CN115058113A - Fiber-reinforced polyurethane composite material and preparation method and application thereof - Google Patents
Fiber-reinforced polyurethane composite material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115058113A CN115058113A CN202210815211.5A CN202210815211A CN115058113A CN 115058113 A CN115058113 A CN 115058113A CN 202210815211 A CN202210815211 A CN 202210815211A CN 115058113 A CN115058113 A CN 115058113A
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- Prior art keywords
- fiber
- composite
- fiber reinforced
- composite material
- reinforced polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 51
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
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- 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
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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Abstract
The invention relates to the field of composite materials, in particular to a fiber-reinforced polyurethane composite material and a preparation method thereof. The composite material contains hard polyurethane foam and reinforcing fiber, and the density of the material is 300-500Kg/m 3 (ii) a The composite material HAs water absorption rate not more than 5%, Shore hardness not less than 60HA, bending strength not less than 50MPa, shear strength not less than 10MPa, and dimensional stability not more than 1%, and HAs no change in appearance after being soaked in acid solution or alkali solution for 30 days, heat conduction coefficient not more than 0.05W/(m.K), and linearityThe coefficient of thermal expansion (1/deg.C) is less than or equal to 1 × 10 ‑5 . The composite material has the advantages of light weight, high strength, mechanical properties (shearing resistance, compression resistance and the like), heat preservation, heat insulation, acid and alkali resistance, corrosion resistance, moisture resistance and good dimensional stability, and can be used for low-density materials (non-structural materials) such as doors and windows, filling, external decoration and the like.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a fiber-reinforced polyurethane composite material and a preparation method thereof.
Background
The natural wood has ecological environmental protection, proper elasticity and hardness and good performance effect, so the natural wood is widely applied to various aspects of buildings, furniture, outdoor products and the like, the poor natural corrosion resistance of the fast-growing wood is considered, before the natural wood is used, the natural wood is usually subjected to corrosion prevention treatment, no matter which corrosion prevention impregnation treatment mode is adopted, the preservative enters the interior of the wood from the exterior of the wood, the preservative drug-loading rate of the outer layer of the wood is the highest, the preservative drug-loading rate is lower towards the heart layer, the medicament loss of the wood with high drug-loading rate is higher, and the preservative wood impregnated by the preservative solution is influenced by frequent temperature change, ultraviolet radiation and atmospheric humidity along with the prolonging of the service time, has rapid damage effect on the preservative wood, and gradually loses the preservative in the outer layer contacting with the environment, the durability of the wood is gradually reduced, such as water absorption deformation, cracking, mildew, worm damage, rot and the like, and the durability duration of the anticorrosive wood cannot meet the use requirement of actual engineering. If maintenance or replacement is required, a large amount of timber is consumed for the purpose, which causes damage to forest resources for a long time and also consumes a large amount of maintenance personnel.
The national of this year puts forward higher requirements on energy conservation and environmental protection, so that it is urgent to find a novel material which has low cost, mechanical property equivalent to or even higher than that of solid wood, corrosion resistance and moisture resistance higher than that of the existing anticorrosive wood, safety, no toxicity and environmental protection.
Disclosure of Invention
The invention aims to provide the fiber reinforced polyurethane composite material which is low in water absorption, good in mechanical property, resistant to acid and alkali corrosion and high in dimensional stability.
In order to achieve the purpose, the invention adopts the following technical scheme: the composite material contains hard polyurethane foam and reinforcing fiber, and the density of the material is 300-500Kg/m 3 (ii) a The composite material HAs water absorption rate not more than 5%, Shore hardness not less than 60HA, bending strength not less than 50MPa, shear strength not less than 10MPa, and dimensional stability not more than 1.5%, and HAs no change in appearance after being soaked in acid solution or alkali solution for 30 days, heat conduction coefficient not more than 0.05W/(m.K), and linear thermal expansion coefficient not more than 1.0 × 10 (1/deg.C) -5 。
The composite material has the advantages that:
(1) in terms of material density, the density of the composite material is 300-500Kg/m 3 Density of wood (400 Kg/m) and wood of poplar and pine 3 About) is equivalent to or even lower than that of natural basswood (500-550 Kg/m) 3 ) The equal density is close, so the processing can be carried out by cutting, sawing, planing and the like as natural solid wood; in the aspect of water absorption, the water absorption of the composite material is less than or equal to 5%, and compared with a solid wood material, the water absorption is lower and the performance is more excellent;
(2) in the aspect of heat preservation and heat insulation, the heat conduction coefficient of the composite material is less than or equal to 0.05W/(m.K), the heat conduction coefficient expansion is low, compared with natural dry solid wood (the heat conduction coefficient is greater than or equal to 0.08W/(m.K)), the heat preservation performance is higher, and the composite material can be used as a heat preservation material for wall bodies, door and window core materials with higher requirements on heat preservation and heat insulation;
(3) compared with natural wood (or natural wood subjected to preservative treatment, namely, anticorrosive wood), the mechanical property of the composite material is greatly improved, the shear resistance, bending resistance and other capabilities of the composite material are higher than those of the natural wood, the hardness is higher, and the composite material has the characteristics of light weight and high strength, and the mechanical property of the composite material cannot be lost even being exposed in the air for a long time, so that the composite material can completely replace the natural wood (anticorrosive wood) on the market from the aspect of mechanical property and can be widely applied to the fields of door and window furniture, tourist properties, building energy conservation and the like;
compared with natural wood which needs a certain growth period, the anticorrosion wood is required to be processed by an anticorrosion process, and the composite material can be rapidly produced in a factory, has higher production efficiency and higher cost performance;
in addition, in the production process of the composite material, chemical raw materials are fully reacted, no toxic residue exists, the environmental protection grade reaches E0 grade, and the highest anticorrosive wood on the market is E1 grade, so that the environment protection performance is more excellent.
