CN117624883A - Floating-fiber-free easy-demolding reinforced PA6 material and preparation method thereof - Google Patents
Floating-fiber-free easy-demolding reinforced PA6 material and preparation method thereof Download PDFInfo
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- CN117624883A CN117624883A CN202311521930.7A CN202311521930A CN117624883A CN 117624883 A CN117624883 A CN 117624883A CN 202311521930 A CN202311521930 A CN 202311521930A CN 117624883 A CN117624883 A CN 117624883A
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- 239000000463 material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title abstract description 23
- 239000003365 glass fiber Substances 0.000 claims abstract description 92
- 229920005989 resin Polymers 0.000 claims abstract description 78
- 239000011347 resin Substances 0.000 claims abstract description 78
- 239000004677 Nylon Substances 0.000 claims abstract description 48
- 229920001778 nylon Polymers 0.000 claims abstract description 48
- 238000002425 crystallisation Methods 0.000 claims abstract description 43
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 38
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 34
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims abstract description 31
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 claims abstract description 29
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 230000005764 inhibitory process Effects 0.000 claims abstract description 23
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
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- 230000003078 antioxidant effect Effects 0.000 claims abstract description 17
- 239000000314 lubricant Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000001110 calcium chloride Substances 0.000 claims abstract description 13
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 13
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
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- 230000002401 inhibitory effect Effects 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
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- 238000005507 spraying Methods 0.000 claims description 5
- 238000000265 homogenisation Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 2
- 238000001746 injection moulding Methods 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 5
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 2
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
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- 235000011037 adipic acid Nutrition 0.000 description 1
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- 125000003368 amide group Chemical group 0.000 description 1
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- 229910052626 biotite Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
- C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- Health & Medical Sciences (AREA)
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Abstract
The application relates to the field of polymer composite materials, and particularly discloses a fiber-free and easy-to-release reinforced PA6 material and a preparation method thereof. The fiber-floating-free easy-demolding reinforced PA6 material comprises the following raw materials in parts by weight: 26.7-72.1 parts of PA6 resin, 20-50 parts of chopped glass fiber, 5-15 parts of MXD6 nylon resin, 0.4-0.8 part of compound antioxidant, 0.5-1.5 parts of lubricant and 2-6 parts of crystallization inhibition master batch; the crystallization inhibition master batch comprises the following raw materials in parts by weight: 60.6-64.5 parts of nylon resin, 4-5 parts of chlorine-containing compound, 30-35 parts of polyvinylpyrrolidone and 0.4-0.5 part of compound antioxidant, wherein the chlorine-containing compound is lithium chloride or/and calcium chloride. The fiber-floating-free easy-demolding reinforced PA6 material has the advantage that glass fiber leakage caused by rapid cooling of the surface of a mold in the injection molding process is avoided.
Description
Technical Field
The application relates to the technical field of polymer composite materials, in particular to a fiber-free and easy-to-demold reinforced PA6 material and a preparation method thereof.
Background
Polyamide 6 (PA 6 for short, also called nylon 6) belongs to crystalline thermoplastic engineering plastics and has the advantages of better toughness, chemical resistance, self-lubricating property and the like, but the polyamide 6 is used as a structural member, and the application range of the structural member is limited due to the reasons of high hygroscopicity, high creep, low heat resistance, high molding shrinkage, poor dimensional stability and the like. The glass fiber is adopted to add and modify the glass fiber, so that the defects can be greatly improved, and the application range of the glass fiber is widened.
In general, the tensile strength and bending strength of the PA6 after glass fiber reinforcement and modification can be improved by 2-3 times, the bending modulus can be improved by 2-5 times, and the creep property is reduced to one fourth or lower than that of the PA. However, the processing difficulty of the glass fiber reinforced PA composite material is high, and the main reasons are that the diameter of the glass fiber is small, the surface lacks active groups, the PA cannot be fully impregnated when being contacted with the glass fiber, the glass fiber floats on the outer surface in the molding flow process of the plastic melt, radial white marks are formed on the surface of a plastic part after condensation molding, when the plastic part is black, the color difference is increased, the PA6 part has the defects of exposed glass fiber, product mucosa, incapability of demolding, very rough inner and outer surfaces and the like, and the appearance aesthetic property of the PA6 part is affected.
