CN114507438A - Polyamide and silicate composite material and preparation method thereof - Google Patents
Polyamide and silicate composite material and preparation method thereof Download PDFInfo
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- CN114507438A CN114507438A CN202111024878.5A CN202111024878A CN114507438A CN 114507438 A CN114507438 A CN 114507438A CN 202111024878 A CN202111024878 A CN 202111024878A CN 114507438 A CN114507438 A CN 114507438A
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- polyamide
- silicate
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 63
- 229920002647 polyamide Polymers 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 30
- 239000003607 modifier Substances 0.000 claims abstract description 29
- 239000003365 glass fiber Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000000835 fiber Substances 0.000 claims description 28
- 239000005357 flat glass Substances 0.000 claims description 26
- -1 amine compounds Chemical class 0.000 claims description 23
- 229920000578 graft copolymer Polymers 0.000 claims description 22
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 5
- 150000008045 alkali metal halides Chemical class 0.000 claims description 5
- 229910052615 phyllosilicate Inorganic materials 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 5
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 229920000571 Nylon 11 Polymers 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 125000005375 organosiloxane group Chemical group 0.000 claims description 3
- 239000002530 phenolic antioxidant Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 2
- 150000004760 silicates Chemical class 0.000 claims description 2
- 229910052610 inosilicate Inorganic materials 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 239000003017 thermal stabilizer Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 28
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 24
- SLUKQUGVTITNSY-UHFFFAOYSA-N 2,6-di-tert-butyl-4-methoxyphenol Chemical compound COC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SLUKQUGVTITNSY-UHFFFAOYSA-N 0.000 description 18
- 229910052901 montmorillonite Inorganic materials 0.000 description 17
- 239000004698 Polyethylene Substances 0.000 description 15
- 229920000573 polyethylene Polymers 0.000 description 15
- 239000002245 particle Substances 0.000 description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 10
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 9
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 235000012216 bentonite Nutrition 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229910000273 nontronite Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Classifications
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- 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
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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
-
- 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
- C08K3/346—Clay
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/19—Quaternary ammonium 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- 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
- C08K7/14—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
- C08K9/04—Ingredients treated with organic 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a polyamide and silicate composite material, which comprises the following raw materials in parts by weight: 40-60 parts of polyamide, 10-30 parts of glass fiber, 5-15 parts of silicate, 0.4-4.5 parts of heat stabilizer, 0.1-5 parts of antioxidant, 0.2-5 parts of compatilizer and 0.1-2 parts of surface modifier; the prepared composite material has the advantages of simple preparation process, high production efficiency, excellent stability, heat resistance and mechanical property, and wide application prospect in the aspects of electronic parts, automobile parts, mechanical structural parts and the like.
Description
Technical Field
The invention relates to the technical field of engineering plastics (C08L77/00), in particular to a polyamide and silicate composite material and a preparation method thereof.
Background
Polyamides are a general term for a series of high molecular polymers containing amide groups in the repeating units of the main chain of the macromolecule. Compared with common plastics, the polyamide has the advantages of wear resistance, light weight, toughness, drug resistance, heat resistance, self lubrication, easy molding, easy dyeing and no toxicity. Polyamide is one of the most common engineering plastics and is widely applied to automobile parts, electronic products, living homes, mechanical parts and the like. However, the presence of polar amide groups leads to high water absorption of the polyamide, which deteriorates its dimensional stability. The heat distortion temperature is low, which causes the deterioration of mechanical and physical properties and limits the application.
Chinese patent (CN201480021846.1) discloses a glass fiber reinforced polyamide resin composition which can improve the strength, rigidity and dimensional stability, but increase the density of the material and have insufficient heat resistance. Furthermore, chinese patent (cn200910252473.x) relates to a polyamide phyllosilicate composition comprising an untreated clay mineral and a water-soluble polyamide, which reduces the cost of the polyamide, improves the dimensional stability and increases the stiffness, but results in a decrease in the toughness of the material.
