CN116253991B - Reinforced nylon material with improved processability - Google Patents
Reinforced nylon material with improved processability Download PDFInfo
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- CN116253991B CN116253991B CN202310083914.8A CN202310083914A CN116253991B CN 116253991 B CN116253991 B CN 116253991B CN 202310083914 A CN202310083914 A CN 202310083914A CN 116253991 B CN116253991 B CN 116253991B
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- calcium carbonate
- nano calcium
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- 239000004677 Nylon Substances 0.000 title claims abstract description 61
- 229920001778 nylon Polymers 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 50
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 194
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 97
- 239000013078 crystal Substances 0.000 claims abstract description 67
- 239000003365 glass fiber Substances 0.000 claims abstract description 44
- 230000001788 irregular Effects 0.000 claims abstract description 42
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 59
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 238000003763 carbonization Methods 0.000 claims description 23
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 18
- 239000000920 calcium hydroxide Substances 0.000 claims description 18
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 18
- 238000001354 calcination Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000003607 modifier Substances 0.000 claims description 13
- 239000004611 light stabiliser Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 239000012528 membrane Substances 0.000 claims description 11
- 239000003822 epoxy resin Substances 0.000 claims description 10
- 229920000647 polyepoxide Polymers 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 10
- 150000003505 terpenes Chemical class 0.000 claims description 10
- 235000007586 terpenes Nutrition 0.000 claims description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 9
- 239000011976 maleic acid Substances 0.000 claims description 9
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 235000019738 Limestone Nutrition 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000006028 limestone Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- DUIOPKIIICUYRZ-UHFFFAOYSA-N semicarbazide Chemical compound NNC(N)=O DUIOPKIIICUYRZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract 1
- -1 PA56 Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 229920002292 Nylon 6 Polymers 0.000 description 8
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 230000029087 digestion Effects 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 1
- 229920000856 Amylose Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 1
- 229920006117 poly(hexamethylene terephthalamide)-co- polycaprolactam Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000005491 wire drawing Methods 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
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- 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
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention provides a reinforced nylon material having improved processability comprising: 30-60 parts of nylon, 20-40 parts of glass fiber, 10-20 parts of nano calcium carbonate with irregular crystal forms and 0.1-3 parts of auxiliary agent. The invention also provides a preparation method of the composite.
Description
Technical Field
The application relates to the technical field of high polymer materials, in particular to a reinforced nylon material with improved processability and a preparation method thereof.
Background
Nylon (PA) is an engineering plastic with the most wide application and the most variety, and the material has good mechanical properties, heat resistance, wear resistance, chemical solvent resistance, self-lubricating property and certain flame retardance, and is widely used in the fields of automobiles, electronic appliances, machinery, rail transit, sports equipment and the like. However, nylon is a semi-crystalline material with a relatively high melting point, making it difficult to process in hot melt connections such as ultrasonic welding. In order to improve the processability of nylon, one useful way is to reduce the crystallinity of the nylon material, which in turn reduces the melting point. However, this method inevitably results in a decrease in the rigidity of the nylon material, impairing the mechanical properties of the nylon material.
Thus, there is a need in the art for an easy to process nylon material with good mechanical properties.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel reinforced nylon material which has excellent mechanical properties and a low melting point, and is easy to use for processing, such as hot melt connection, such as ultrasonic welding.
In particular, the present invention relates to a reinforced nylon material comprising: 30-60 parts of nylon, 20-40 parts of glass fiber, 10-20 parts of nano calcium carbonate with irregular crystal forms and 0.1-3 parts of auxiliary agent.
The nylon used to prepare the reinforced nylon material of the present invention is not limited. For example, the nylon may include at least one of PA6, PA66, PA56, PA66/6T, PA T/66, PA6T/6, PA6T/66/6, PA 6T/6I. Preferably, the nylon may be PA6 (i.e., polycaprolactam) or PA66 (i.e., polyhexamethylene adipamide).
The glass fibers used to prepare the reinforced nylon material of the present invention are not limited. For example, the glass fibers may include any one or a mixture of several of continuous glass fibers, chopped glass fibers, milled glass fibers, alkali-free glass fibers, medium alkali glass fibers, and high alkali glass fibers. For example, the glass fiber may be an E-type alkali-free long glass fiber.
