CN109337353B - Surface modified fiber reinforced polyurethane composite material and preparation method thereof - Google Patents
Surface modified fiber reinforced polyurethane composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a surface modified fiber reinforced polyurethane composite material and a preparation method thereof, wherein the composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.3-1.5 parts of silicone oil, 0.8-1.4 parts of catalyst, 1-3 parts of coupling agent, 6.7-12.5 parts of composite foaming agent, 4-9 parts of flame retardant, 27-36 parts of isocyanate and 12-20 parts of surface modified palm fiber. According to the invention, the fiber-reinforced polyurethane composite material is constructed by adopting the surface modified palm fibers, the strength of the polyurethane composite material is improved by utilizing the characteristics of stronger elasticity and toughness and higher fracture toughness of the palm fibers, and the interface bonding condition of the fibers and the material matrix is improved by the surface modification of the palm fibers. The surface modified fiber reinforced polyurethane composite material provided by the invention has high mechanical strength and good fireproof and flame-retardant properties.
Description
Technical Field
The invention relates to the technical field of polyurethane materials, in particular to a surface modified fiber reinforced polyurethane composite material and a preparation method thereof.
Background
The polyurethane material is a polymer with repeated-NHCOO-groups on the main chain obtained by the reaction of polyol and polyisocyanate, and is a synthetic material between rubber and plastic. Wherein, the rigid polyurethane foam is a material which does not deform obviously under a certain load and can not recover to the initial state after being deformed under an overlarge load. The rigid polyurethane foam material is usually obtained by compounding polyol, isocyanate and various auxiliary agents, has lower heat conductivity coefficient, lower density, certain strength and hardness, can effectively improve the flame retardance, water resistance and corrosion resistance after being treated by the additive, and is widely applied to the field of furniture.
Although the rigid polyurethane foam has a certain strength, it has not been able to satisfy the use requirements in many cases, and therefore, it is necessary to improve the mechanical properties thereof. The fiber reinforcement is one of the effective ways at present, but the combination of untreated fibers and polyurethane is only simple mechanical combination, the interface combination is poor, the compatibility is poor, the fibers are easy to pull out on the broken surface of the polyurethane, and the untreated fibers are easy to agglomerate in the polyurethane material and are not uniformly distributed, so that the fiber reinforcement effect is influenced.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a surface modified fiber reinforced polyurethane composite material and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.3-1.5 parts of silicone oil, 0.8-1.4 parts of catalyst, 1-3 parts of coupling agent, 6.7-12.5 parts of composite foaming agent, 4-9 parts of flame retardant, 27-36 parts of isocyanate and 12-20 parts of surface modified palm fiber.
The type of the plant fiber is an important factor influencing the performance of the composite material, and the type of the fiber determines the physical and mechanical properties of the fiber, and also determines the characteristics of the surface free energy, the surface polarity, the water absorption and the like of the fiber. The palm fiber has lower crystallinity, so that the tensile property of the palm fiber is poorer than that of natural fibers such as jute, ramie and the like, but the palm fiber has stronger elasticity and toughness and higher fracture toughness.
According to the invention, the fiber-reinforced polyurethane composite material is constructed by adopting the surface modified palm fibers, and the strength of the polyurethane composite material is improved by utilizing the characteristics of stronger elasticity and toughness and higher fracture toughness of the palm fibers. The interface combination condition of the fiber and the material matrix is improved through the surface modification of the palm fiber. The surface modified fiber reinforced polyurethane composite material obtained by compounding various additives not only maintains the mechanical strength of the polyurethane material, but also has good fireproof and flame retardant properties, so that the surface modified fiber reinforced polyurethane composite material still maintains good performance at higher temperature.
As a preferred embodiment of the surface-modified fiber-reinforced polyurethane composite material according to the present invention, the method for preparing the surface-modified palm fibers comprises: carrying out alkali treatment on the palm fibers by using alkali liquor, and then carrying out heat treatment at 75-85 ℃ for 20-30 min; and soaking the palm fiber after heat treatment in an aluminate coupling agent, reacting for 1-2 h, and drying to obtain the surface modified palm fiber.