Along with the continuous development of technology and the continuous improvement of human demands, not only is the material performance required to meet the standard, but also the appearance of an injection molding part is required to be good, if the floating fiber phenomenon is not allowed to occur, the decoration or coating process is reduced, and the cost is saved, such as a bus seat framework backrest, an engine hood, a rearview mirror bracket and the like. Aiming at the related technology, the glass fiber reinforced PA6 material which has no floating fiber and is easy to demould is researched, and the glass fiber reinforced PA6 material has wide application prospect.
Disclosure of Invention
In order to improve the fiber floating phenomenon of a glass fiber reinforced PA6 injection molding part and improve the easy demolding effect, the application provides a fiber floating-free easy-demolding reinforced PA6 material and a preparation method thereof.
In a first aspect, the present application provides a fiber-free easy-to-demold reinforced PA6 material, which adopts the following technical scheme: the fiber-free easy-demolding reinforced PA6 material comprises the following raw materials in parts by weight: 26.7-72.1 parts of PA6 resin, 20-50 parts of chopped glass fiber, 5-15 parts of MXD6 nylon resin, 0.4-0.8 part of compound antioxidant, 0.5-1.5 parts of lubricant and 2-6 parts of crystallization inhibition master batch;
the crystallization inhibition master batch comprises the following raw materials in parts by weight: 60.6-64.5 parts of nylon resin, 4-5 parts of chlorine-containing compound, 30-35 parts of polyvinylpyrrolidone and 0.4-0.5 part of compound antioxidant, wherein the chlorine-containing compound is lithium chloride or/and calcium chloride.
By adopting the technical scheme, the PA6 resin is taken as a main base material, the chopped glass fiber is added as a reinforcing material, and the components such as the MXD6 nylon resin, the crystallization inhibition master batch and the like are added, wherein the chopped glass fiber can be taken as a framework of the material in the PA6 material, effectively transfer stress, improve the rigidity, strength and hardness of a product, has a certain toughening effect, can reduce friction and wear resistance, increase the dimensional stability of the product, the MXD6 nylon resin is a semi-crystalline aromatic polymer formed by polycondensation of m-phenylenediamine and adipic acid, has the characteristics of high strength, good heat resistance, low shrinkage and excellent barrier property, is a special nylon material with high barrier property, has weak crystallinity, can reduce the crystallinity of PA6, can reduce the water absorption rate of the material, improve the strength of the material, and the crystallization inhibition master batch is prepared by taking the nylon resin as a compatilizer, the lithium chloride or calcium chloride serving as the chlorine-containing compound can inhibit crystallization of the PA6 material by increasing the dispersibility of the chlorine-containing compound and the PA6 resin matrix, and because the complexation reaction of the lithium chloride or calcium chloride and the PA6 resin damages hydrogen bonds among PA6 molecules, the complex forms to severely limit movement of PA6 molecular chains, so that PA6 crystallization is difficult, carbonyl in polyvinylpyrrolidone can form intermolecular hydrogen bonds with N-H on a PA6 resin main chain, the formation of the intermolecular hydrogen bonds influences the crystallization process of the PA6 resin, the crystallization degree is reduced, the compounding of the MXD6 nylon resin and crystallization inhibition master batch can not only effectively reduce the crystallization degree of the PA6 material, thereby reducing the cooling speed of the material on the surface of a die, enabling chopped glass fibers not to be quickly punched to the surface of a workpiece to form floating fibers, but also improving the mechanical strength.
Optionally, the chlorine-containing compound comprises calcium chloride and lithium chloride with the mass ratio of 1:0.8-1, by adopting the technical scheme, the mixture of the calcium chloride and the lithium chloride is added into the PA6 resin, the complexing coordination of metal ions and amide groups damages a hydrogen bond structure in PA6 molecules, which is conducive to the regular arrangement of the molecules, the complexing effect forms multiple ligands, so that a plurality of molecular chains are crosslinked together to form a chain end limited structure similar to a disperse phase in a blending system, the movement of the PA6 chain segments is difficult, the molecular chains are not easy to be discharged into a crystal lattice, and crystallization is further hindered.
Optionally, the crystallization inhibition master batch is prepared by the following method: drying nylon resin, mixing with chlorine-containing compound, polyvinylpyrrolidone and compound antioxidant, extruding at 190-235 deg.C, and granulating.
By adopting the technical scheme, nylon resin, chlorine-containing compounds, polyvinylpyrrolidone and other components are mixed, extruded and granulated, and the prepared crystallization inhibition master batch can reduce the crystallinity of the PA6 resin, improve the cooling speed of the PA6 material on the surface of a die and reduce the fiber floating phenomenon.
