CN110818885A - Polyurethane-coated hollow glass bead toughened cast nylon 6 composite material and preparation method thereof - Google Patents
Polyurethane-coated hollow glass bead toughened cast nylon 6 composite material and preparation method thereof Download PDFInfo
- Publication number
- CN110818885A CN110818885A CN201911165286.8A CN201911165286A CN110818885A CN 110818885 A CN110818885 A CN 110818885A CN 201911165286 A CN201911165286 A CN 201911165286A CN 110818885 A CN110818885 A CN 110818885A
- Authority
- CN
- China
- Prior art keywords
- hollow glass
- polyurethane
- composite material
- glass bead
- coated hollow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- 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
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/28—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a preparation method of a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material, which comprises the steps of coating a certain proportion of a polybasic hydroxyl raw material and diisocyanate on the surface of a hollow glass bead in a spraying mode, mixing the polybasic hydroxyl raw material and diisocyanate, carrying out in-situ polymerization on the surface of the hollow glass bead at a proper polymerization temperature to prepare the polyurethane-coated hollow glass bead, then intermittently adding lactam, the polyurethane-coated hollow glass bead, a catalyst and an activator into a reaction kettle according to a proportion for pre-polymerization and activation, finally injecting hot slurry with a certain viscosity into a hot mold for polymerization and solidification, cooling and demolding to obtain the composite material. The polyurethane is used for coating the hollow glass bead toughened nylon, so that the toughness of the composite material is improved on the premise of ensuring that the strength, the modulus, the rigidity, the hardness and the heat resistance of the composite material are not reduced.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a polyurethane-coated hollow glass microsphere toughened cast nylon 6 composite material and a preparation method thereof.
Background
The lactam belongs to heterocycle, has larger ring tension and ring opening tendency, and can initiate anionic polymerization by adopting an alkaline catalyst to obtain monomer casting nylon (MCPA). The monomer casting nylon has more advantages than common polycondensation nylon, mainly shows that the molecular weight is as high as 7-10 ten thousand, is more than 2 times of common polycondensation nylon, and has narrower molecular weight distribution; the mechanical property is better than that of the polycondensation nylon; the reaction speed is high, the polymerization temperature is low, and the catalyst, the activator and the molten monomer are injected into the hot die under normal pressure and can be quickly polymerized into a solid product; the polymerization and the molding processing are completed in one step, and the nylon particles do not need to be polymerized first and then the molding processing is carried out like polycondensation nylon.
At present, cast nylon is gradually replacing metal materials and becoming a widely used general engineering plastic. However, unmodified cast nylon is a quasi-tough plastic, and the impact strength needs to be improved to further expand the application. Therefore, the method has important practical significance for toughening and modifying the cast nylon. In general, elastomer, polyolefin and the like are added into a matrix to prepare high polymer alloy for toughening and modifying cast nylon, however, the addition of the elastomer and other components can reduce the strength, modulus, rigidity, hardness, heat resistance and the like of the composite material. When inorganic rigid particles such as calcium carbonate, silicon dioxide, titanium dioxide, silicon carbide and other toughened polyamides are adopted, although the modulus, rigidity and hardness of the material can be ensured, the tensile strength is reduced and the toughening effect is poor due to poor compatibility of the inorganic rigid particles and an organic polymer material, and the density of the composite material is increased after the inorganic rigid particles are added, so that the lightweight of the material is very unfavorable.
Disclosure of Invention
The invention provides a preparation method of a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material, which comprises the following steps:
(1) carrying out in-situ polymerization reaction on the surfaces of the hollow glass microspheres by using a diisocyanate solution and a polybasic hydroxyl raw material to obtain polyurethane-coated hollow glass microspheres, wherein the polybasic hydroxyl raw material is polyol or polyester polyol;
(2) and polymerizing and curing the polyurethane-coated hollow glass bead, lactam, a catalyst and an activating agent to obtain the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material.
Based on the above, the step (1) comprises: dissolving the polyol or the polyester polyol in an organic solvent A to prepare a solution A with the concentration of 0.1-20%, and dissolving diisocyanate in an organic solvent B to prepare a solution B with the concentration of 2-40%; and mixing the solution A and the solution B, spraying the mixture on the surfaces of the hollow glass beads, performing addition polymerization reaction for 0.5 to 3 hours at the temperature of between 50 and 150 ℃, and generating a polyurethane layer on the surfaces of the hollow glass beads to obtain the polyurethane-coated hollow glass beads.