Disclosure of Invention
In order to solve the above problems, a first aspect of the present invention provides a polyamide and silicate composite material, which comprises the following raw materials in parts by weight: 40-60 parts of polyamide, 10-30 parts of glass fiber, 5-15 parts of silicate, 0.4-4.5 parts of heat stabilizer, 0.1-5 parts of antioxidant, 0.2-5 parts of compatilizer and 0.1-2 parts of surface modifier.
As a preferable technical solution, the polyamide is one selected from polyamide 6, polyamide 66, polyamide 11, polyamide 12, and polyamide 46.
As a preferred technical solution, the silicate is selected from one or more of chain silicate and layered silicate.
Further, the silicate is preferably one of layered silicates.
Further, the phyllosilicate is selected from one or more of montmorillonite, rectorite, hectorite, sepiolite, bentonite, kaolin, beidellite, talc and nontronite.
Further, the phyllosilicate is preferably one of montmorillonite.
Further, the montmorillonite is selected from one or more of sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite and lithium montmorillonite.
Further, the montmorillonite is preferably sodium montmorillonite.
Further, the mean particle size of the sodium montmorillonite is 300-2500 meshes.
As a preferred technical solution, the glass fiber is selected from one of round glass fiber and flat glass fiber.
Further, the glass fiber is preferably a flat glass fiber.
Further, the aspect ratio (major axis/minor axis) of the non-circular cross-section of the flat glass fiber is 1: 3 to 4.
As a preferable embodiment, the heat stabilizer is one selected from a hindered phenol compound, a hindered amine compound, and an alkali metal halide.
Further, the heat stabilizer is preferably one of alkali metal halides.
Further, the alkali metal halide is selected from one or more of sodium chloride, potassium bromide, potassium iodide and cuprous iodide.
Further, the alkali metal halide is preferably potassium iodide and cuprous iodide.
Further, the molar ratio of the cuprous iodide to the potassium iodide is 1: 5.
as a preferable technical scheme, the antioxidant is selected from one or more of amine antioxidants, phenol antioxidants and ester antioxidants.
Further, the antioxidant is preferably one of phenolic antioxidants.
Further, the phenolic antioxidant is selected from one or more of 2, 6-di-tert-butyl-4-methylphenol, 2, 4-dioctylthiomethyl-6-methylphenol, 2, 6-di-tert-butyl-4-methoxyphenol and 2, 5-di-tert-butylhydroquinone.
As a preferable technical scheme, the compatilizer is selected from one or more of maleic anhydride graft copolymer, glycidyl methacrylate, acrylic acid, epoxy acrylate and methacrylic acid.
Further, the compatibilizer is preferably one of maleic anhydride graft copolymers.
Further, the maleic anhydride graft copolymer is selected from one or more of a maleic anhydride graft copolymer of polyethylene, a maleic anhydride graft copolymer of polypropylene, a maleic anhydride graft copolymer of ethylene-propylene copolymer, an ethylene-vinyl acetate-maleic anhydride copolymer, and an ethylene-acrylate-maleic anhydride copolymer.
As a preferable technical scheme, the surface modifier is selected from one or more of organic siloxane, polysiloxane, organic titanate and organic quaternary ammonium salt.
Further, the surface modifier is preferably one of an organosiloxane and an organic quaternary ammonium salt.
Further, the organosiloxane is preferably γ -aminopropyltriethoxysilane.
Further, the organic quaternary ammonium salt is preferably cetyltrimethylammonium bromide.
A second aspect of the present invention provides a method for preparing a polyamide and silicate composite material, comprising the steps of:
(1) the material comprises the following components in parts by weight: 40-60 parts of polyamide, 10-30 parts of glass fiber, 5-15 parts of silicate, 0.4-4.5 parts of heat stabilizer, 0.1-5 parts of antioxidant, 0.2-5 parts of compatilizer and 0.1-2 parts of surface modifier;
(2) stirring and mixing polyamide, silicate, glass fiber, compatilizer and surface modifier; stirring and mixing for 1-2.5 h, and preferably for 1.2 h;
(3) continuously adding the antioxidant and the heat stabilizer, and mixing for 1.5-3 h, preferably for 2 h;
(4) and adding the mixture into a double-screw extruder, and melting and extruding the material through the double-screw extruder to obtain the composite material. The reaction temperature in the double-screw extruder is 220-290 ℃, and the screw revolution is 200-500 rpm/min.
