 1.6kg of deionized water, adding the materials into a reaction vessel, and stirring and reacting for 10 hours at 80 ℃ to obtain a solution containing oxidized basalt fiber;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: 400g of the oxidized basalt fiber obtained in the step S20, 280g of tetrabutyl orthosilicate and 2.0kg of deionized water are weighed, added into a reaction vessel, stirred and reacted for 8 hours at 60 ℃ to obtain a product containing SiO 2 A solution of coated basalt fibers;
s40: step S30 contains SiO 2 Filtering, washing and drying the coated basalt fiber solution to obtain SiO 2 And (3) coating basalt fiber N2.
(3) Preparation of PA6 composite material
S100: weighing 100 parts of PA6, 12 parts of M2 prepared in the step (1) and 20 parts of SiO prepared in the step (2) 2 Mixing and uniformly stirring the coated basalt fiber N2, 0.1 part of antioxidant 1010, 0.2 part of antioxidant 168 and 0.2 part of antioxidant 1330 to obtain a mixture;
s200: extruding and granulating the mixture obtained in the step S100 from an extruder to obtain a PA6 composite material P2;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 220 ℃, the temperature of the second area is 260 ℃, the temperature of the third area is 260 ℃, the temperature of the fourth area is 260 ℃, the temperature of the fifth area is 260 ℃, the temperature of the sixth area is 260 ℃, the temperature of the machine head is 260 ℃, and the rotating speed of the screw is 280r/min.
Example 3
(1) Preparation of rare earth surface modified talcum powder and glass bead composite filler
S1: 350g PrCl was weighed out 3 ·6H 2 O, 1.8kg deionized water, prCl 3 ·6H 2 O is added into deionized water to prepare PrCl 3 A solution;
s2: 450g of talcum powder, 80g of glass beads and 1.4kg of PrCl obtained in the step S1 3 Placing the solution into a beaker containing 350g of concentrated nitric acid, placing the beaker into a water bath kettle at 40 ℃ for 11 hours, and then washing the filler with deionized water until the pH of the deionized water for washing is neutral, thus obtaining a modified composite filler wet material;
s3: and (3) putting the modified composite filler wet material obtained in the step (S2) into a vacuum drying oven at 60 ℃ for drying for 6 hours to obtain the rare earth surface modified talcum powder and glass microsphere composite filler M3.
(2)SiO 2 Preparation of coated basalt fiber
S10: weighing 40g of oxidant potassium persulfate, 7g of catalyst silver nitrate, 450g of basalt fiber and 1.4kg of deionized water, adding the materials into a reaction vessel, and stirring and reacting for 9 hours at 70 ℃ until a solution containing oxidized basalt fiber is obtained;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: weighing 350g of oxidized basalt fiber obtained in the step S20, 260g of tetrabutyl orthosilicate and 1.8kg of deionized water, adding the materials into a reaction vessel, and stirring and reacting for 7h at 50 ℃ to obtain a product containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the coated basalt fiber solution to obtain SiO 2 And (3) coating basalt fibers N3.
(3) Preparation of PA6 composite material
S100: weighing 90 parts of PA6, 10 parts of composite filler M3 prepared in the step (1) and 18 parts of SiO prepared in the step (2) 2 Mixing and uniformly stirring the coated basalt fiber N3, 0.1 part of antioxidant 168 and 0.2 part of antioxidant 1010 to obtain a mixture;
s200: extruding and granulating the mixture obtained in the step S100 from a double-screw extruder to obtain a PA6 composite material P3;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 210 ℃, the temperature of the second area is 250 ℃, the temperature of the third area is 250 ℃, the temperature of the fourth area is 250 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 250 ℃, the temperature of the machine head is 250 ℃, and the rotating speed of the screw is 240r/min.
Example 4
(1) Preparation of rare earth surface modified talcum powder and glass bead composite filler
S1: 380g YCl is weighed 3 ·6H 2 O, 1.75kg ethanol, YCl 3 ·6H 2 Adding O into ethanol to obtain YCl 3 A solution;
s2: 480g of talcum powder, 75g of glass beads and 1.45kg of YCl obtained in the step S1 3 Putting the solution into a beaker containing 390g of concentrated nitric acid, putting the beaker into a water bath kettle with the temperature of 35 ℃ for 11 hours, and then washing the filler with deionized water until the filler is deionizedThe pH value of the water is neutral, and the modified composite filler wet material is obtained;
s3: and (3) putting the modified composite filler wet material obtained in the step (S2) into a vacuum drying oven at 55 ℃ for drying for 6 hours to obtain the rare earth surface modified talcum powder and glass microsphere composite filler M4.