(4) In the aspects of acid and alkali resistance, corrosion resistance and moisture resistance, the natural wood contains cellulose, gum and the like, the plant polysaccharide is water-soluble and is easy to decompose and rot by mould and bacteria in the environment, and the acid and alkali resistance, the corrosion resistance and the moisture resistance are crossed. In the composite material, chemical bonds formed by chemical reaction of the hard polyurethane foam are stable in the environment, are not easy to hydrolyze, are difficult to decompose bacteria and mold in the environment, and have no change in appearance after being soaked in acid liquor or alkali liquor for 30 days.
(5) In terms of dimensional stability, the dimensional stability is not more than 1.5%, and the coefficient of linear thermal expansion (1/DEG C) is not more than 1X 10 -5 The deformation rate is low, the stability can be kept when the extreme temperature is changed, and the cracking resistance is strong.
In conclusion, the composite material has high strength, high density, excellent mechanical properties (shearing resistance, compression resistance and the like), good heat preservation and insulation, acid and alkali resistance, corrosion resistance, moisture resistance and dimensional stability, and can be used for non-structural materials such as core materials of doors, windows and walls.
Further, the density of the rigid polyurethane foam is 100-300 Kg/m 3 The density of the reinforcing fiber is 1-2.7 g/cm 3 (ii) a The mass part ratio of the hard polyurethane foam to the reinforcing fiber is 1: 1-4: 1.
When the reinforcing fiber is non-combustible fiber, the proportion of the fiber can be obtained by calculating the combustion composite material test piece according to the GB/T2577-.
The inventor finds that, due to the high density of the reinforcing fibers, if the ratio of the total mass of the composite material is less than 20%, the polyurethane mixture absorbed by the fibers (such as the maximum resin absorption of each fiber is 120% of the mass of the polyurethane mixture) is not enough to fill the cavity of the product during foaming, and void and hole defects are formed, which affects the quality of the product, but if the ratio of the total mass of the composite material exceeds 50%, the lightweight effect of the composite material is affected. Therefore, the proportion of the reinforced fiber in the composite material is 20-50% which is an ideal content, so that the quality of the finished product can be improved without influencing the light weight effect of the finished product.
Furthermore, the nail holding power of the composite material is larger than or equal to 500N, the nail holding power is close to that of natural wood (such as pine), after the nail enters the board, the nail hole is easy to fix and not easy to loosen and fall, the nail hole can be recycled, and vice versa.
Further, the reinforced fiber is continuous glass fiber or glassOne or more of glass fiber felt, bamboo fiber and polymer fiber are mixed, and different fibers are selected: continuous glass fiber (density 2.6 g/cm) 3 ) Continuous glass fiber mat (density 2.6 g/cm) 3 ) Bamboo fiber (1.49 g/cm) 3 ) Chemical fiber (common PP/PET spun fiber with density of 1.0-1.2 g/cm) 3 ) According to different fiber densities and design amounts, the composite material keeps the characteristics of light weight and high strength through formula design.
Further, the raw materials of the rigid polyurethane foam comprise a material A and a material B, wherein the mass part ratio of the material A to the material B is 1: 0.9-1: 1.2.
The polyurethane foam prepared by adopting the proportion has good performance in the aspects of heat insulation, acid and alkali resistance, corrosion and moisture resistance, size stability and the like.
Further, the material B is isocyanate or modified isocyanate, and the material A comprises the following raw materials in parts by weight:
100 parts of combined polyether;
0.5-1.5 parts of a catalyst;
1.0-3 parts of a surfactant;
0.6-1 part of foaming agent.