Optionally, the mass ratio of the MXD6 nylon resin to the crystallization inhibition master batch is 2-2.5:1.
By adopting the technical scheme, the MXD6 nylon resin and the crystallization inhibition master batch with the mass ratio can more effectively inhibit the crystallinity of the PA6 material, reduce the cooling speed of the PA6 material on a die and prevent floating fibers.
Alternatively, the viscosity of the PA6 resin is 2.2-2.5, and the viscosity of the mxd6 nylon resin is 2.45-2.7.
By adopting the technical scheme, the viscosity of the PA6 resin is smaller than that of the MXD6 nylon resin, the melting point of the MXD6 nylon resin is about 20 ℃ higher than that of the PA6, when the PA6 resin is hot melted, the MXD6 nylon resin is not completely hot melted, the viscosity of the MXD6 nylon resin is high, the fluidity is poor, and when the blend injection molding is carried out, the MXD6 nylon resin can play a role in dragging chopped glass fibers, so that the PA6 resin can rapidly form a coating on a die, the fibers can be better coated in the resin, the effect of preventing floating fibers is achieved, the surface of the PA6 material is smoother, the surface glossiness is high, and the demolding is easy.
Optionally, the chopped glass fibers are pretreated by the following steps:
immersing the chopped glass fibers in an aqueous solution of a silane coupling agent, taking out and drying to obtain pretreated chopped glass fibers;
dissolving polyvinylidene fluoride in a solvent to prepare a solution with the concentration of 50-55wt%, adding a hyper-dispersant and nano silicon dioxide, and carrying out ultrasonic homogenization to prepare a blend solution;
and uniformly spraying the blending liquid on the pretreated chopped glass fiber, and drying.
By adopting the technical scheme, the chopped glass fiber is pretreated by the silane coupling agent, the molecular structure of the silane coupling agent contains silicon-oxygen bonds and organic groups, the silicon-oxygen bonds can react with hydroxyl groups on the surface of the chopped glass fiber to form chemical bonds, the organic groups can form physical bonds with the polyvinylidene fluoride, so that the surface morphology and activity of the chopped glass fiber are improved, the wettability of the chopped glass fiber is increased, the surface roughness of the chopped glass fiber is increased, the mechanical anchoring force and the chemical bond binding force of the chopped glass fiber with the polyvinylidene fluoride are increased, the blend liquid formed by the polyvinylidene fluoride, the super-dispersant and the nano silicon dioxide is sprayed on the chopped glass fiber treated by the coupling agent, the polar groups contained in the super-dispersant can generate strong attractive force with the long chain ends of the silane coupling agent on the surface of the chopped glass fiber through van der Waals force, phase interfaces are eliminated, the super-dispersant and the chopped glass fiber form a phase, solvated chain segments in the super-dispersant and a PA6 matrix have certain properties, the PA6 resin and the MXD6 nylon resin form similar anchoring points, namely the crosslinking points are enhanced, the adhesion strength between the fiber and the surface of the chopped glass fiber is improved, the adhesion strength of the chopped glass fiber is improved, the surface is smooth, the surface of the chopped glass fiber is smooth, the surface is smooth, and has good adhesion strength to the surface strength.
Optionally, when the chopped glass fibers are pretreated, the following raw materials are in parts by weight: 40-50 parts of chopped glass fiber, 40-50 parts of aqueous solution of silane coupling agent, 5-10.5 parts of polyvinylidene fluoride, 3-6 parts of hyperdispersant and 4-8 parts of nano silicon dioxide.
By adopting the technical scheme, the raw materials with the above dosages can increase the wettability of the chopped glass fibers, improve the dispersibility of the chopped glass fibers in the PA6 resin, and promote the surface smoothness and compactness of the chopped glass fibers, thereby reducing the floating fibers and improving the glossiness.
Optionally, the lubricant is selected from at least one of silicone powder, modified ethylene bis stearamide and calcium stearate.
By adopting the technical scheme, the friction and shearing between the high polymer materials such as PA6 resin and the metal mold wall parts can be reduced by taking the silicone powder, the calcium stearate and the modified ethylene bis stearamide as the lubricant, and the uniformity of material flow, the demolding effect and the extrusion quality are improved.