As used herein, nano calcium carbonate having an irregular crystalline form refers to crystals of nano calcium carbonate having an irregular shape, such as, but not limited to, an asymmetric polyhedron, such as the exemplary shape shown in fig. 1.
In a specific embodiment, the aspect ratio of the nano calcium carbonate having an irregular crystal form is greater than 1.
In a specific embodiment, the specific surface area of the nano calcium carbonate having an irregular crystal form is 16-20m 2 /g, e.g. 16, 17, 18, 19, 20m 2 /g and any range therebetween.
In a specific embodiment, the nano calcium carbonate having an irregular crystal form is prepared by using a crystal form controlling agent a and a crystal form controlling agent B in stages in the preparation process of the nano calcium carbonate, wherein the crystal form controlling agent a is a mixture of malic acid and starch in a mass ratio of 3-5:1, and the crystal form controlling agent B is a mixture of sodium carbonate and cellulose in a mass ratio of 2-3:1.
In an exemplary embodiment, the starch is amylose and has a molecular weight of 50000.
In an exemplary embodiment, the cellulose has a molecular weight of 100000 to 150000.
In a specific embodiment, the preparation of nano calcium carbonate having an irregular crystal form comprises the steps of:
1) Calcining limestone into calcium oxide, adding water to prepare slurry, sieving and aging to obtain calcium hydroxide slurry;
2) Adding a crystal form control agent A into the calcium hydroxide slurry;
3) Delivering the slurry obtained in the step 2) to a membrane dispersion carbonization device for carbonization reaction, adding a crystal form control agent B when the pH of a reaction system is reduced to 9.0, and continuing the carbonization reaction until the pH is less than or equal to 7.0 to obtain nano calcium carbonate slurry;
4) And (3) modifying the nano calcium carbonate slurry, dehydrating, drying and crushing to obtain the nano calcium carbonate with irregular crystal forms.
In one exemplary embodiment, the preparation of nano calcium carbonate having an irregular crystal form includes the steps of:
1) Placing limestone with magnesium oxide content less than 0.3% in a vertical kiln for calcination, wherein the calcination temperature is controlled between 950 ℃ and 1150 ℃; after calcining, carrying out digestion reaction on lime and tap water according to the mass ratio of 1:5, sieving and removing impurities by a hydrocyclone, and aging for 72 hours to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 10-15%, controlling the temperature to 20-25 ℃, and then adding a crystal form control agent A, wherein the addition amount is 0.5-1.0% of the dry weight of the calcium hydroxide;
3) Delivering the slurry obtained in the step 2) to a membrane dispersion carbonization device for carbonization reaction, wherein the pore diameter of a membrane hole is 0.3-0.8mm, adding a crystal form control agent B when the pH value of a reaction system is reduced to 9.0, and continuously performing carbonization reaction until the pH value is less than or equal to 7.0, thereby obtaining nano calcium carbonate slurry;
4) And (3) modifying the calcium carbonate slurry obtained in the step (3), dehydrating, drying, and crushing to obtain the nano calcium carbonate with irregular crystal forms.
In a specific embodiment, the nano calcium carbonate having an irregular crystal form is first modified with a terpene oligomer, an epoxy resin, and maleic acid, and second modified with a diamino urea polymer.
Preferably, the terpene oligomer of step 4) has a number average molecular weight of 650-850g/mol.
Preferably, the epoxy resin of step 4) has an epoxy equivalent weight of 180-190g/mol.
Preferably, the mass ratio of the terpene oligomer, the epoxy resin and the maleic acid in the step 4) is 1: (0.08-0.12): (0.05-0.15).
In a specific embodiment, the modification of the nano calcium carbonate having an irregular crystal form comprises the steps of:
1) Mixing terpene oligomer, epoxy resin and maleic acid for reaction to obtain a modifier;
2) Mixing the nano calcium carbonate slurry with a modifier, performing first modification, adding a diamino urea polymer, and performing second modification to obtain the modified nano calcium carbonate slurry.