The modified isocyanate adopted by the material B is a product obtained by the chemical reaction of isocyanate, the material A can ensure that the rising time of the polyurethane foam is more than or equal to 2min and the density of the foamed polyurethane foam is 100-300 Kg/m through the mixture ratio 3 。
The polyether composition is prepared by end-capping polymerization of propylene oxide with polyol and/or polyamine as an initiator and propylene oxide as a polymerization monomer, and has a hydroxyl value of 30-500 mg KOH/g, an average functionality of 2-6 (preferably 3-4.5), and a number average molecular weight of 200-4800 (preferably 400-3000).
The initiator may optionally comprise one or more of glycerol, triethanolamine, pentaerythritol, diethylene glycol, sorbitol and sucrose, preferably one or more of pentaerythritol, diethylene glycol, sorbitol and sucrose;
the average functionality of the combined polyether is more than 2, so that the crosslinking degree, the hardness and the strength of the composite material and the chemical dissolution/corrosion resistance can be improved, but the higher the functionality of the polyether is, the higher the viscosity is, the lower the flowability is, and the lower the flowability is controlled below 6.
Further, the isocyanate or modified isocyanate is an aliphatic, cycloaliphatic, araliphatic, aromatic isocyanate, or a combination thereof.
Wherein the aliphatic isocyanate may be selected from alkylene diisocyanates, particularly alkylene diisocyanates containing 4 to 12 carbon atoms in the alkylene group, such as 1, 12-dodecane diisocyanate, 2-ethyltetramethylene-1, 4-diisocyanate, 2-methyl-pentamethylene-1, 5-diisocyanate, 2-ethyl-2-butyl pentamethylene-1, 5-diisocyanate, tetramethylene-1, 4-diisocyanate, hexamethylene-1, 6-diisocyanate, and the like;
the alicyclic isocyanate may be selected from cyclohexane-1, 3-diisocyanate, cyclohexane-1, 4-diisocyanate, 1-isocyanate-3, 3, 5-trimethyl-5-isocyanato-methylcyclohexane (isophorone diisocyanate), 2, 4-hexahydrotoluene diisocyanate, 2, 6-hexahydrotoluene diisocyanate, 4 ' -dicyclohexylmethane diisocyanate, 2 ' -dicyclohexylmethane diisocyanate, 2,4 ' -dicyclohexylmethane diisocyanate, etc.;
the aromatic isocyanate may be selected from diphenylmethane diisocyanate (such as 4,4 '-diphenylmethane diisocyanate, 2' -diphenylmethane diisocyanate), polymethylene polyphenyl isocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, etc.
The araliphatic isocyanate may be selected from xylylene diisocyanate (e.g., m-xylylene diisocyanate, p-xylylene diisocyanate) and the like, and these isocyanates may be used alone or in combination.
Furthermore, the catalyst is mainly a thermosensitive delayed catalyst, and before the environment does not reach the catalyst deblocking temperature (50-60 ℃), the catalytic action of the catalyst is weaker, the chemical reaction of polyurethane is relatively slow, and the curing reaction can be carried out after the polyurethane and the reinforcing fiber are fully infiltrated.
Selecting a heat-sensitive delay catalyst, specifically selecting one or more of an amine catalyst, an organic bismuth/organic tin catalyst and a trimerization catalyst of a heat-sensitive group. The thermosensitive catalyst contains nitrogen family element compounds and organic metal compounds of thermosensitive groups such as N-heterocyclic carbines, quaternary ammonium salts, aldimines, phenol sulfonates and the like as trimerization catalysts of aliphatic and aromatic isocyanates, and is characterized in that under the condition that a system is heated, active centers protected by the thermosensitive groups are separated to form active centers, and-NCO and-OH groups are activated to catalyze and carry out polyurethane gel reaction. The heat-sensitive catalyst can effectively delay the reaction time of a system, ensure the sufficient soaking time (generally required time is 4-10 min) of the polyurethane raw material and the continuous fiber at the early stage, and can be heated to quickly react and solidify after entering a plate chain line at the later stage (ensure the time for completing solidification is 25-40 min). Formate salts such as 2-hydroxy-N, N, N-trimethyl-1-propylamine, N, N' -tris (dimethylaminopropyl) -hexahydrotriazine, 2,4, 6-tris (dimethylaminomethyl) phenol are commonly used tertiary amine trimerization catalysts.
Furthermore, the foaming agent is water, and the traditional foaming agent adopts small-molecular hydrocarbons such as Freon and cyclopentane, which can generate substances with great harm to the environment such as fluorine, and the foaming agent is more environment-friendly when water is used.