Based on the above, the ratio of the molar amount of hydroxyl species in the alcohol component in the solution a to the molar amount of isocyanate group species in the solution B is 1: (1-5).
Based on the above, the polyhydric alcohol is one or more of ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol and glycerol; the polyester polyol is one or a mixture of more of polyethylene glycol glutarate, polypropylene glycol glutarate and polybutylene glycol glutarate.
Based on the above, the diisocyanate is one or a mixture of several of diphenylmethane diisocyanate (MDI), 2, 4-Toluene Diisocyanate (TDI) and Hexamethylene Diisocyanate (HDI).
Based on the above, the organic solvent A is one or a mixture of several of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, ethyl acetate, benzene and 1, 4-dioxane; the organic solvent B is one or a mixture of more of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, ethyl acetate, benzene and 1, 4-dioxane.
Based on the above, the step (2) comprises: according to the mass parts, 100 parts of lactam monomer and 0.01-10 parts of polyurethane coated hollow glass microsphere are melted, mixed and insulated for 30-60 min under the vacuum state and the temperature of 120-155 ℃; obtaining a mixed molten mass;
removing vacuum, adding 0.1-2.5 parts of sodium hydroxide into the mixed molten mass, continuously vacuumizing, stirring, heating to 145-170 ℃, and keeping the temperature for 30-60 min; obtaining a catalytic molten mass;
and (3) removing vacuum, adding 0.1-2.5 parts of diphenylmethane diisocyanate into the catalytic molten mass, stirring, heating to 160-190 ℃, standing for 30-90 min, cooling, and demolding to obtain the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material.
Based on the above, the lactam monomer is one or a mixture of several of butyrolactam, caprolactam, nonanolactam and laurolactam.
Based on the above, the true density of the hollow glass beads is 0.5 g/cm3～0.65 g/cm3The bulk density was 0.3g/cm3～0.4 g/cm3And the particle diameter is 10-40 μm.
The invention also provides a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material, which is prepared by the preparation method, wherein the tensile strength of the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is 70-90 MPa, and the notch impact strength of the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is 9.8kJ/m2～13.3kJ/m2。
Compared with the prior art, the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material prepared by the invention has outstanding substantive characteristics and obvious progress, and particularly, the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material takes the polyurethane-coated hollow glass bead as an inner core, and overcomes the problem of reduction of strength, modulus, rigidity, hardness and heat resistance of the composite material caused by the toughening of nylon by a common elastomer by utilizing the characteristics of high strength, high modulus, high hardness and good rigidity of the glass bead.
Meanwhile, the surfaces of the glass beads are coated with polyurethane, the polyurethane and the nylon are organic polymers, and the polarity is similar, so that the problems of strength reduction and poor toughening effect caused by poor compatibility of inorganic particles and organic polymer materials when the nylon is toughened by the inorganic rigid particles are solved.
Furthermore, the polyurethane-coated inner core is hollow glass beads, the true density and the stacking density are very low, the problem that the density of the composite material is increased after inorganic rigid particles are added is solved, and the composite material can achieve light weight while the nylon material is toughenedThe effect of the composition is improved. The experimental result shows that the polyurethane layer is uniformly coated on the surface of the glass microsphere, and incomplete coating or agglomeration of the glass microsphere can not be caused. The prepared nylon composite material has the tensile strength of 70 MPa to 90 MPa and the notch impact strength of 9.8kJ/m2～13.3kJ/m2。
Drawings
FIG. 1 is an optical micrograph of hollow glass microspheres which are not coated with polyurethane.
FIG. 2 is an optical micrograph of polyurethane-coated hollow glass microspheres prepared according to the preparation method described in example 1.
FIG. 3 is an optical micrograph of polyurethane-coated hollow glass microspheres prepared according to the preparation method described in example 2.
FIG. 4 is an optical micrograph of polyurethane-coated hollow glass microspheres prepared according to the preparation method described in example 3.