Has the advantages that:
(1) by adding 40-60 parts of polyamide, 10-30 parts of glass fiber and 5-15 parts of silicate, the obtained composite material has excellent stability, heat resistance and mechanical property, and has wide application prospect in the aspects of electronic parts, automobile parts, mechanical structural parts and the like.
(2) According to the invention, the flat glass fiber is added as a reinforcing material, so that the polyamide has excellent mechanical properties and processability; in particular, the aspect ratio of the non-circular cross section of the flat glass fiber is 1: 3-4, it will penetrate sufficiently into the polyamide matrix to flow in a planar state like mica, rather than rolling and tumbling as in conventional round glass monofilaments, which will help provide more isotropic dispersion and, due to the more dense packing of the fibers, a high packing density, resulting in higher flexural modulus, higher mechanical strength (especially in the direction of the fibers), and increased strength of the polyamide.
(3) By adding the phyllosilicate montmorillonite, the polyamide molecular chain can be inserted between montmorillonite layers, so that the thermal stability of the polyamide is improved; particularly, the sodium-based montmorillonite has the average particle size of 300-2500 meshes and very large interface area, can improve the crystallinity of polyamide, enables an amorphous area to be small, and reduces the water absorption capacity of the polyamide; the expansibility and the cation exchange property of the sodium montmorillonite can be improved, the melt dripping phenomenon of the polyamide is improved, and the rigidity and the high heat resistance of the polyamide composite material are improved.
(4) The surface modifier organic siloxane and the organic quaternary ammonium salt are added, so that the polyamide composite material has better toughness. The cetyl trimethyl ammonium bromide can exchange sodium ions in the sodium-based montmorillonite out, and organized into sheets on the surface, so that firm chemical bonding is generated between polyamide molecular chains and the sheets, and long-chain alkane can be inserted between the sheets to increase the space between the sheets, so that the sodium-based montmorillonite can better achieve uniform and stable nano-scale dispersibility in the polyamide; after the surface of the glass fiber is treated by gamma-aminopropyltriethoxysilane, the compatibility between the glass fiber and polyamide is increased; the coaction of the hexadecyl trimethyl ammonium bromide and the gamma-aminopropyl triethoxysilane can increase the system stability and the solvent resistance of the composite material, and further improve the mechanical property and the thermal deformation temperature of the composite material.
(5) The polyamide composite material with high performance can be better prepared by mixing polyamide, glass fiber and silicate with a certain amount of heat stabilizer, antioxidant, compatilizer and surface modifier, and has simple process and high production efficiency.