Optionally, the lubricant comprises silicone powder and modified ethylene bis stearamide in a mass ratio of 1:0.875-1.
By adopting the technical scheme, the silicone powder and the modified ethylene bis stearamide are used as the lubricant, the fluidity of materials can be further improved, the friction between the physical and the mold is reduced, the demolding effect is improved, the surface finish of the composite material is improved, the modified ethylene bis stearamide contains a polar group structure which can be combined with a polar group on the surface part of the chopped glass fiber, in a glass fiber reinforced or inorganic filling PA6 system, a similar anchoring node is formed between the chopped glass fiber and the PA6 resin, the bonding state of the chopped glass fiber and the PA6 resin is improved, and the dispersibility in the PA6 resin is improved.
Optionally, the compound antioxidant comprises an antioxidant 1098 and an antioxidant 168 in a mass ratio of 2-2.5:1.
By adopting the technical scheme, the antioxidant 1098 and the antioxidant 168 are used as compound antioxidants, so that the ageing resistance and the ultraviolet resistance of the PA6 material can be improved, and yellowing or cracking of the product due to oxidization can be avoided.
In a second aspect, the present application provides a method for preparing a fiber-free easy-to-release reinforced PA6 material, which adopts the following technical scheme:
a preparation method of a fiber-free easy-demolding reinforced PA6 material comprises the following steps:
uniformly mixing PA6 resin, MXD6 nylon resin, a compound antioxidant, a lubricant and crystallization inhibition master batch, adding chopped glass fibers from a side feeding port, blending, extruding, granulating and vacuum drying to obtain the floating-fiber-free reinforced PA6 material easy to release.
By adopting the technical scheme, other raw materials except the chopped glass fibers are blended, the chopped glass fibers are added through the side feeding port, so that the chopped glass fibers and matrix resin and the like can be uniformly blended, and the phenomenon of fiber floating is reduced.
In summary, the present application has the following beneficial effects:
1. because the PA6 material is prepared by adopting components such as PA6 resin, MXD6 nylon resin, crystallization inhibition master batch and the like, the crystallization inhibition master batch contains nylon resin, polyvinylpyrrolidone and chlorine-containing compounds (lithium chloride and/or calcium chloride), the crystallization inhibition master batch and MXD6 can limit the movement of a PA6 molecular chain, and the crystallization degree of the PA6 resin is reduced, so that the cooling speed of the PA6 material on the surface of a mould is reduced, the chopped glass fibers are not easy to be quickly punched on the surface of a finished piece to form floating fibers, and the PA6 material which has no floating fibers on the surface and is easy to demould is prepared.
2. In the application, the MXD6 nylon resin with the viscosity larger than that of the PA6 resin is adopted, the melting point of the MXD6 nylon resin is higher than that of the PA6 resin, the PA6 resin flows after being completely hot-melted during injection molding, the MXD6 with the viscosity not being completely hot-melted is larger, the fluidity is slower, the chopped glass fiber can be dragged, the PA6 resin can rapidly form a coating on the surface of a die, and therefore the chopped glass fiber is better coated, and a better anti-floating fiber effect is achieved.
3. In the application, blend liquid formed by polyvinylidene fluoride, hyperdispersant, nano silicon dioxide and the like is preferably adopted to carry out spraying treatment on the chopped glass fibers pretreated by the silane coupling agent, so that the wettability of the prepared chopped glass fibers is improved, the surface smoothness and the compactness are improved, the surface smoothness of a workpiece is improved, and the glossiness is increased.
Detailed Description
Preparation examples 1 to 6 of crystallization-inhibiting master batch
Preparation example 1: mixing 64.5g of nylon resin after drying (120 ℃ C., 4 h) with 5g of chlorine-containing compound, 30g of polyvinylpyrrolidone and 0.5g of compound antioxidant uniformly, adding into a main feeding port of an extruder, melting, extruding, granulating and drying to obtain crystallization inhibition master batch, wherein the chlorine-containing compound comprises calcium chloride and lithium chloride in a mass ratio of 1:1, the compound antioxidant comprises antioxidant 1098 and antioxidant 168 in a mass ratio of 2:1, the viscosity of the nylon resin is 2.45, the nylon resin is selected from the sea-sun technology and technology Co., ltd., model number is HY2500A, the polyvinylpyrrolidone model number is K30, the screw speed of the extruder is 350rpm, the first zone temperature is 190 ℃, the second zone temperature is 200 ℃, the third zone temperature is 220 ℃, the fourth zone temperature is 220 ℃, the fifth zone temperature is 230 ℃, the sixth zone temperature is 225 ℃, the seventh zone temperature is 230 ℃, the eighth zone temperature is 230 ℃, the ninth zone temperature is 235 ℃, and the tenth zone temperature is 235 ℃.