Detailed Description
Example 1
The embodiment provides a preparation method of a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material, which specifically comprises the following steps:
(1) weighing 10g of ethylene glycol, and dissolving the ethylene glycol in 140g of acetone solvent to prepare a solution A with the concentration of 6.67 percent; weighing 73.5g of diphenylmethane diisocyanate (MDI) and dissolving in 700g of acetone solvent to prepare a solution B with the concentration of 9.50 percent;
mixing the solution A and the solution B, and stirring, vibrating and ultrasonically treating the two solutions to form a uniform mixed solution; wherein the mixed system contains 10g (0.147 mol) of ethylene glycol and 73.5g (0.294 mol) of diphenylmethane diisocyanate (MDI), and the ratio of the amount of hydroxyl substances to the amount of isocyanate group substances in the mixed solution is 1: 2;
adding the mixed solution into a high-pressure sprayer, atomizing the mixed solution in a spraying mode, spraying the atomized mixed solution on the surfaces of the glass beads, and quickly stirring to preliminarily wet the surfaces of the glass beads;
and (2) placing the wetted glass beads in an environment of 90 ℃, drying by air to remove the acetone solvent, carrying out addition polymerization on the alcohol component and the diisocyanate component on the surfaces of the glass beads at the temperature, and tightly coating the polyurethane layer of the polymerization product on the surfaces of the glass beads, wherein the process lasts for 1.5 hours. The atomization spraying-drying polymerization process is repeated for 4 times to prepare the polyurethane-coated hollow glass bead.
(2) Continuously heating 100 parts of laurolactam monomer and 1 part of polyurethane-coated hollow glass microsphere in a vacuum state, melting the laurolactam monomer when the temperature reaches 153 ℃, starting stirring, continuously heating to 150 ℃, keeping the temperature, vacuumizing, and stirring for 30 min;
removing vacuum, adding 0.3 part of catalyst sodium hydroxide, continuously maintaining vacuum and stirring state, raising temperature, keeping the temperature when the temperature reaches 160 ℃, vacuumizing, and stirring for 45 min;
removing vacuum, adding 0.25 part of activator TDI, and rapidly and uniformly stirring; adding activator, increasing system viscosity, rapidly injecting into mold preheated to 180 deg.C when viscosity is moderate, maintaining temperature, standing for 70 min, cooling, and demolding; and obtaining the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material.
The photo of the polyurethane-coated hollow glass bead under an optical microscope is shown in fig. 2, and as is obvious from the optical microscope photo of the hollow glass bead with the surface not coated with polyurethane in fig. 1, the surface of the hollow glass bead in fig. 2 is coated with a coating layer.
The embodiment also provides a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material prepared by the preparation method, and through testing, the mechanical property test result of the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is as follows: the tensile strength is 71.5MPa, and the notch impact strength is 9.8kJ/m2。
Example 2
The embodiment provides a preparation method of a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material, which specifically comprises the following steps:
(1) weighing 9.2g of glycerol, and dissolving in 40g of benzene solvent to prepare a solution A with the concentration of 18.70%; 31.32g of 2, 4-Toluene Diisocyanate (TDI) is weighed and dissolved in 150g of benzene solvent to prepare a solution B with the concentration of 17.21%;
mixing the solution A and the solution B, stirring, vibrating and ultrasonically treating the two solutions to form a uniform mixed solution, wherein the mixed system contains 9.2g (0.1 mol) of glycerol and 31.32g (0.18 mol) of 2, 4-toluene diisocyanate, and the ratio of the amount of hydroxyl substances to the amount of isocyanate group substances in the mixed solution is 1: 1.2;
adding the mixed solution into a high-pressure sprayer, atomizing the mixed solution in a spraying mode, spraying the atomized mixed solution on the surfaces of the glass beads, and quickly stirring to preliminarily wet the surfaces of the glass beads; placing the wetted glass beads in an environment of 100 ℃, blowing and drying to remove a benzene solvent, carrying out addition polymerization on the alcohol component and the diisocyanate component on the surfaces of the glass beads at the temperature, and tightly coating a polyurethane layer of a polymerization product on the surfaces of the glass beads, wherein the process lasts for 1 hour; the atomization spraying-drying polymerization process was repeated 3 times to prepare polyurethane-coated hollow glass microspheres.
(2) Continuously heating 100 parts of caprolactam monomer and 0.5 part of polyurethane-coated hollow glass microsphere in a vacuum state, melting the caprolactam monomer when the temperature reaches 70 ℃, starting stirring, continuously heating to 135 ℃, keeping the temperature, vacuumizing and stirring for 45 min;
removing vacuum, adding 0.25 part of catalyst sodium hydroxide, continuously maintaining vacuum and stirring state, raising temperature, keeping the temperature when the temperature reaches 165 ℃, vacuumizing, and stirring for 50 min;
the vacuum is released, 0.3 part of activator TDI is added, and the mixture is stirred rapidly and uniformly. And (3) adding an activating agent to increase the viscosity of the system, when the viscosity is moderate, quickly injecting the mixture into a mold preheated to 170 ℃, preserving the temperature, standing for 60min, cooling and demolding to obtain the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material.