(2)SiO 2 Preparation of coated basalt fiber
S10: weighing 35g of oxidant potassium persulfate, 7.5g of catalyst silver nitrate, 425g of basalt fiber and 1.35kg of deionized water, adding the materials into a reaction vessel, and stirring and reacting for 10 hours at 72 ℃ to obtain a solution containing oxidized basalt fiber;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: 380g of the oxidized basalt fiber obtained in the step S20, 265g of tetrabutyl orthosilicate and 1.75kg of deionized water are weighed, added into a reaction vessel, stirred and reacted for 6 hours at 45 ℃ to obtain a product containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the coated basalt fiber solution to obtain SiO 2 And (3) coating basalt fibers N4.
(3) Preparation of PA6 composite material
S100: weighing 95 parts of PA6, 9 parts of the composite filler M4 prepared in the step (1) and 17 parts of SiO prepared in the step (2) 2 Mixing and uniformly stirring the coated basalt fiber N4, 0.1 part of antioxidant 1010 and 0.2 part of antioxidant 1330 to obtain a mixture;
s200: extruding and granulating the mixture obtained in the step S100 from a double-screw extruder to obtain a PA6 composite material P4;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 215 ℃, the temperature of the second area is 245 ℃, the temperature of the third area is 245 ℃, the temperature of the fourth area is 245 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the machine head is 245 ℃, and the rotating speed of the screw is 245r/min.
Example 5
(1) Preparation of rare earth surface modified talcum powder and glass bead composite filler
S1: 325g of LaCl was weighed out 3 ·6H 2 O, 1.95kg acetone, laCl 3 ·6H 2 Adding O into acetone solution to obtain LaCl 3 A solution;
s2: 415g of talcum powder, 90g of glass beads and 1.45kg of LaCl obtained in the step S1 3 Putting the solution into a beaker containing 380g of concentrated nitric acid, putting the beaker into a water bath kettle at 45 ℃ for 12 hours, and then washing the filler with deionized water until the pH value of the deionized water for washing is neutral, thus obtaining a modified composite filler wet material;
s3: and (3) putting the modified composite filler wet material obtained in the step (S2) into a vacuum drying oven at 65 ℃ for drying for 6 hours to obtain the composite filler M5 of the rare earth surface modified talcum powder and the glass beads.
(2)SiO 2 Preparation of coated basalt fiber
S10: weighing 35g of oxidant potassium persulfate, 6.5g of catalyst silver nitrate, 480g of basalt fiber and 1.35kg of deionized water, adding the materials into a reaction vessel, and stirring and reacting for 8 hours at 75 ℃ until a solution containing oxidized basalt fiber is obtained;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: weighing 315g of oxidized basalt fiber obtained in the step S20, 265g of tetrabutyl orthosilicate and 1.85kg of deionized water, adding the materials into a reaction vessel, and stirring and reacting for 6h at 55 ℃ to obtain a product containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the coated basalt fiber solution to obtain SiO 2 And (5) coating basalt fibers N5.
(3) Preparation of PA6 composite material
S100: weighing 95 parts of PA6, 10 parts of the composite filler M5 prepared in the step (1) and 19 parts of the SiO prepared in the step (2) 2 The coated basalt fiber N5, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168 are mixed and stirredUniformly stirring to obtain a mixture;
s200: extruding and granulating the mixture obtained in the step S100 from a double-screw extruder to obtain a PA6 composite material P5;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 215 ℃, the temperature of the second area is 245 ℃, the temperature of the third area is 245 ℃, the temperature of the fourth area is 245 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the machine head is 245 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 1
(1) Weighing 95 parts of PA6, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168, mixing and stirring uniformly to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from a double-screw extruder to obtain the PA6 composite material, which is marked as D1.
Wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 215 ℃, the temperature of the second area is 245 ℃, the temperature of the third area is 245 ℃, the temperature of the fourth area is 245 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the machine head is 245 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 2
(1) Weighing 95 parts of PA6, 10 parts of rare earth surface modified talcum powder (the modification process is the same as that of the step (1) of the example 5, except that glass beads are not added), and 19 parts of SiO prepared in the step (2) of the example 5 2 Mixing and uniformly stirring the coated basalt fiber N5, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168 to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from a double-screw extruder to obtain a PA6 composite material, which is marked as D2;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 215 ℃, the temperature of the second area is 245 ℃, the temperature of the third area is 245 ℃, the temperature of the fourth area is 245 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the machine head is 245 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 3
(1) 95 parts of PA6 and 10 parts of rare earth surface-modified glass beads were weighed (the modification procedure was the same as in step (1) of example 5, except thatNo talc added), 19 parts of SiO obtained in step (2) of example 5 2 Mixing and uniformly stirring the coated basalt fiber N5, 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168 to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from a double-screw extruder to obtain a PA6 composite material, which is marked as D3;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 215 ℃, the temperature of the second area is 245 ℃, the temperature of the third area is 245 ℃, the temperature of the fourth area is 245 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the machine head is 245 ℃, and the rotating speed of the screw is 245r/min.