Preparation example 2: mixing 60.6g of nylon resin after drying (120 ℃ C., 4 h) with 4g of chlorine-containing compound, 35g of polyvinylpyrrolidone and 0.4g of compound antioxidant uniformly, adding into a main feeding port of an extruder, melting, extruding, granulating and drying to obtain crystallization inhibition master batch, wherein the chlorine-containing compound comprises calcium chloride and lithium chloride with the mass ratio of 1:0.8, the compound antioxidant comprises antioxidant 1098 and antioxidant 168 with the mass ratio of 2:1, the viscosity of the nylon resin is 2.45, the nylon resin is selected from the sea-sun technology and technology Co., ltd., model number is HY2500A, the polyvinylpyrrolidone model number is K30, the screw speed of the extruder is 350rpm, the first zone temperature is 190 ℃, the second zone temperature is 200 ℃, the third zone temperature is 220 ℃, the fourth zone temperature is 220 ℃, the fifth zone temperature is 230 ℃, the sixth zone temperature is 225 ℃, the seventh zone temperature is 230 ℃, the eighth zone temperature is 230 ℃, and the ninth zone temperature is 235 ℃ and the tenth zone temperature is 235 ℃.
Preparation example 3: the difference from preparation example 1 is that the chlorine-containing compound is calcium chloride.
Preparation example 4: the difference from preparation example 1 is that the chlorine-containing compound is lithium chloride.
Preparation example 5: the difference from preparation example 1 is that no chlorine-containing compound was added.
Preparation example 6: the difference from preparation example 1 is that polyvinylpyrrolidone was not added.
Examples
Example 1: the raw material proportion (in kg) of the reinforced PA6 material is shown in Table 1, the viscosity of the PA6 resin in Table 1 is 2.45, the PA6 material is selected from sea technologies and technologies, inc., model HY2500A, the relative viscosity of the MXD6 nylon resin is 2.65, and the specific gravity is 1.22g/cm 3 The melt index is 2g/10min, the product is selected from Mitsubishi gas chemical Co., ltd, the model is ME1007, the crystallization inhibition master batch is prepared from preparation example 1, the length of the chopped glass fiber is 3mm, the diameter is 10 μm, the product is selected from China boulder GmbH, the model is 568H, the compound antioxidant comprises antioxidant 1098 and antioxidant 168 in a mass ratio of 2:1, the lubricant is modified ethylene bis stearamide, and the product is selected from Suzhou Xingtailand photochemical auxiliary agent Co.
The preparation method of the floating-fiber-free easy-demolding reinforced PA6 material comprises the following steps:
uniformly mixing PA6 resin, MXD6 nylon resin, a compound antioxidant, a lubricant and crystallization inhibition master batch, adding chopped glass fibers from a side feeding port, blending, extruding, granulating, vacuum drying, injection molding, wherein the screw speed is 250r/min, the vacuum drying temperature is 120 ℃, and the temperature of each region during extrusion is as follows: the temperature of the first area is 190 ℃, the temperature of the second area is 190 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 250 ℃, the temperature of the sixth area is 240 ℃, the temperature of the seventh area is 220 ℃, the temperature of the eighth area is 220 ℃, the temperature of the ninth area is 220 ℃, and the temperature of the tenth area is 220 ℃, so that the reinforced PA6 material without floating fiber and easy to demould is prepared.
TABLE 1 raw material ratios of the free-fiber easy-to-demold reinforced PA6 materials in examples 1-6
Example 2: a fiber-free easy-to-release reinforced PA6 material is different from example 1 in that the lubricant comprises silicone powder and modified ethylene bis-stearamide in a mass ratio of 1:1, wherein the silicone powder is selected from the group consisting of Chengdu Siro technology Co., ltd, and the model number is LYSI-100.
Examples 3 to 6: the difference between the free-floating fiber and the easy-demolding reinforced PA6 material and the example 1 is that the raw materials are shown in the table 1.
Example 7: the difference between the fiber-free easy-release reinforced PA6 material and the material of example 4 is that the crystallization-inhibiting master batch is prepared in preparation example 3.