The photo of the polyurethane-coated hollow glass bead under an optical microscope is shown in fig. 3, and as can be clearly seen from the optical micrograph of the hollow glass bead of which the surface is not coated with polyurethane in fig. 1, the surface of the hollow glass bead in fig. 3 has a thicker polyurethane coating layer.
The embodiment also provides a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material prepared by the preparation method, and through testing, the mechanical property test result of the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is as follows: tensile strength of 82.6 MPa and notch impact strength of 11.5 kJ/m2。
Example 3
The embodiment provides a preparation method of a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material, which specifically comprises the following steps:
(1) weighing 12g of polyethylene glycol glutarate with molecular weight of 800, dissolving in 200g of ethyl acetate solvent to prepare a solution A with the concentration of 10.71%; 3.78g of Hexamethylene Diisocyanate (HDI) is weighed and dissolved in 100g of ethyl acetate solvent to prepare a solution B with the concentration of 3.64%;
and mixing the solution A and the solution B, and stirring, vibrating and ultrasonically treating the two solutions to form a uniform mixed solution. The mixed system contained 12g (0.015 mol) of polyethylene glycol glutarate, 3.78g of Hexamethylene Diisocyanate (HDI) (0.0225 mol), and the ratio of the amount of the hydroxyl substance to the amount of the isocyanate group substance in the mixed solution was 1: 1.5;
adding the mixed solution into a high-pressure sprayer, atomizing the mixed solution in a spraying mode, spraying the atomized mixed solution on the surfaces of the glass beads, and quickly stirring to preliminarily wet the surfaces of the glass beads; placing the wetted glass beads in an environment of 80 ℃, blowing and drying to remove a benzene solvent, carrying out addition polymerization on the alcohol component and the diisocyanate component on the surfaces of the glass beads at the temperature, and tightly coating a polyurethane layer of a polymerization product on the surfaces of the glass beads, wherein the process lasts for 0.5 h; the atomization spraying-drying polymerization process is repeated for 5 times to prepare the polyurethane-coated hollow glass bead.
(2) Continuously heating 100 parts of caprolactam monomer and 0.1 part of polyurethane-coated hollow glass microsphere in a vacuum state, melting the caprolactam monomer when the temperature reaches 70 ℃, starting stirring, continuously heating to 140 ℃, keeping the temperature, vacuumizing, and stirring for 60 min;
removing vacuum, adding 0.2 part of catalyst sodium hydroxide, continuously maintaining vacuum and stirring state, raising temperature, keeping the temperature when the temperature reaches 155 ℃, vacuumizing, and stirring for 60 min;
removing vacuum, adding 0.35 part of activator TDI, and rapidly and uniformly stirring; and (3) adding an activating agent to increase the viscosity of the system, when the viscosity is moderate, quickly injecting the mixture into a mold preheated to 175 ℃, preserving the temperature, standing for 80 min, cooling and demolding to obtain the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material.
The photo of the polyurethane-coated hollow glass bead under an optical microscope is shown in fig. 4, and as can be clearly seen from the optical micrograph of the hollow glass bead of which the surface is not coated with polyurethane in fig. 1, the surface of the hollow glass bead in fig. 4 has a thicker polyurethane coating layer.
The embodiment also provides a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material prepared by the preparation method, and through testing, the mechanical property test result of the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is as follows: tensile strength of 85MPa and notch impact strength of 12.3 kJ/m2。
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention and not to limit it; although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art will understand that: modifications to the specific embodiments of the invention or equivalent substitutions for parts of the technical features may be made; without departing from the spirit of the present invention, it is intended to cover all aspects of the invention as defined by the appended claims.
Claims (10)
1. A preparation method of a polyurethane-coated hollow glass bead toughened cast nylon 6 composite material comprises the following steps:
(1) carrying out in-situ polymerization reaction on the surfaces of the hollow glass microspheres by using a diisocyanate solution and a polybasic hydroxyl raw material to obtain polyurethane-coated hollow glass microspheres, wherein the polybasic hydroxyl raw material is polyol or polyester polyol;
(2) and polymerizing and curing the polyurethane-coated hollow glass bead, lactam, a catalyst and an activating agent to obtain the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material.