Detailed Description
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Example 1
Embodiment 1 provides a polyamide and silicate composite material, which comprises the following raw materials in parts by weight: 640 parts of polyamide, 30 parts of flat glass fiber, 15 parts of sodium montmorillonite with the average particle size of 300 meshes, 0.4 part of heat stabilizer, 0.1 part of 2, 6-di-tert-butyl-4-methoxyphenol, 5 parts of maleic anhydride graft copolymer of polyethylene and 2 parts of surface modifier;
the molar ratio of cuprous iodide to potassium iodide in the heat stabilizer is 1: 5;
the weight ratio of gamma-aminopropyltriethoxysilane to cetyl trimethyl ammonium bromide in the surface modifier is 1: 1;
polyamide 6 was obtained from Shanghai Fuchen Plastic materials Ltd;
flat glass fibers were purchased from the international composite materials corporation ESC301-HF, having an aspect ratio of 1: 4;
na-montmorillonite is purchased from processing plants of Chengshou county Chengzun mineral products;
cuprous iodide CAS No.: 7681-65-4;
potassium iodide CAS No.: 7681-11-0;
2, 6-di-tert-butyl-4-methoxyphenol CAS No.: 489-01-0;
maleic anhydride graft copolymer of polyethylene CAS No.: 106343-08-2;
gamma-aminopropyltriethoxysilane CAS number: 919-30-2;
cetyltrimethylammonium bromide CAS number: 57-09-0;
the preparation method comprises the following steps:
(1) the material comprises the following components in parts by weight: 640 parts of polyamide, 30 parts of flat glass fiber, 15 parts of sodium montmorillonite with the average particle size of 300 meshes, 0.4 part of heat stabilizer, 0.1 part of 2, 6-di-tert-butyl-4-methoxyphenol, 5 parts of maleic anhydride graft copolymer of polyethylene and 2 parts of surface modifier;
(2) stirring and mixing polyamide 6, sodium montmorillonite with the average particle size of 300 meshes, flat glass fiber, maleic anhydride graft copolymer of polyethylene and a surface modifier for 1 h;
(3) continuously adding 2, 6-di-tert-butyl-4-methoxyphenol and a heat stabilizer, and mixing for 1.5 h;
(4) and adding the mixture into a double-screw extruder, and melting and extruding the material through the double-screw extruder to obtain the composite material. The reaction temperature in the twin-screw extruder was 220 ℃ and the number of screw revolutions was 200 rpm/min.
Example 2
Embodiment 2 provides a polyamide and silicate composite material, which comprises the following raw materials in parts by weight: polyamide 6650 parts, flat glass fiber 20 parts, Na-montmorillonite 10 parts with average particle size of 1500 meshes, heat stabilizer 2.5 parts, 2.5 parts of 2, 6-di-tert-butyl-4-methoxyphenol, 0.2 part of maleic anhydride graft copolymer of polyethylene and 1 part of surface modifier;
the molar ratio of cuprous iodide to potassium iodide in the heat stabilizer is 1: 5;
the weight ratio of the gamma-aminopropyl triethoxy silane hexadecyl trimethyl ammonium bromide in the surface modifier is 1: 1;
polyamide 66 was obtained from Shanghai Fuchen Plastic materials Ltd;
flat glass fibers were purchased from the international composite materials corporation ESC301-HF, having an aspect ratio of 1: 4;
the preparation method comprises the following steps: (1) the material comprises the following components in parts by weight: polyamide 6650 parts, flat glass fiber 20 parts, Na-montmorillonite 10 parts with average particle size of 1500 meshes, heat stabilizer 2.5 parts, 2.5 parts of 2, 6-di-tert-butyl-4-methoxyphenol, 0.2 part of maleic anhydride graft copolymer of polyethylene and 1 part of surface modifier;
(2) stirring and mixing polyamide 66, sodium montmorillonite with the average particle size of 1500 meshes, flat glass fiber, a maleic anhydride graft copolymer of polyethylene and a surface modifier for 1.2 h;
(3) continuously adding 2, 6-di-tert-butyl-4-methoxyphenol and a heat stabilizer, and mixing for 2 hours;
(4) and adding the mixture into a double-screw extruder, and melting and extruding the material through the double-screw extruder to obtain the composite material. The reaction temperature in the twin-screw extruder was 250 ℃ and the number of screw revolutions was 400 rpm/min.