Example 8: the difference between the fiber-free easy-release reinforced PA6 material and the material of example 4 is that the crystallization-inhibiting master batch is prepared in preparation example 4.
Example 9: the difference between the non-floating fiber and the easy-demolding reinforced PA6 material in example 4 is that the chopped glass fiber is pretreated by the following steps:
immersing 50kg of chopped glass fibers in 50kg of aqueous solution of a silane coupling agent KH550 with the concentration of 2.5wt%, taking out, and drying to prepare pretreated chopped glass fibers;
dissolving 10.5kg of polyvinylidene fluoride in N, N-dimethylformamide to prepare a solution with the concentration of 55wt%, adding 6kg of hyperdispersant and 8kg of nano silicon dioxide, and carrying out ultrasonic homogenization to prepare a blend solution, wherein the polyvinylidene fluoride is selected from the group consisting of asuwei, model 6010, the hyperdispersant is selected from the group consisting of Lubo 17000, the silicon dioxide is fumed silica, and the model is Wak HDK H15;
and uniformly spraying the blending liquid on the pretreated chopped glass fiber, and drying.
Example 10: the difference between the non-floating fiber and the easy-demolding reinforced PA6 material in example 4 is that the chopped glass fiber is pretreated by the following steps:
immersing 40kg of chopped glass fibers in 40kg of an aqueous solution of a silane coupling agent KH550 with the concentration of 2.5wt%, taking out, and drying to obtain pretreated chopped glass fibers;
dissolving 5kg of polyvinylidene fluoride in N, N-dimethylformamide to prepare a solution with the concentration of 50wt%, adding 3kg of hyperdispersant and 4kg of nano silicon dioxide, and carrying out ultrasonic homogenization to prepare a blend solution, wherein the polyvinylidene fluoride is selected from the group consisting of asuwei, model 6010, the hyperdispersant is selected from the group consisting of lubo 17000, the silicon dioxide is fumed silica and the model is Wak HDK H15;
and uniformly spraying the blending liquid on the pretreated chopped glass fiber, and drying.
Example 11: the difference between the fiber-free easy-demolding reinforced PA6 material and the material of the example 10 is that no nano silicon dioxide is added into the blending liquid.
Example 12: the difference between the free-floating fiber easy-demolding reinforced PA6 material and the embodiment 10 is that no hyperdispersant is added into the blending liquid.
Example 13: the fiber-free easy-release reinforced PA6 material differs from example 10 in that an equal amount of water is used instead of the blend.
Example 14: the difference between the free-floating fiber and the easy-demolding reinforced PA6 material and the embodiment 10 is that the chopped glass fiber is not pretreated by a silane coupling agent.
Comparative example
Comparative examples 1 to 7: the difference between the free-floating fiber and the easy-demolding reinforced PA6 material and the difference between the free-floating fiber and the easy-demolding reinforced PA6 material in example 1 is shown in the following table 2.
Table 2 raw material ratios of the non-float easily releasable reinforced PA6 materials of comparative examples 1 to 7
Comparative example 8: a fiber-free easy-release reinforced PA6 material is different from example 1 in that a crystallization-inhibiting master batch is produced from production example 5.
Comparative example 9: a fiber-free easy-to-release reinforced PA6 material is different from example 1 in that a crystallization-inhibiting master batch is produced from preparation example 6.
Example 10: a fiber-free easy-to-release reinforced PA6 material is different from example 4 in that the PA6 resin is selected from Baling petrochemical, the model is BL3280H, and the relative viscosity is 2.8.
Comparative example 11: the warp-resistant glass fiber reinforced nylon material consists of the following components: 40 parts of nylon 66; 30 parts of glass fiber; urea-formaldehyde resin 5 parts; the mineral filler is biotite, 20 parts; 5 parts of acidic high-temperature ionic liquid, wherein the viscosity of nylon is medium viscosity, the relative viscosity is 2.45-2.8, and the anion in the acidic high-temperature ionic liquid is BF 4 - 。
The preparation process of the warp-resistant glass fiber reinforced nylon material comprises the following steps:
s1, carrying out ultrasonic treatment, cleaning and drying on glass fibers after carrying out surface treatment; the surface treatment is to soak glass fiber in 20% hydrofluoric acid for 3 hr, and the glass fiber is selected from low oriented glass fiber with elliptic cross section.