2. The preparation method of the polyurethane coated hollow glass bead toughened and cast nylon 6 composite material according to claim 1, which is characterized by comprising the following steps: the step (1) comprises the following steps: dissolving the polybasic hydroxyl raw material in an organic solvent A to prepare a solution A with the concentration of 0.1-20%, and dissolving diisocyanate in an organic solvent B to prepare a solution B with the concentration of 2-40%; and mixing the solution A and the solution B, spraying the mixture on the surfaces of the hollow glass beads, performing addition polymerization reaction for 0.5 to 3 hours at the temperature of between 50 and 150 ℃, and generating a polyurethane layer on the surfaces of the hollow glass beads to obtain the polyurethane-coated hollow glass beads.
3. The preparation method of the polyurethane coated hollow glass bead toughened and cast nylon 6 composite material according to claim 2, which is characterized by comprising the following steps: the ratio of the molar amount of hydroxyl species in the alcohol component in solution a to the molar amount of isocyanate group species in solution B is 1: (1-5).
4. The preparation method of the polyurethane coated hollow glass bead toughened and cast nylon 6 composite material according to claim 3, characterized by comprising the following steps: the polyalcohol is one or more of ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol and glycerol; the polyester polyol is one or a mixture of more of polyethylene glycol glutarate, polypropylene glycol glutarate and polybutylene glycol glutarate.
5. The preparation method of the polyurethane coated hollow glass bead toughened and cast nylon 6 composite material according to claim 4, which is characterized by comprising the following steps: the diisocyanate is one or a mixture of more of diphenylmethane diisocyanate (MDI), 2, 4-Toluene Diisocyanate (TDI) and Hexamethylene Diisocyanate (HDI).
6. The preparation method of the polyurethane coated hollow glass bead toughened and cast nylon 6 composite material according to claim 5, characterized in that: the organic solvent A is one or a mixture of more of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, ethyl acetate, benzene and 1, 4-dioxane; the organic solvent B is one or a mixture of more of Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, ethyl acetate, benzene and 1, 4-dioxane.
7. The preparation method of the polyurethane coated hollow glass bead toughened and cast nylon 6 composite material according to any one of claims 1 to 6, characterized by comprising the following steps: the step (2) comprises the following steps:
according to the mass parts, 100 parts of lactam monomer and 0.01-10 parts of polyurethane coated hollow glass microsphere are melted, mixed and insulated for 30-60 min under the vacuum state and the temperature of 120-155 ℃; obtaining a mixed molten mass;
removing vacuum, adding 0.1-2.5 parts of sodium hydroxide into the mixed molten mass, continuously vacuumizing, stirring, heating to 145-170 ℃, and keeping the temperature for 30-60 min; obtaining a catalytic molten mass;
and (3) removing vacuum, adding 0.1-2.5 parts of diphenylmethane diisocyanate into the catalytic molten mass, stirring, heating to 160-190 ℃, standing for 30-90 min, cooling, and demolding to obtain the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material.
8. The preparation method of the polyurethane coated hollow glass bead toughened cast nylon 6 composite material according to claim 7, which is characterized by comprising the following steps: the lactam monomer is one or a mixture of several of butyrolactam, caprolactam, nonanolactam and laurolactam.
9. The polyurethane-coated hollow glass bead toughened cast nylon of claim 86 the preparation method of the composite material is characterized in that: the true density of the hollow glass beads is 0.5 g/cm3～0.65 g/cm3The bulk density was 0.3g/cm3～0.4 g/cm3And the particle diameter is 10-40 μm.