Comparative example 4
(1) Weighing 95 parts of PA6, 10 parts of composite filler M5 prepared in the step (1) of the example 5 and 19 parts of basalt fiber (without SiO) 2 Cladding), 0.1 part of antioxidant 1010 and 0.1 part of antioxidant 168 are mixed and stirred uniformly to obtain a mixture;
(2) Extruding and granulating the mixture obtained in the step (1) from a double-screw extruder to obtain a PA6 composite material, which is marked as D4;
wherein, each district temperature and screw rod rotational speed of twin-screw extruder are respectively: the temperature of the first area is 215 ℃, the temperature of the second area is 245 ℃, the temperature of the third area is 245 ℃, the temperature of the fourth area is 245 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the machine head is 245 ℃, and the rotating speed of the screw is 245r/min.
The PA6 composite materials prepared in the above examples and comparative examples were tested for properties, and the test results are shown in table 1.
TABLE 1
Compared with the PA6 composite material of the comparative example, the PA6 composite material of the embodiment of the application has obviously improved mechanical properties, the difference between the longitudinal shrinkage and the transverse shrinkage is only 0.01 to 0.02 percent, which is greatly improved compared with the original difference of 0.31 percent, the ratio of the longitudinal shrinkage to the transverse shrinkage is nearly 1, and the longitudinal shrinkage and the transverse shrinkage are more uniform, so that the surface regularity of a product (such as a secondary outer handle) manufactured by the PA6 composite material of the embodiment of the application is more perfect, the surface of the product has good appearance, and the surface treatment procedure is reduced, thereby reducing the production cost of the product.
And compared with the PA6 composite material added with talcum powder or glass beads alone, the PA6 composite material containing talcum powder and glass beads simultaneously has better material performance, and the talcum powder and the glass beads are compounded to generate a synergistic effect.
In addition, the basalt fiber added in the PA6 composite material of the embodiment of the application adopts SiO 2 The coated basalt fiber can improve the mechanical property and the longitudinal and transverse shrinkage uniformity of the PA6 composite material.
Although the embodiments of the present application are described above, the embodiments are only used for facilitating understanding of the present application, and are not intended to limit the present application. Any person skilled in the art can make any modification and variation in form and detail without departing from the spirit and scope of the present disclosure, but the scope of the present disclosure is to be determined by the appended claims.
Claims (14)
1. The PA6 composite material is characterized by comprising the following components in parts by weight:
the modified composite filler is a composite filler of talcum powder and glass beads, wherein the talcum powder is modified on the surface of a rare earth metal salt solution, the glass beads and the rare earth metal salt solution are mixed according to the mass ratio of (40-50): 6-10): 120-160;
the modified basalt fiber is SiO 2 Coated basalt fiber, said SiO 2 The coated basalt fiber is made of an oxidant, a catalyst and basalt fiber, wherein the oxidant, the catalyst and the basalt fiberThe dimensional mass ratio is (2 to 6): (0.6 to 0.8): (40 to 50).
2. The PA6 composite material of claim 1, wherein the rare earth surface modified talc powder and glass bead composite filler is obtained by the following method:
s1: dissolving rare earth metal salt in a solvent to obtain rare earth metal salt solution;
s2: mixing talcum powder, glass beads and the rare earth metal salt solution obtained in the step S1 with inorganic acid, carrying out modification reaction on the talcum powder and the glass beads, and cleaning the modified talcum powder and the modified glass beads by deionized water until the pH value of the deionized water for cleaning is neutral, thus obtaining modified composite filler wet material;
s3: and (3) drying the modified composite filler wet material obtained in the step (S2) to obtain the composite filler of the rare earth surface modified talcum powder and the glass beads.
3. The PA6 composite material of claim 2, wherein the rare earth metal salt is selected from any one or more of lanthanum chloride, lanthanum nitrate, cerium chloride, cerium nitrate, praseodymium chloride, praseodymium nitrate, yttrium chloride, and yttrium nitrate.
4. The PA6 composite material of claim 2, wherein in step S1, the solvent is selected from any one or more of deionized water, acetone, ethanol, and isopropanol;
in step S2, the inorganic acid is selected from any one or more of concentrated nitric acid, concentrated sulfuric acid, concentrated hydrochloric acid and concentrated phosphoric acid.