As a preferred embodiment of the surface modified fiber reinforced polyurethane composite material, the concentration of NaOH in the alkali liquor is 5-8 wt%, and Na is added2The concentration of S is 0.25-1 wt%, Na2S2O4The concentration of (B) is 0.5 to 1.5 wt%.
Under the action of alkali liquor, part of pectin, hemicellulose and low molecular impurities of an extract in the palm fiber are dissolved, the cellulose expands, the roughness of the surface of the fiber is increased, the capability of mutual combination of the fiber and a matrix is improved, and the strength of the palm fiber is reduced along with the dissolution of the low molecular substances and the decomposition of part of the cellulose. During the lye treatment, Na on the one hand2S and Na2S2O4Chemically reacting with aldehyde end of cellulose, hemicellulose, etc., reducing peeling reaction, protecting cellulose, and adding Na2S and Na2S2O4The content of the sodium hydroxide is increased, and the sodium hydroxide is added,the degree of the protection of the fibers is increased, and on the other hand, the damage degree of the crystalline regions of the palm fibers is small, so that alkali liquor is difficult to permeate into the fibers, the surface roughness is reduced, and the improvement of the interface bonding force of the palm fibers and a polyurethane matrix is not facilitated. Through repeated tests, NaOH and Na in alkali liquor are preferably selected2S and Na2S2O4To a suitable concentration.
As a preferred embodiment of the surface modified fiber reinforced polyurethane composite material according to the present invention, the volume concentration of the aluminate coupling agent is 3% to 7%.
The aluminate can effectively remove hydroxyl on the surface of the palm fiber, so that the surface of the fiber is coated with hydrophobic molecules, thereby being beneficial to improving the dispersibility of the palm fiber in a polyurethane matrix, improving the interface compatibility of the composite material and improving the mechanical property of the composite material.
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.8 part of silicone oil, 1.2 parts of catalyst, 2.4 parts of coupling agent, 10 parts of composite foaming agent, 5 parts of flame retardant, 30 parts of isocyanate and 16 parts of surface modified palm fiber.
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 1.4 parts of silicone oil, 0.9 part of catalyst, 1.8 parts of coupling agent, 12 parts of composite foaming agent, 6 parts of flame retardant, 28 parts of isocyanate and 20 parts of surface modified palm fiber.
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.6 part of silicone oil, 0.8-1.4 parts of catalyst, 1.5 parts of coupling agent, 8 parts of composite foaming agent, 8 parts of flame retardant, 35 parts of isocyanate and 14 parts of surface modified palm fiber.
As a preferable embodiment of the surface modified fiber reinforced polyurethane composite material, the composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, the hydroxyl value of the polyether polyol 1 is 140-250 mgKOH/g, the functionality is 1-2, the hydroxyl value of the polyether polyol 2 is 300-500 mgKOH/g, the functionality is 1-3, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 12-5: 88-95.
The composite polyether polyol with different functionality can effectively improve the intersolubility of the composite polyether polyol with other raw material components, and avoid overlarge brittleness of the composite material.
As a preferred embodiment of the surface modified fiber reinforced polyurethane composite material of the present invention, the catalyst is at least one of triethylamine, triethanolamine, and triethylenediamine; the flame retardant comprises aluminum hypophosphite, dimethyl methyl phosphonate and cyclic phosphonate, and the weight ratio of the aluminum hypophosphite to the cyclic phosphonate is 1-4: 1-3: 2-3; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 3-5: 5-3; the coupling agent is a silane coupling agent.
The invention also provides a preparation method of the surface modified fiber reinforced polyurethane composite material, which comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fibers, and stirring at 500-700 rpm for 20-30 min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, and stirring at 800-1000 rpm until the reaction starts to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the fiber-reinforced polyurethane composite material is constructed by adopting the surface modified palm fibers, the strength of the polyurethane composite material is improved by utilizing the characteristics of stronger elasticity and toughness and higher fracture toughness of the palm fibers, and the interface bonding condition of the fibers and the material matrix is improved by the surface modification of the palm fibers. The surface modified fiber reinforced polyurethane composite material provided by the invention has high mechanical strength and good fireproof and flame-retardant properties.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It will be understood by those skilled in the art that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the examples, the experimental methods used were all conventional methods unless otherwise specified, and the materials, reagents and the like used were commercially available without otherwise specified.