10. A polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is characterized in that: the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is prepared by the preparation method of the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material as claimed in any one of claims 1 to 9, wherein the tensile strength of the polyurethane-coated hollow glass bead toughened cast nylon 6 composite material is 70 MPa to 90 MPa, and the notch impact strength is 9.8kJ/m2～13.3kJ/m2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911165286.8A CN110818885A (en) | 2019-11-25 | 2019-11-25 | Polyurethane-coated hollow glass bead toughened cast nylon 6 composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911165286.8A CN110818885A (en) | 2019-11-25 | 2019-11-25 | Polyurethane-coated hollow glass bead toughened cast nylon 6 composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110818885A true CN110818885A (en) | 2020-02-21 |
Family
ID=69559118
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911165286.8A Pending CN110818885A (en) | 2019-11-25 | 2019-11-25 | Polyurethane-coated hollow glass bead toughened cast nylon 6 composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110818885A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752232A (en) * | 2022-04-21 | 2022-07-15 | 郑州圣莱特空心微珠新材料有限公司 | Elastomer-coated hollow glass bead and preparation method and application thereof |
| CN115449099A (en) * | 2022-08-29 | 2022-12-09 | 哈尔滨工程大学 | Preparation method, product and application of hollow glass bead composite polyimide film coated with polyimide precursor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861428A (en) * | 2014-10-08 | 2015-08-26 | 青岛欣展塑胶有限公司 | Composite material for toughening polyesters by covering rigid particles with elastomers |
| CN109957236A (en) * | 2019-04-03 | 2019-07-02 | 河南城建学院 | Activeness and quietness wearable lightweight cast nylon composite material and preparation method |
-
2019
- 2019-11-25 CN CN201911165286.8A patent/CN110818885A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104861428A (en) * | 2014-10-08 | 2015-08-26 | 青岛欣展塑胶有限公司 | Composite material for toughening polyesters by covering rigid particles with elastomers |
| CN109957236A (en) * | 2019-04-03 | 2019-07-02 | 河南城建学院 | Activeness and quietness wearable lightweight cast nylon composite material and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 白战争等: "聚氨酯包覆空心玻璃微珠改性环氧复合材料的制备与性能研究", 《塑料工业》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752232A (en) * | 2022-04-21 | 2022-07-15 | 郑州圣莱特空心微珠新材料有限公司 | Elastomer-coated hollow glass bead and preparation method and application thereof |
| CN114752232B (en) * | 2022-04-21 | 2024-02-02 | 郑州圣莱特空心微珠新材料有限公司 | Elastomer-coated hollow glass bead and preparation method and application thereof |
| CN115449099A (en) * | 2022-08-29 | 2022-12-09 | 哈尔滨工程大学 | Preparation method, product and application of hollow glass bead composite polyimide film coated with polyimide precursor |
| CN115449099B (en) * | 2022-08-29 | 2023-07-14 | 哈尔滨工程大学 | Preparation method, product and application of hollow glass bead composite polyimide film coated with polyimide precursor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110130094B (en) | Activated plant fiber, preparation method thereof and application thereof in polylactic acid composite material | |
| US3860565A (en) | Encapsulated isocyanurate catalyst | |
| US9108364B2 (en) | Solvent-promoted self-healing materials | |
| Xu et al. | Chain extension of polyamide 6 using multifunctional chain extenders and reactive extrusion for melt foaming | |
| CN110818885A (en) | Polyurethane-coated hollow glass bead toughened cast nylon 6 composite material and preparation method thereof | |
| JP6328553B2 (en) | Solid particles containing lactam, activator and catalyst, method for producing the solid particles, and method for using the solid particles | |
| CN101077910B (en) | Method for preparing particle diameter controllable high molecular weight nylon micro-sphere | |
| CN105283286B (en) | The method for preparing fibre reinforced composites | |
| CN108727752B (en) | Method for preparing high-strength polyvinyl alcohol composite hydrogel by utilizing in-situ fiber forming | |
| CN111286074B (en) | Polylactic acid/nano hydroxyapatite composite material and preparation method and application thereof | |
| JPH0149732B2 (en) | ||
| CN109517376B (en) | Preparation method of nylon powder material for selective laser sintering | |
| US3377323A (en) | Method for pulverizing polymers | |
| CN102477138B (en) | Silica cross-linking shape memory polymer material | |
| Kim et al. | Self-healing green polymers and composites | |
| CN107849240B (en) | Caprolactam formulation | |
| US20160251499A1 (en) | Process for Increasing the Adhesion of a Reinforcing Inorganic Material in a Polymeric Matrix, a Reinforcing Inorganic Material, a Process for Obtaining a Thermoplastic Composite Material, a Thermoplastic Composite Material, and a Thermoplastic Composite Article | |
| CN108976678B (en) | Preparation method of PBAT micro-nanofiber reinforced carboxymethyl chitosan/polyvinyl alcohol composite hydrogel | |
| JP2003503521A (en) | Nylon 6-silicone blend | |
| CN108822310B (en) | Preparation method of PBS micro-nanofiber/carboxymethyl chitosan/polyvinyl alcohol composite hydrogel | |
| KR20140139580A (en) | Method for producing polyamide molded bodies from a polymerizable composition by means of a rotational molding process | |
| JP2010173291A (en) | Method for manufacturing fiber-reinforced polyamide resin composite | |
| JP2003503518A (en) | Amide-type polymer / silicone polymer blend and method for producing the same | |
| KR101956534B1 (en) | Method for producing molded articles | |
| HUT72759A (en) | Gelled reactive resin compositions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200221 |