S2, mixing nylon 66, urea-formaldehyde resin, mineral filler and an auxiliary agent, then placing the mixture in a double-screw extruder, simultaneously adding glass fiber subjected to surface treatment from a feed inlet, and performing injection molding to obtain the warp-resistant glass fiber reinforced nylon material, wherein the process control conditions of the double-screw extruder are as follows: first zone 230 ℃, second zone 230 ℃, third zone 235 ℃, fourth zone 235 ℃, fifth zone 240 ℃, sixth zone 240 ℃, seventh zone 240 ℃, eighth zone 240 ℃, ninth zone 240 ℃, tenth zone 240 ℃; the residence time was 2min and the pressure was 12MPa.
Performance test
PA6 materials were prepared according to the methods in examples and comparative examples, and performance tests were performed with reference to the following methods, and the test results are recorded in table 3.
1. Density: detection is carried out according to GB/T1033-1986 test method for Density and relative Density of plastics;
2. tensile strength: detection is carried out according to GB/T1040-1992 method for testing tensile Property of plastics;
3. flexural strength: detection is carried out according to GB/T9341-2008 'determination of Plastic bending Property';
4. notched Izod impact Strength: detecting according to GB/T1843-2008 'determination of impact strength of Plastic cantilever beam';
5. whether the appearance has floating fiber and whether easy demoulding: adding 1.5% of cabot 2014 black master batch into the prepared PA6 material, uniformly stirring, performing injection molding to obtain a color plate with the thickness of 120mm multiplied by 2.5mm, wherein the injection molding range temperature is 230-270 ℃, the mold temperature is 70 ℃, observing the surface effect and observing the mucous membrane property;
6. gloss level: the detection is carried out according to GB/T8807-1988 method for testing specular gloss of plastics, and 60-degree angle illumination is adopted for detecting signals.
TABLE 3 Performance test results of fiber-free easy-to-demold reinforced PA6 Material
As can be seen from the data in examples 1-6 and Table 3, the mechanical strength of the PA6 material is gradually enhanced with the increase of the amount of chopped glass fibers in examples 1-4, the appearance and the mold release property are also better, the same amount of chopped glass fibers in examples 4-6, the performances of examples 4 and 5 are basically similar, and the amount of MXD6 nylon resin in example 6 is smaller, so that each performance is reduced.
Example 7 and example 8 use only calcium chloride and lithium chloride as chlorine-containing compounds, respectively, and are added to the crystallization inhibitor, and the PA6 materials prepared in example 7 and example 8 are excellent in various properties, as compared with example 4.
The chopped glass fibers in the examples 9 and 10 are pretreated, so that the tensile strength, the bending strength and the impact resistance of the prepared PA6 material are improved, the surface is free of floating fibers, the demolding is easy, and the surface glossiness is improved.
When the chopped strand glass fibers were pretreated in example 11, no silica was added, and the mechanical strength such as the tensile strength of the PA6 material in example 11 was reduced and the surface gloss was reduced as compared with example 7.
In example 12, compared with example 10, when the chopped glass fibers are pretreated, no hyperdispersant is added, and the mechanical strength of the PA6 material prepared in example 12 is not greatly changed, but the surface glossiness is reduced.
The blend of pre-treated chopped strand glass fibers in example 13 was replaced with water to produce a PA6 material having similar properties to example 4 as compared to example 10.
The absence of coupling agent pretreatment of chopped strand glass fibers in example 14 resulted in a decrease in the tensile strength and impact strength of the PA6 material and a decrease in gloss.
In comparative example 1, when MXD6 nylon resin and crystallization-inhibiting master batch were not added, although the chopped glass fiber content was small, a fiber floating phenomenon still occurred, and in comparative example 7, only crystallization-inhibiting master batch was not added, a fiber floating phenomenon occurred, and release was still easy.
In the comparative example 2 and the comparative example 3, the compounding ratio of the MXD6 nylon resin to the crystallization inhibition master batch is respectively 10:1 and 4:6, and the surface of the PA6 material is floated due to the unsuitable compounding ratio, but the demolding is easy; the comparative example 4 was too large in the amount of MXD6 nylon resin, the comparative example 5 was too large in the amount of the crystallization-inhibiting master batch, and the comparative example 5 was not found to have the floating fiber, but the crystallization ability was severely affected, resulting in unsatisfactory demolding, affecting the processability, the comparative example 6 was too high in the chopped glass fiber content, resulting in floating fiber, and at the same time, the crystallization ability was weakened, resulting in a mucous membrane, the comparative example 7 was not added with the crystallization-inhibiting master batch, the floating fiber was found to be serious, and the demolding was difficult.