Example 3
Embodiment 3 provides a polyamide and silicate composite material, comprising the following raw materials in parts by weight: 1160 parts of polyamide, 10 parts of flat glass fiber, 5 parts of 2500-mesh sodium montmorillonite, 4.5 parts of heat stabilizer, 5 parts of 2, 6-di-tert-butyl-4-methoxyphenol, 2.5 parts of maleic anhydride graft copolymer of polyethylene and 0.2 part of surface modifier;
the molar ratio of cuprous iodide to potassium iodide in the heat stabilizer is 1: 5;
the weight ratio of gamma-aminopropyl triethoxy silane hexadecyl trimethyl ammonium bromide in the surface modifier is 1: 1;
polyamide 11 was obtained from Shanghai Fuchen Plastic materials Ltd;
flat glass fibers were purchased from the international composite materials corporation ESC301T, having an aspect ratio of 1: 3;
the preparation method comprises the following steps: (1) the material comprises the following components in parts by weight: polyamide 6640 parts, flat glass fiber 10 parts, 2500 mesh sodium montmorillonite 5 parts, heat stabilizer 4.5 parts, 2, 6-di-tert-butyl-4-methoxyphenol 5 parts, polyethylene maleic anhydride graft copolymer 2.5 parts, and surface modifier 0.2 part;
(2) stirring and mixing polyamide 66, sodium montmorillonite with the average particle size of 2500 meshes, flat glass fiber, a maleic anhydride graft copolymer of polyethylene and a surface modifier for 2.5 hours;
(3) continuously adding 2, 6-di-tert-butyl-4-methoxyphenol and a heat stabilizer, and mixing for 3 hours;
(4) and adding the mixture into a double-screw extruder, and melting and extruding the material through the double-screw extruder to obtain the composite material. The reaction temperature in the twin-screw extruder was 290 ℃ and the number of screw revolutions was 500 rpm/min.
Comparative example 1
Comparative example 1 provides a polyamide and silicate composite comprising the following raw materials in parts by weight: polyamide 6650 parts, flat glass fiber 20 parts, Na-montmorillonite 10 parts with average particle size of 1500 meshes, heat stabilizer 2.5 parts, 2.5 parts of 2, 6-di-tert-butyl-4-methoxyphenol and 0.2 part of maleic anhydride graft copolymer of polyethylene;
the molar ratio of cuprous iodide to potassium iodide in the heat stabilizer is 1: 5;
the weight ratio of the gamma-aminopropyl triethoxy silane hexadecyl trimethyl ammonium bromide in the surface modifier is 1: 1;
flat glass fibers were purchased from the international composite materials corporation ESC301-HF, having an aspect ratio of 1: 4;
the preparation method comprises the following steps: (1) the material comprises the following components in parts by weight: polyamide 6650 parts, flat glass fiber 20 parts, Na-montmorillonite 10 parts with average particle size of 1500 meshes, heat stabilizer 2.5 parts, 2.5 parts of 2, 6-di-tert-butyl-4-methoxyphenol and 0.2 part of maleic anhydride graft copolymer of polyethylene;
(2) stirring and mixing polyamide 66, sodium montmorillonite with the average particle size of 1500 meshes, flat glass fiber and a maleic anhydride graft copolymer of polyethylene for 1.2 h;
(3) continuously adding 2, 6-di-tert-butyl-4-methoxyphenol and a heat stabilizer, and mixing for 2 hours;
(4) and adding the mixture into a double-screw extruder, and melting and extruding the material through the double-screw extruder to obtain the composite material. The reaction temperature in the twin-screw extruder was 250 ℃ and the number of screw revolutions was 400 rpm/min.
Comparative example 2
Comparative example 2 provides a polyamide and silicate composite comprising the following raw materials in parts by weight: polyamide 6650 parts, flat glass fiber 20 parts, heat stabilizer 2.5 parts, 2, 6-di-tert-butyl-4-methoxyphenol 2.5 parts, compatibilizer 0.2 part, and surface modifier 1 part;
the molar ratio of cuprous iodide to potassium iodide in the heat stabilizer is 1: 5;
the weight ratio of the gamma-aminopropyl triethoxy silane hexadecyl trimethyl ammonium bromide in the surface modifier is 1: 1;
the flat glass fiber is purchased from ESC301-HF, International composite materials corporation of weight celebration, and has an aspect ratio of 1: 4;
the preparation method comprises the following steps: the preparation method comprises the following steps: (1) the material comprises the following components in parts by weight: polyamide 6650 parts, flat glass fiber 20 parts, heat stabilizer 2.5 parts, 2, 6-di-tert-butyl-4-methoxyphenol 2.5 parts, maleic anhydride graft copolymer of polyethylene 0.2 parts, and surface modifier 1 part;
(2) stirring and mixing polyamide 66, flat glass fiber, a maleic anhydride graft copolymer of polyethylene and a surface modifier for 1.2 h;
(3) continuously adding 2, 6-di-tert-butyl-4-methoxyphenol and a heat stabilizer, and mixing for 2 hours;
(4) and adding the mixture into a double-screw extruder, and melting and extruding the material through the double-screw extruder to obtain the composite material. The reaction temperature in the twin-screw extruder was 250 ℃ and the number of screw revolutions was 400 rpm/min.