In one exemplary embodiment, the modification of the nano calcium carbonate having an irregular crystal form includes the steps of:
1) Terpene oligomer, epoxy resin and maleic acid are mixed according to the mass ratio of 1:0.08:0.10, allowed to react for 2.5 hours under the condition of 150 ℃ and 0.2MPa, and cooled to 80 ℃ to obtain a modifier;
2) Adding the nano calcium carbonate slurry prepared in the above way into an activation kettle, heating to 90 ℃, adding a modifier accounting for 2.2% of the dry basis weight of the nano calcium carbonate slurry, stirring for 45min, adding a semicarbazide polymer accounting for 1.0% of the dry basis weight of the nano calcium carbonate slurry, and stirring for 40min to obtain the modified nano calcium carbonate slurry.
Thus, in a specific embodiment, a nano calcium carbonate having an irregular crystalline form as described herein is prepared by a process comprising the steps of:
1) Calcining limestone into calcium oxide, adding water to prepare slurry, sieving and aging to obtain calcium hydroxide slurry;
2) Adding a crystal form control agent A into the calcium hydroxide slurry;
3) Delivering the slurry obtained in the step 2) to a membrane dispersion carbonization device for carbonization reaction, adding a crystal form control agent B when the pH of a reaction system is reduced to 9.0, and continuing the carbonization reaction until the pH is less than or equal to 7.0 to obtain nano calcium carbonate slurry;
4) Mixing terpene oligomer, epoxy resin and maleic acid for reaction to obtain a modifier;
5) Mixing the nano calcium carbonate slurry in the step 3) with the modifier in the step 4), performing first modification, adding a semicarbazide polymer, and performing second modification to obtain modified nano calcium carbonate slurry;
6) Dehydrating and drying the modified nano calcium carbonate slurry in the step 5), drying, and crushing to obtain the nano calcium carbonate with irregular crystal forms.
In one exemplary embodiment, a nano calcium carbonate having an irregular crystalline form as described herein is prepared by a process comprising the steps of:
1) Placing limestone with magnesium oxide content less than 0.3% in a vertical kiln for calcination, wherein the calcination temperature is controlled between 950 ℃ and 1150 ℃; after calcining, carrying out digestion reaction on lime and tap water according to the mass ratio of 1:5, sieving and removing impurities by a hydrocyclone, and aging for 72 hours to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 10-15%, controlling the temperature to 20-25 ℃, and then adding a crystal form control agent A, wherein the addition amount is 0.5-1.0% of the dry weight of the calcium hydroxide;
3) Delivering the slurry obtained in the step 2) to a membrane dispersion carbonization device for carbonization reaction, wherein the pore diameter of a membrane hole is 0.3-0.8mm, adding a crystal form control agent B when the pH value of a reaction system is reduced to 9.0, and continuously performing carbonization reaction until the pH value is less than or equal to 7.0, thereby obtaining nano calcium carbonate slurry;
4) Terpene oligomer, epoxy resin and maleic acid are mixed according to the mass ratio of 1:0.08:0.10, allowed to react for 2.5 hours under the condition of 150 ℃ and 0.2MPa, and cooled to 80 ℃ to obtain a modifier;
5) Adding the nano calcium carbonate slurry obtained in the step 3) into an activation kettle, heating to 90 ℃, adding a modifier accounting for 2.2% of the dry basis weight of the nano calcium carbonate slurry, stirring for 45min, adding a semicarbazide polymer accounting for 1.0% of the dry basis weight of the nano calcium carbonate slurry, and stirring for 40min to obtain modified nano calcium carbonate slurry;
6) And (3) dehydrating and drying the modified nano calcium carbonate slurry obtained in the step (5), drying, and crushing to obtain the nano calcium carbonate with irregular crystal forms.
The auxiliary agent for preparing the reinforced nylon material can comprise one or more of an antioxidant, a glass fiber leakage preventing agent, a lubricant and a light stabilizer.