Example 1
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 1.0 part of silicone oil, 1.2 parts of catalyst, 1 part of coupling agent, 8 parts of composite foaming agent, 5 parts of flame retardant, 30 parts of isocyanate and 18 parts of surface modified palm fiber.
The preparation method of the surface modified palm fiber comprises the following steps: carrying out alkali treatment on the palm fibers for 1h by using alkali liquor, and then carrying out heat treatment at 80 ℃ for 30 min; soaking the palm fiber after heat treatment in an aluminate coupling agent with the volume concentration of 5%, reacting for 1h, and drying to obtain the surface modified palm fiber; the components of the alkali liquor are shown in tables 1-2 respectively.
TABLE 1
TABLE 2
The composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, wherein the hydroxyl value of the polyether polyol 1 is 150mgKOH/g, the hydroxyl value of the polyether polyol 2 is 450mgKOH/g, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 10: 90.
The catalyst is triethylamine; the flame retardant comprises aluminum hypophosphite, dimethyl methylphosphonate and cyclic phosphonate ester in a weight ratio of 1:1: 3; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 4: 4; the coupling agent is a silane coupling agent.
The preparation method of the surface modified fiber reinforced polyurethane composite material of the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fiber, and stirring at 600rpm for 30min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, stirring at 900rpm until the reaction starts, and generating a small amount of bubbles to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing at 110 ℃ for 2h, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
In this example, after the palm fibers were treated with different alkali solutions, the tensile strength of the surface-modified fiber-reinforced polyurethane composite material was measured, and an appropriate alkali solution was selected, and the results are shown in tables 1 and 2.
From the results in tables 1 and 2, it is understood that, in the palm fibers, a part of pectin, hemicellulose and low molecular weight impurities of the extract are dissolved by the action of the alkali solution, the cellulose swells, the roughness of the fiber surface increases, and the improvement of the ability of the interface between the fibers and the matrix is facilitated, but the strength of the palm fibers itself is reduced with the dissolution of the low molecular weight substances and the decomposition of a part of the cellulose. During the lye treatment, Na on the one hand2S and Na2S2O4Chemically reacting with aldehyde end of cellulose, hemicellulose, etc., reducing peeling reaction, protecting cellulose, and adding Na2S and Na2S2O4The content is increased, the degree of protection of the fiber is increased, on the other hand, the damage degree of the crystalline region of the palm fiber is smaller, so that alkali liquor is difficult to permeate into the fiber, the surface roughness is reduced,is not beneficial to improving the interface bonding force of the palm fiber and the polyurethane matrix. Through repeated experiments, the concentration of NaOH in the alkali liquor is preferably 6 wt%, and Na is preferably selected2The concentration of S was 0.5 wt%, Na2S2O4Is 1.0 wt%.
Example 2
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.8 part of silicone oil, 1.2 parts of catalyst, 2.4 parts of coupling agent, 10 parts of composite foaming agent, 5 parts of flame retardant, 30 parts of isocyanate and 16 parts of surface modified palm fiber.
The preparation method of the surface modified palm fiber comprises the following steps: carrying out alkali treatment on the palm fibers by using alkali liquor, and then carrying out heat treatment at 80 ℃ for 25 min; soaking the palm fiber after heat treatment in an aluminate coupling agent with the volume concentration of 5%, reacting for 1h, and drying to obtain the surface modified palm fiber; the concentration of NaOH in the alkali liquor is 6 wt%, Na2The concentration of S was 0.5 wt%, Na2S2O4Is 1.0 wt%.
The composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, wherein the hydroxyl value of the polyether polyol 1 is 200mgKOH/g, the hydroxyl value of the polyether polyol 2 is 450mgKOH/g, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 10: 90.
The catalyst is triethanolamine; the flame retardant comprises aluminum hypophosphite, dimethyl methylphosphonate and cyclic phosphonate ester in a weight ratio of 1:2: 2; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 4: 6; the coupling agent is a silane coupling agent.