Performance testing
1. Mechanical properties: the composite materials provided in examples 1 to 3 and comparative examples 1 to 2 were tested for tensile and flexural properties on a mechanical testing machine according to ISO527-2:1993, ISO178: 2001.
2. Toughness: the composites provided in examples 1-3 and comparative examples 1-2 were tested for notched Izod impact strength according to ISO180: 2001.
3. Heat distortion temperature: the composite materials provided in examples 1 to 3 and comparative examples 1 to 2 were subjected to a load of 1.82MPa to measure the heat distortion temperature.
The test results are shown in table 1:
TABLE 1 test results
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content of the above disclosure into equivalent embodiments with equivalent changes, but all those simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The polyamide and silicate composite material is characterized by comprising the following raw materials in parts by weight: 40-60 parts of polyamide, 10-30 parts of glass fiber, 5-15 parts of silicate, 0.4-4.5 parts of heat stabilizer, 0.1-5 parts of antioxidant, 0.2-5 parts of compatilizer and 0.1-2 parts of surface modifier.
2. Polyamide and silicate composite according to claim 1, characterized in that the polyamide is selected from one of polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 46.
3. Polyamide and silicate composite material according to claim 1, characterized in that the silicate is selected from one or more of chain silicates, layer silicates.
4. Polyamide and silicate composite according to claim 1, characterized in that the silicate is selected from one of the phyllosilicates.
5. The polyamide and silicate composite material of claim 1, wherein the glass fibers are selected from one of round glass fibers and flat glass fibers.
6. The polyamide and silicate composite material of claim 1, wherein the thermal stabilizer is selected from one of hindered phenol compounds, hindered amine compounds, and alkali metal halides.
7. The polyamide and silicate composite material as claimed in claim 1, wherein the antioxidant is selected from one or more of amine antioxidants, phenolic antioxidants and ester antioxidants.
8. The polyamide and silicate composite material according to claim 1, wherein the compatibilizer is selected from one or more of maleic anhydride graft copolymers, glycidyl methacrylate, acrylic acid, epoxy acrylate, methacrylic acid.
9. The polyamide and silicate composite material according to claim 1, characterized in that the surface modifier is selected from one or more of the group consisting of organosiloxanes, polysiloxanes, organotitanates, organic quaternary ammonium salts.
10. A method for preparing a polyamide and silicate composite material according to any one of claims 1 to 9, characterized in that it comprises the following steps:
(1) the material comprises the following components in parts by weight: 40-60 parts of polyamide, 10-30 parts of glass fiber, 5-15 parts of silicate, 0.4-4.5 parts of heat stabilizer, 0.1-5 parts of antioxidant, 0.2-5 parts of compatilizer and 0.1-2 parts of surface modifier;
(2) stirring and mixing polyamide, silicate, glass fiber, compatilizer and surface modifier; stirring and mixing for 1-2.5 h;
(3) continuously adding the antioxidant and the heat stabilizer, and mixing for 1.5-3 h;
(4) and adding the mixture into a double-screw extruder, and melting and extruding the material through the double-screw extruder to obtain the composite material, wherein the reaction temperature in the double-screw extruder is 220-290 ℃, and the screw revolution is 200-500 rpm/min.
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