Examples of the antioxidant may be at least one of hindered phenols and phosphite antioxidants; specifically, the antioxidant is at least one of antioxidants 168, 264, 1010, 1076, 1098; more specifically, the antioxidant is a compound antioxidant comprising an antioxidant 1010 and an antioxidant 168 in a mass ratio of 1:1.
Examples of the glass fiber leakage preventing agent may include ethylene bis-stearamide grafts (TAF).
Examples of the lubricant may include at least one of calcium stearate, stearic acid, ethylene bis-stearamide, pentaerythritol stearate, silicone powder, polyethylene wax.
Examples of the light stabilizer may include hindered amine light stabilizers such as light stabilizer 622, chemical name: a polymer of succinic acid and (4-hydroxy-2, 6-tetramethyl-1-piperidinol) and a light stabilizer 770, the chemical name of which is bis (2, 6-tetramethyl-4-piperidyl) sebacate.
The preparation method of the reinforced nylon material of the invention can comprise the following steps:
1) Preparing nano calcium carbonate having an irregular crystal form as described herein,
2) Nylon, glass fiber, nano calcium carbonate with irregular crystal form in the step 1) and auxiliary agent are mixed according to the weight parts,
3) And (3) carrying out melt blending, extrusion wire drawing and granulating on the mixture obtained in the step (2) to obtain the reinforced nylon material.
The beneficial effects of the invention are that
According to the invention, the crystal morphology of the nano calcium carbonate is controlled by adopting different crystal form control agents step by step in the crystal form forming stage of the nano calcium carbonate, and the uniform growth of {104} crystal faces is inhibited, so that the nano calcium carbonate crystal with an irregular crystal form, the length-diameter ratio of which is larger than 1, can be obtained, the nucleation effect is inhibited in a nylon/glass fiber system, the crystallinity of a nylon material can be reduced, and the melting point of the nylon material is further reduced, so that the nylon material is easy to use for processing, such as hot melt connection, such as ultrasonic welding.
On the other hand, the present invention also surface-modifies nano calcium carbonate having an irregular crystal form so that it can be highly dispersed in a nylon material without agglomeration, thereby enabling filling of the nylon material in a higher amount. In addition, compared with the method for carrying out surface modification by using fatty acid or fatty acid salt commonly used in the prior art, the modification of the invention also ensures that the surface of the nano calcium carbonate has no residual carboxyl and hydroxyl, thereby avoiding the formation of hydrogen bonds between the nano calcium carbonate and nylon and leading to the increase of crystallinity.
The glass fiber and nylon are blended, so that mechanical properties such as rigidity of the nylon material are enhanced, mechanical property loss caused by the reduction of crystallinity is compensated, and the nylon material is easy to weld by hot melting due to the increase of rigidity. The modified nano calcium carbonate with irregular crystal forms can also play the effect of a toughening agent, so that the nylon material has excellent rigidity, certain toughness and wide industrial application value.
Drawings
Fig. 1 shows an exemplary image of nano calcium carbonate having an irregular crystal form according to the present invention.
Examples
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Example 1:
1. preparation of unmodified nano calcium carbonate with irregular crystal form:
1) Calcining limestone with magnesium oxide content of 0.18% in a vertical kiln at 950-1150 ℃; after calcining, carrying out digestion reaction on lime and tap water according to the mass ratio of 1:5, sieving and removing impurities by a hydrocyclone, and aging for 72 hours to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 15%, controlling the temperature to 25 ℃, and then adding a crystal form control agent A (malic acid: starch=5:1), wherein the addition amount is 0.85% of the dry weight of the calcium hydroxide;
3) Uniformly stirring the slurry obtained in the step 2), conveying the slurry to a membrane dispersion carbonization device for carbonization reaction, wherein the pore diameter of a membrane is 0.3-0.8mm, adding a crystal form control agent B (sodium carbonate: cellulose=3:1) when the pH value of a reaction system is reduced to 9.0, and continuously performing carbonization reaction until the pH value is less than or equal to 7.0, thereby obtaining nano calcium carbonate slurry; through test, the specific surface area of the nano calcium carbonate obtained by carbonization reaction is 18.5m 2 /g; crystal length-diameter ratio is 2.5:1;
4) Dehydrating and drying the nano calcium carbonate slurry obtained in the step 3), drying until the water content is less than or equal to 0.25%, and crushing to obtain the nano calcium carbonate with irregular crystal forms.