The preparation method of the surface modified fiber reinforced polyurethane composite material of the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fiber, and stirring at 650rpm for 25min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, stirring at 1000rpm until the reaction starts, and generating a small amount of bubbles to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing at 120 ℃ for 1h, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
Example 3
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 1.4 parts of silicone oil, 0.9 part of catalyst, 1.8 parts of coupling agent, 12 parts of composite foaming agent, 6 parts of flame retardant, 28 parts of isocyanate and 20 parts of surface modified palm fiber.
The preparation method of the surface modified palm fiber comprises the following steps: carrying out alkali treatment on the palm fibers by using alkali liquor, and then carrying out heat treatment at 80 ℃ for 25 min; soaking the palm fiber after heat treatment in an aluminate coupling agent with the volume concentration of 4%, reacting for 1h, and drying to obtain the surface modified palm fiber; the concentration of NaOH in the alkali liquor is 6 wt%, Na2The concentration of S was 0.5 wt%, Na2S2O4Is 1.0 wt%.
The composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, wherein the hydroxyl value of the polyether polyol 1 is 180mgKOH/g, the hydroxyl value of the polyether polyol 2 is 500mgKOH/g, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 8: 92.
The catalyst is triethylene diamine; the flame retardant comprises aluminum hypophosphite, dimethyl methylphosphonate and cyclic phosphonate ester in a weight ratio of 1:3: 2; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 3: 3; the coupling agent is a silane coupling agent.
The preparation method of the surface modified fiber reinforced polyurethane composite material of the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fiber, and stirring at 600rpm for 25min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, stirring at 850rpm until the reaction starts, and generating a small amount of bubbles to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing at 100 ℃ for 2h, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
Example 4
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.6 part of silicone oil, 1.2 parts of catalyst, 1.5 parts of coupling agent, 8 parts of composite foaming agent, 8 parts of flame retardant, 35 parts of isocyanate and 14 parts of surface modified palm fiber.
The preparation method of the surface modified palm fiber comprises the following steps: carrying out alkali treatment on the palm fibers by using alkali liquor, and then carrying out heat treatment at 75 ℃ for 30 min; soaking the palm fiber after heat treatment in an aluminate coupling agent with the volume concentration of 6%, reacting for 2h, and drying to obtain the surface modified palm fiber; the concentration of NaOH in the alkali liquor is 6 wt%, Na2The concentration of S was 0.5 wt%, Na2S2O4Is 1.0 wt%.
The composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, wherein the hydroxyl value of the polyether polyol 1 is 140mgKOH/g, the hydroxyl value of the polyether polyol 2 is 300mgKOH/g, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 12: 88.
The catalyst is triethylamine and triethanolamine, and the weight ratio is 1: 1; the flame retardant comprises aluminum hypophosphite, dimethyl methylphosphonate and cyclic phosphonate ester in a weight ratio of 4:2: 2; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 5: 3; the coupling agent is a silane coupling agent.
The preparation method of the surface modified fiber reinforced polyurethane composite material of the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fiber, and stirring at 550rpm for 30min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, stirring at 950rpm until the reaction starts, and generating a small amount of bubbles to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing at 120 ℃ for 1h, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
Example 5
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 1.5 parts of silicone oil, 1.4 parts of catalyst, 1 part of coupling agent, 6.7 parts of composite foaming agent, 4 parts of flame retardant, 36 parts of isocyanate and 12 parts of surface modified palm fiber.
The preparation method of the surface modified palm fiber comprises the following steps: carrying out alkali treatment on the palm fibers by using alkali liquor, and then carrying out heat treatment at 85 ℃ for 20 min; soaking the palm fiber after heat treatment in an aluminate coupling agent with the volume concentration of 3%, reacting for 2h, and drying to obtain the surface modified palm fiber; the concentration of NaOH in the alkali liquor is 6 wt%, Na2The concentration of S was 0.5 wt%, Na2S2O4Is 1.0 wt%.
The composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, wherein the hydroxyl value of the polyether polyol 1 is 250mgKOH/g, the hydroxyl value of the polyether polyol 2 is 450mgKOH/g, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 5: 95.