5. The PA6 composite material according to any one of claims 2-4, wherein in step S1, the mass ratio of the rare earth metal salt to the solvent is (30-40): 160-200;
in the step S2, the mass ratio of the talcum powder to the glass beads to the rare earth metal salt solution to the inorganic acid is (40-50): (6-10): (120-160): (30-40).
6. The PA6 composite material according to claim 2, wherein in step S2, the reaction temperature for the modification reaction of the talc powder and the glass beads is 30 ℃ to 50 ℃ and the reaction time is 10 hours to 12 hours;
in step S3, the drying temperature is 50 ℃ to 70 ℃ and the drying time is 5 hours to 7 hours.
7. The PA6 composite material of claim 6, wherein the SiO 2 The coated basalt fiber is obtained by the following method:
s10: mixing an oxidant, a catalyst, basalt fibers and deionized water, and carrying out an oxidation reaction of the basalt fibers under a stirring condition to obtain a solution containing oxidized basalt fibers;
s20: filtering, washing and drying the solution containing the oxidized basalt fiber obtained in the step S10 to obtain the oxidized basalt fiber;
s30: mixing the oxidized basalt fiber obtained in the step S20, tetrabutyl orthosilicate and deionized water, and reacting under the stirring condition to obtain a composite material containing SiO 2 A solution of coated basalt fibers;
s40: the SiO-containing material obtained in the step S30 is mixed with 2 Filtering, washing and drying the solution of the coated basalt fiber to obtain the SiO 2 Coated basalt fiber.
8. The PA6 composite material of claim 7, wherein in step S10, the reaction temperature of the oxidation reaction is 60 ℃ to 80 ℃ and the reaction time is 8h to 10h.
9. The PA6 composite material of claim 7 or 8, wherein in step S10, the mass ratio of the oxidizing agent, the catalyst, the basalt fiber, and the deionized water is (2 to 6): 0.6 to 0.8): 40 to 50): 120 to 160.
10. The PA6 composite material of claim 7, wherein the reaction temperature of the reaction is 40 ℃ to 60 ℃ and the reaction time is 6h to 8h in step S30.
11. The PA6 composite material of claim 7, wherein in step S30, the mass ratio of the oxidized basalt fiber, the tetrabutyl orthosilicate, and the deionized water is (30 to 40): 24 to 28): 160 to 200.
12. The method of producing a PA6 composite material according to any one of claims 1 to 11, characterized by comprising:
s100: weighing 80 to 100 parts by weight of PA6, 8 to 12 parts by weight of talcum powder and glass microsphere composite filler, 16 to 20 parts by weight of basalt fiber and 0.1 to 0.5 part by weight of antioxidant, mixing and stirring uniformly to obtain a mixture;
s200: and (3) extruding and granulating the mixture obtained in the step (S100) to obtain the PA6 composite material.
13. The production method according to claim 12, wherein the extrusion granulation of step S200 is performed in a twin-screw extruder comprising six temperature zones arranged in sequence: the temperature of the first area is 200 ℃ to 220 ℃, the temperature of the second area is 240 ℃ to 260 ℃, the temperature of the third area is 240 ℃ to 260 ℃, the temperature of the fourth area is 240 ℃ to 260 ℃, the temperature of the fifth area is 240 ℃ to 260 ℃, the temperature of the sixth area is 240 ℃ to 260 ℃, the temperature of the machine head is 240 ℃ to 260 ℃, and the rotating speed of the screw is 200r/min to 280r/min.
14. Use of a PA 6-composite according to any one of claims 1-11 for producing an automotive exterior door handle.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106566234A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | A flame retardance-enhanced high-temperature resistant nylon composite material and a preparing method |
| CN107200867A (en) * | 2017-06-15 | 2017-09-26 | 中北大学 | Basalt fibre nano surface coats the preparation method and application of multi-scale reinforcing body |
| CN108034231A (en) * | 2017-11-24 | 2018-05-15 | 广东威林工程塑料股份有限公司 | A kind of outdoor used in air exchange fan high-low temperature resistant high-dimensional stability and the PA composite materials of anti-UV agings and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106566234A (en) * | 2015-10-13 | 2017-04-19 | 上海杰事杰新材料(集团)股份有限公司 | A flame retardance-enhanced high-temperature resistant nylon composite material and a preparing method |
| CN107200867A (en) * | 2017-06-15 | 2017-09-26 | 中北大学 | Basalt fibre nano surface coats the preparation method and application of multi-scale reinforcing body |
| CN108034231A (en) * | 2017-11-24 | 2018-05-15 | 广东威林工程塑料股份有限公司 | A kind of outdoor used in air exchange fan high-low temperature resistant high-dimensional stability and the PA composite materials of anti-UV agings and preparation method thereof |
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