2. Preparation of modified nano calcium carbonate with irregular crystal form:
1) Calcining limestone with magnesium oxide content of 0.18% in a vertical kiln at 950-1150 ℃; after calcining, carrying out digestion reaction on lime and tap water according to the mass ratio of 1:5, sieving and removing impurities by a hydrocyclone, and aging for 72 hours to obtain calcium hydroxide slurry;
2) Adjusting the concentration of the calcium hydroxide slurry in the step 1) to 15%, controlling the temperature to 25 ℃, and then adding a crystal form control agent A (malic acid: starch=5:1), wherein the addition amount is 0.85% of the dry weight of the calcium hydroxide;
3) Uniformly stirring the slurry obtained in the step 2), conveying the slurry to a membrane dispersion carbonization device for carbonization reaction, wherein the pore diameter of a membrane is 0.3-0.8mm, adding a crystal form control agent B (sodium carbonate: cellulose=3:1) when the pH value of a reaction system is reduced to 9.0, and continuously performing carbonization reaction until the pH value is less than or equal to 7.0, thereby obtaining nano calcium carbonate slurry; through test, the specific surface area of the nano calcium carbonate obtained by carbonization reaction is 18.5m 2 /g; crystal length-diameter ratio is 2.5:1;
4) Mixing terpene oligomer with the number average molecular weight of 700g/mol, epoxy resin with the epoxy equivalent of 185g/mol and maleic acid according to the mass ratio of 1:0.08:0.10, reacting for 2.5 hours at 150 ℃ under the condition of 0.2MPa, and cooling to 80 ℃ to obtain a modifier;
5) Adding the nano calcium carbonate slurry obtained in the step 3) into an activation kettle, heating to 90 ℃, adding a modifier accounting for 2.2% of the dry basis weight of the nano calcium carbonate slurry, stirring for 45min, adding a diamino urea polymer accounting for 1.0% of the dry basis weight of the nano calcium carbonate slurry and having a number average molecular weight of 2500g/mol, and stirring for 40min to obtain modified nano calcium carbonate slurry;
6) Dehydrating and drying the modified nano calcium carbonate slurry obtained in the step 5), drying until the water content is less than or equal to 0.25%, and crushing to obtain the nano calcium carbonate with irregular crystal forms.
Fig. 1 shows a schematic representation of nano calcium carbonate having an irregular crystal form.
3. Preparation of modified conventional nano calcium carbonate:
unmodified conventional nano calcium carbonate is purchased from International trade company, shanghai, white Dan Gai, with particle size of 80-100nm.
Uniformly dispersing unmodified conventional nano calcium carbonate in water, heating to 90 ℃ on a constant-temperature water bath oscillator, adding a modifier accounting for 2.2% of the dry basis weight of the nano calcium carbonate, stirring for 45min, adding a diamino urea polymer accounting for 1.0% of the dry basis weight of the nano calcium carbonate and having a number average molecular weight of 2500g/mol, stirring for 40min, dehydrating and drying the obtained modified nano calcium carbonate slurry, drying until the moisture content is less than or equal to 0.25%, and crushing to obtain the modified conventional nano calcium carbonate.
4. Conventional nano calcium carbonate modified by fatty acid surface treatment is purchased from white Dan Gai (Shanghai) International trade company, and has a particle size of 80-100nm.
Example 2:
the reinforced nylon material is prepared by the following steps:
1) 52 parts by weight of nylon 6, 16 parts by weight of modified nano calcium carbonate with irregular crystal forms, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, 1.0 part by weight of glass fiber leakage preventing agent TAF, 0.6 part by weight of lubricant polyethylene wax and 0.2 part by weight of light stabilizer 622 are added into a high-speed mixer to be mixed for 3 minutes at a high speed, then are added into a double-screw extruder to be melted, and 30 parts by weight of E-type alkali-free long glass fibers are added from a glass fiber inlet of the double-screw extruder to be extruded together to obtain the reinforced nylon material.