The catalyst is triethylamine; the flame retardant comprises aluminum hypophosphite, dimethyl methylphosphonate and cyclic phosphonate ester in a weight ratio of 1:1: 2; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 4: 3; the coupling agent is a silane coupling agent.
The preparation method of the surface modified fiber reinforced polyurethane composite material of the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fiber, and stirring at 500rpm for 30min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, stirring at 800rpm until the reaction starts, and generating a small amount of bubbles to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing at 100 ℃ for 2h, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
Example 6
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.3 part of silicone oil, 0.8 part of catalyst, 3 parts of coupling agent, 12.5 parts of composite foaming agent, 9 parts of flame retardant, 27 parts of isocyanate and 20 parts of surface modified palm fiber.
The preparation method of the surface modified palm fiber comprises the following steps: carrying out alkali treatment on the palm fibers by using alkali liquor, and then carrying out heat treatment at 80 ℃ for 30 min; soaking the palm fiber after heat treatment in an aluminate coupling agent with the volume concentration of 7%, reacting for 1h, and drying to obtain the surface modified palm fiber; the concentration of NaOH in the alkali liquor is 6 wt%, Na2The concentration of S was 0.5 wt%, Na2S2O4Is 1.0 wt%.
The composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, wherein the hydroxyl value of the polyether polyol 1 is 210mgKOH/g, the hydroxyl value of the polyether polyol 2 is 400mgKOH/g, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 7: 93.
The catalyst is triethylamine; the flame retardant comprises aluminum hypophosphite, dimethyl methylphosphonate and cyclic phosphonate ester in a weight ratio of 2:1: 3; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 4: 5; the coupling agent is a silane coupling agent.
The preparation method of the surface modified fiber reinforced polyurethane composite material of the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fiber, and stirring at 700rpm for 20min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, stirring at 1000rpm until the reaction starts, and generating a small amount of bubbles to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing at 110 ℃ for 2h, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
Example 7
The surface modified fiber reinforced polyurethane composite material comprises the following components in parts by weight: 100 parts of composite polyether polyol, 0.3 part of silicone oil, 0.8 part of catalyst, 3 parts of coupling agent, 12.5 parts of composite foaming agent, 9 parts of flame retardant, 27 parts of isocyanate and 20 parts of surface modified jute fiber.
The preparation method of the surface modified jute fiber comprises the following steps: performing alkali treatment on jute fibers by using alkali liquor, and performing heat treatment at 80 ℃ for 30 min; soaking the jute fiber after heat treatment in an aluminate coupling agent with the volume concentration of 7%, reacting for 1h, and drying to obtain the surface modified jute fiber; the concentration of NaOH in the alkali liquor is 6 wt%, Na2The concentration of S was 0.5 wt%, Na2S2O4Is 1.0 wt%.
The composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, wherein the hydroxyl value of the polyether polyol 1 is 210mgKOH/g, the hydroxyl value of the polyether polyol 2 is 400mgKOH/g, and the weight ratio of the polyether polyol 1 to the polyether polyol 2 is 7: 93.
The catalyst is triethylamine; the flame retardant comprises aluminum hypophosphite, dimethyl methylphosphonate and cyclic phosphonate ester in a weight ratio of 2:1: 3; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 4: 5; the coupling agent is a silane coupling agent.
The preparation method of the surface modified fiber reinforced polyurethane composite material of the embodiment comprises the following steps:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface-modified jute fiber, and stirring at 700rpm for 20min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, stirring at 1000rpm until the reaction starts, and generating a small amount of bubbles to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing at 110 ℃ for 2h, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
The performance parameters of the surface-modified fiber-reinforced polyurethane composite materials prepared in examples 2 to 7 are shown in table 3.