In comparative examples 8 and 9, no chlorine compound and polyvinylpyrrolidone were added, respectively, and the surface of the PA6 material showed fiber floating and the mechanical strength was also affected due to unsatisfactory demolding compared with example 1, and PA6 resin having a relatively large viscosity was used in comparative example 10, and the flow rate of PA6 resin was slow compared with example 1, so that MXD6 nylon resin hardly had the effect of pulling chopped glass fiber, and the surface of the PA6 material thus produced showed fiber floating and decreased gloss.
The nylon and glass fiber composite material of comparative example 11 was not prior art, but had higher tensile strength and flexural strength, but had surface float fiber and was not easily released from the mold.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (10)
1. The fiber-free easy-demolding reinforced PA6 material is characterized by comprising the following raw materials in parts by weight: 26.7-72.1 parts of PA6 resin, 20-50 parts of chopped glass fiber, 5-15 parts of MXD6 nylon resin, 0.4-0.8 part of compound antioxidant, 0.5-1.5 parts of lubricant and 2-6 parts of crystallization inhibition master batch;
the crystallization inhibition master batch comprises the following raw materials in parts by weight: 60.6-64.5 parts of nylon resin, 4-5 parts of chlorine-containing compound, 30-35 parts of polyvinylpyrrolidone and 0.4-0.5 part of compound antioxidant, wherein the chlorine-containing compound is lithium chloride or/and calcium chloride.
2. The fiber-free easy-release reinforced PA6 material according to claim 1, wherein: the chlorine-containing compound comprises calcium chloride and lithium chloride in a mass ratio of 1:0.8-1.
3. The fiber-free easy-release reinforced PA6 material according to claim 1, wherein the mass ratio of MXD6 nylon resin to crystallization-inhibiting master batch is 2-2.5:1.
4. The fiber-free easy release reinforced PA6 material according to claim 1, wherein the PA6 resin has a viscosity of 2.2-2.5 and mxd6 nylon resin has a viscosity of 2.45-2.7.
5. The fiber-free easy-to-release reinforced PA6 material according to claim 1, wherein the chopped glass fiber is subjected to the following pretreatment:
immersing the chopped glass fibers in an aqueous solution of a silane coupling agent, taking out and drying to obtain pretreated chopped glass fibers;
dissolving polyvinylidene fluoride in a solvent to prepare a solution with the concentration of 50-55wt%, adding a hyper-dispersant and nano silicon dioxide, and carrying out ultrasonic homogenization to prepare a blend solution;
and uniformly spraying the blending liquid on the pretreated chopped glass fiber, and drying.
6. The fiber-free easy-to-release reinforced PA6 material according to claim 5, wherein when the chopped glass fiber is pretreated, the following raw materials are in parts by weight: 40-50 parts of chopped glass fiber, 40-50 parts of aqueous solution of silane coupling agent, 5-10.5 parts of polyvinylidene fluoride, 3-6 parts of hyperdispersant and 4-8 parts of nano silicon dioxide.
7. The fiber-free easy release reinforced PA6 material of claim 1, wherein the lubricant is selected from at least one of silicone powder, modified ethylene bis stearamide, and calcium stearate.
8. The fiber-free easy release reinforced PA6 material of claim 7, wherein the lubricant comprises silicone powder and modified ethylene bis stearamide in a mass ratio of 1:0.875-1.
9. The fiber-free easy release reinforced PA6 material of claim 1, wherein the compounded antioxidant comprises an antioxidant 1098 and an antioxidant 168 in a mass ratio of 2-2.5:1.
10. The method for preparing the fiber-free easy-to-release reinforced PA6 material according to any one of claims 1 to 9, comprising the following steps:
uniformly mixing PA6 resin, MXD6 nylon resin, a compound antioxidant, a lubricant and crystallization inhibition master batch, adding chopped glass fibers from a side feeding port, blending, extruding, granulating and vacuum drying to obtain the floating-fiber-free reinforced PA6 material easy to release.
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| CN115746542B (en) * | 2022-09-01 | 2024-04-05 | 厦门东鑫达模塑科技有限公司 | High-performance long glass fiber reinforced thermoplastic composite material and preparation method thereof |
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