Example 3:
the reinforced nylon material is prepared by the following steps:
1) 40 parts by weight of nylon 6, 20 parts by weight of modified nano calcium carbonate with irregular crystal forms, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, 1.0 part by weight of glass fiber leakage preventing agent TAF, 0.6 part by weight of lubricant polyethylene wax and 0.2 part by weight of light stabilizer 622 are added into a high-speed mixer to be mixed for 3 minutes at a high speed, then are added into a double-screw extruder to be melted, and 38 parts by weight of E-type alkali-free long glass fibers are added from a glass fiber inlet of the double-screw extruder to be extruded together to obtain the reinforced nylon material.
Example 4:
the reinforced nylon material is prepared by the following steps:
1) 60 parts by weight of nylon 6, 10 parts by weight of modified nano calcium carbonate with irregular crystal forms, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, 1.0 part by weight of glass fiber leakage preventing agent TAF, 0.6 part by weight of lubricant polyethylene wax and 0.2 part by weight of light stabilizer 622 are added into a high-speed mixer to be mixed for 3 minutes at a high speed, then are added into a double-screw extruder to be melted, and 28 parts by weight of E-type alkali-free long glass fibers are added from a glass fiber inlet of the double-screw extruder to be extruded together to obtain the reinforced nylon material.
Comparative example 1:
the reinforced nylon material is prepared by the following steps:
1) 52 parts by weight of nylon 6, 16 parts by weight of unmodified nano calcium carbonate with irregular crystal forms, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, 1.0 part by weight of glass fiber leakage preventing agent TAF, 0.6 part by weight of lubricant polyethylene wax and 0.2 part by weight of light stabilizer 622 are added into a high-speed mixer to be mixed for 3 minutes at a high speed, then are added into a double-screw extruder to be melted, and 30 parts by weight of E-type alkali-free long glass fibers are added from a glass fiber inlet of the double-screw extruder to be extruded together to obtain the reinforced nylon material.
Comparative example 2:
the reinforced nylon material is prepared by the following steps:
1) 52 parts by weight of nylon 6, 16 parts by weight of modified conventional nano calcium carbonate, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, 1.0 part by weight of glass fiber leakage preventing agent TAF, 0.6 part by weight of lubricant polyethylene wax and 0.2 part by weight of light stabilizer 622 are added into a high-speed mixer to be mixed for 3 minutes at a high speed, then are added into a double-screw extruder to be melted, and 30 parts by weight of E-type alkali-free long glass fibers are added from a glass fiber inlet of the double-screw extruder to be extruded together after the melting, so that the reinforced nylon material is obtained.
Comparative example 3:
the reinforced nylon material is prepared by the following steps:
1) 52 parts by weight of nylon 6, 16 parts by weight of conventional nano calcium carbonate modified by fatty acid surface treatment, 0.1 part by weight of antioxidant 1010, 0.1 part by weight of antioxidant 168, 1.0 part by weight of glass fiber leakage preventing agent TAF, 0.6 part by weight of lubricant polyethylene wax and 0.2 part by weight of light stabilizer 622 are added into a high-speed mixer to be mixed for 3 minutes at a high speed, then are added into a double-screw extruder to be melted, and 30 parts by weight of E-type alkali-free long glass fibers are added from a glass fiber inlet of the double-screw extruder to be extruded together after the melting, so that the reinforced nylon material is obtained.
Performance testing
1. Mechanical property test
Tensile strength and elongation at break were measured according to the method specified in astm d638, notched impact strength was measured according to the method specified in astm d256, and flexural strength and flexural modulus were measured according to the method specified in astm d 790. The materials obtained in examples 2 to 4 and comparative examples 1 to 3 were subjected to mechanical properties test in accordance with the above-described methods, and the results obtained are shown in Table 1.
2. Melting point, crystallization temperature, crystallinity were determined using DSC test instrument: the sample was warmed from room temperature to 250 ℃ at 10 ℃/min under nitrogen protection, kept at constant temperature for 10min to eliminate the heat history, then cooled to room temperature at 10 ℃/min, the crystallization profile was recorded and the crystallinity calculated, and the results are shown in table 1.