TABLE 3
In conclusion, the fiber-reinforced polyurethane composite material is constructed by adopting the surface-modified palm fibers, the strength of the polyurethane composite material is improved by utilizing the characteristics of stronger elasticity and toughness and higher fracture toughness of the palm fibers, and the interface bonding condition of the fibers and the material matrix is improved by the surface modification of the palm fibers. The surface modified fiber reinforced polyurethane composite material provided by the invention has high mechanical strength and good flame retardance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. The surface modified fiber reinforced polyurethane composite material is characterized by comprising the following components in parts by weight: 100 parts of composite polyether polyol, 0.3-1.5 parts of silicone oil and 0.8-1.4 parts of catalystThe composite material comprises, by weight, 1-3 parts of a coupling agent, 6.7-12.5 parts of a composite foaming agent, 4-9 parts of a flame retardant, 27-36 parts of isocyanate and 12-20 parts of surface modified palm fibers, wherein the preparation method of the surface modified palm fibers comprises the following steps: carrying out alkali treatment on the palm fibers by using alkali liquor, and then carrying out heat treatment at 75-85 ℃ for 20-30 min; soaking the palm fiber after heat treatment in an aluminate coupling agent, reacting for 1-2 h, and drying to obtain the surface modified palm fiber; the concentration of NaOH in the alkali liquor is 5-8 wt%, and Na2The concentration of S is 0.25-1 wt%, Na2S2O4The concentration of (B) is 0.5 to 1.5 wt%.
2. The surface-modified fiber-reinforced polyurethane composite material as claimed in claim 1, wherein the volume concentration of the aluminate coupling agent is 3 to 7%.
3. The surface-modified fiber-reinforced polyurethane composite material according to claim 1, comprising the following components in parts by weight: 100 parts of composite polyether polyol, 0.8 part of silicone oil, 1.2 parts of catalyst, 2.4 parts of coupling agent, 10 parts of composite foaming agent, 5 parts of flame retardant, 30 parts of isocyanate and 16 parts of surface modified palm fiber.
4. The surface-modified fiber-reinforced polyurethane composite material according to claim 1, comprising the following components in parts by weight: 100 parts of composite polyether polyol, 1.4 parts of silicone oil, 0.9 part of catalyst, 1.8 parts of coupling agent, 12 parts of composite foaming agent, 6 parts of flame retardant, 28 parts of isocyanate and 20 parts of surface modified palm fiber.
5. The surface-modified fiber-reinforced polyurethane composite material according to claim 1, comprising the following components in parts by weight: 100 parts of composite polyether polyol, 0.6 part of silicone oil, 0.8-1.4 parts of catalyst, 1.5 parts of coupling agent, 8 parts of composite foaming agent, 8 parts of flame retardant, 35 parts of isocyanate and 14 parts of surface modified palm fiber.
6. The surface-modified fiber-reinforced polyurethane composite material as claimed in claim 1, wherein the composite polyether polyol comprises polyether polyol 1 and polyether polyol 2, the hydroxyl value of polyether polyol 1 is 140-250 mgKOH/g, the functionality is 1-2, the hydroxyl value of polyether polyol 2 is 300-500 mgKOH/g, the functionality is 1-3, and the weight ratio of polyether polyol 1 to polyether polyol 2 is 12-5: 88-95.
7. The surface-modified fiber-reinforced polyurethane composite material according to claim 1, wherein the catalyst is at least one of triethylamine, triethanolamine, and triethylenediamine; the flame retardant comprises aluminum hypophosphite, dimethyl methyl phosphonate and cyclic phosphonate, and the weight ratio of the aluminum hypophosphite to the cyclic phosphonate is 1-4: 1-3: 2-3; the composite foaming agent comprises cyclopentane and methyl formate in a weight ratio of 3-5: 5-3; the coupling agent is a silane coupling agent.
8. The method for preparing the surface-modified fiber-reinforced polyurethane composite material according to any one of claims 1 to 7, comprising the steps of:
(1) weighing raw materials of each component according to a proportion;
(2) mixing composite polyether polyol, silicone oil, a catalyst, a coupling agent, a composite foaming agent, a flame retardant and surface modified palm fibers, and stirring at 500-700 rpm for 20-30 min to obtain a mixture 1;
(3) adding isocyanate into the mixture 1, and stirring at 800-1000 rpm until the reaction starts to obtain a mixture 2;
(4) and pouring the mixture 2 into a mold, standing for foaming, curing, and demolding to obtain the surface modified fiber reinforced polyurethane composite material.
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