TABLE 1
As can be seen from table 1, the melting point of the reinforced nylon materials (i.e., examples 2 to 4) prepared using the modified nano calcium carbonate having an irregular crystal form of the present invention was significantly reduced compared to the reinforced nylon materials (i.e., comparative example 3) prepared using the conventional nano calcium carbonate, the hot melt weldability was significantly improved, and the mechanical properties were not greatly changed, thus having practical value. The reinforced nylon material prepared from the unmodified nano calcium carbonate with irregular crystal forms (namely, comparative example 1) is easy to agglomerate due to larger addition amount, so that the effect of reducing the crystallinity is weakened, and the toughening effect is also obviously weakened. The reinforced nylon material prepared by the modified conventional nano calcium carbonate according to the present invention also has a certain effect of reducing crystallinity compared to the reinforced nylon material prepared by using the conventional modified nano calcium carbonate (i.e., comparative example 3), because the modified nano calcium carbonate has no residual carboxyl and hydroxyl groups on the surface, thereby avoiding the formation of hydrogen bonds between the nano calcium carbonate and nylon, resulting in an increase in crystallinity.
In the description of the specification, reference to the term "one embodiment," "a particular embodiment," "an example," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or by similar arrangements, by those skilled in the art, without departing from the scope of the invention or beyond the scope of the appended claims.
Claims (6)
1. A reinforced nylon material, comprising: 30 to 60 parts by weight of nylon, 20 to 40 parts by weight of glass fiber, 10 to 20 parts by weight of nano calcium carbonate with irregular crystal forms, and 0.1 to 3 parts by weight of auxiliary agent,
wherein the nano calcium carbonate having an irregular crystal form has an aspect ratio of more than 1, and is prepared by using a crystal form controlling agent A and a crystal form controlling agent B in stages in the preparation process of the nano calcium carbonate, wherein the crystal form controlling agent A is a mixture of malic acid and starch in a mass ratio of 3-5:1, the crystal form controlling agent B is a mixture of sodium carbonate and cellulose in a mass ratio of 2-3:1,
wherein the nano calcium carbonate having an irregular crystal form is first modified using a terpene oligomer, an epoxy resin, and maleic acid, and is second modified using a semicarbazide polymer, and the modification of the nano calcium carbonate having an irregular crystal form comprises the steps of:
1) Mixing terpene oligomer, epoxy resin and maleic acid for reaction to obtain a modifier;
2) Mixing the nano calcium carbonate slurry with a modifier, performing first modification, adding a diamino urea polymer, and performing second modification to obtain the modified nano calcium carbonate slurry.
2. The reinforced nylon material of claim 1, said nylon comprising PA6 or PA66.
3. The reinforced nylon material of claim 1, wherein the glass fiber is any one or a mixture of a plurality of continuous glass fibers, chopped glass fibers, milled glass fibers, alkali-free glass fibers, medium alkali glass fibers, and high alkali glass fibers.
4. The reinforced nylon material of claim 1, wherein the nano calcium carbonate having an irregular crystal form has a specific surface area of 16-20m 2 /g。
5. The reinforced nylon material of claim 1, wherein the nano calcium carbonate having an irregular crystalline form is prepared by a process comprising the steps of:
1) Calcining limestone into calcium oxide, adding water to prepare slurry, sieving and aging to obtain calcium hydroxide slurry;
2) Adding a crystal form control agent A into the calcium hydroxide slurry;
3) Delivering the slurry obtained in the step 2) to a membrane dispersion carbonization device for carbonization reaction, adding a crystal form control agent B when the pH of a reaction system is reduced to 9.0, and continuing the carbonization reaction until the pH is less than or equal to 7.0 to obtain nano calcium carbonate slurry;
4) And (3) modifying the nano calcium carbonate slurry, dehydrating, drying and crushing to obtain the nano calcium carbonate with irregular crystal forms.
6. The reinforced nylon material of claim 1, wherein the auxiliary agent is one or more of an antioxidant, a glass fiber leakage preventing agent, a lubricant and a light stabilizer.
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