Further, a flame retardant with the flame retardant grade of more than B1 grade is added into the composite material (divided according to the standard of 'GB 8624 and 2012 building materials and products with graded combustion performance'), and the mass part ratio of the composite material to the flame retardant is 10: 1-10: 4. The fire retardant does not react with the material A, the material B and the reinforced fiber, and the produced material can be used for doors and windows, walls, interior decoration, carriage fillers and other places with higher fire-retardant grade.
Further, since organic flame retardants emit toxic gases during combustion (for example, halogen-containing flame retardants generally emit HX-type toxic and harmful gases such as HCl and HBr), the flame retardant of the present invention is more environmentally friendly due to the selection of inorganic filler flame retardants.
Further, the inorganic filler flame retardant is one or a mixture of several of phosphorus, nitrogen, expanded graphite, magnesium hydroxide and montmorillonite.
For example, the halogen-free phosphorus-based filler halogen includes, but is not limited to, one or more of tris (2-chloropropyl) phosphate (TCPP), tris (2-chloroethyl) phosphate (TCEP), tris (2, 3-dichloropropyl) phosphate (TDCP), tetrakis (2-chloroethyl) diethylene ether diphosphate, tetrakis (2-chloroethyl) ethylene diphosphate and tetrakis (2-chloroethyl) -2, 2-dichloromethyl-1, 3-propylene diphosphate, and is preferably added in an amount of 5 to 20 parts by mass.
The flame retardant also comprises expanded graphite, preferably natural crystalline graphite which can be instantaneously expanded into vermicular shape when being subjected to special treatment and high temperature. Expanded graphite is prepared by procedures known in the art and typically the graphite is first modified with an oxidizing agent such as nitrate, chromate, peroxide, or by electrolytically opening up the crystalline layer, followed by insertion of nitrate or sulfate into the graphite; the expandable graphite can be expandable graphite with the expansion ratio of 100-400 ml/g, the mesh number of 32-325 meshes, the pH value of 4-7 and the moisture content of not more than 1 wt%, preferably expandable graphite with the moisture content of 80-250 meshes, and preferably the addition amount of 5-15 parts by mass.
The invention also discloses a preparation method of the fiber reinforced polyurethane composite material, which comprises the steps of creel yarn arrangement, glue injection, infiltration, curing molding and cutting, wherein in the infiltration step, a glue impregnation tool adopts a semi-closed type vibration glue impregnation mode, firstly, a polyurethane high-pressure glue injection machine uniformly sprays polyurethane raw materials on the surface of the fiber, and then, the reinforced fiber and the polyurethane raw materials are uniformly infiltrated through the mode of continuous left and right vibration and extrusion of the tool.
The glass fiber is mainly longitudinally distributed (similar to longitudinal lines for tree growth) in the continuous traction direction parallel to the plate link line; in addition, due to the action of the left and right transverse movement of the self-made soaking tool, the glass fiber part presents an angle or a direction perpendicular to the continuous traction direction of a plate chain line, and the glass fiber part presents transverse distribution, and a large amount of disordered long fibers also exist in the glass fiber, so that the disordered angular distribution (similar to transverse grains in wood) of the part of the fiber along the traction direction is presented under the vibration and extrusion effects of the soaking tool. The wood grain is mainly provided with longitudinal grains and partially provided with disordered transverse grains with angle distribution, and the wood grain is combined to form unique solid wood texture.
The invention uniformly mixes the fiber and the polyurethane raw material by controlling the steps of yarn arrangement and infiltration, the performance of the product is uniform, the production standardization and scale of the composite material are realized, and particularly, the fiber is regularly distributed in the polyurethane by a semi-closed type vibration impregnation mode to form a shape close to the texture of the natural wood.
The invention also discloses application of the fiber reinforced polyurethane composite material, and the composite material can be used as a heat-insulating filling material on a wall body and a door and window core material.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the invention;
FIG. 2 is a schematic view of the infiltration tool of FIG. 1;
the reference numbers in the drawings are: the device comprises a material barrel A1, a material barrel B2, a polyurethane glue injection machine 3, a creel 4, a soaking tool 5, a soaking groove 51, an eccentric mechanism 52, a vibrating frame 53, a vertical slide rail 54, a transverse slide rail 55, an oscillator 56, a laminating machine 6 and a cutting machine 7.
Detailed Description
The following is further detailed by the specific embodiments:
the fiber reinforced polyurethane composite material comprises the following ingredients:
firstly, preparing raw materials
(I) Material A
The composite polyether foaming agent is composed of 100 parts of composite polyether, 1.5 parts of catalyst, 3 parts of surfactant and 1 part of foaming agent.
(1) Combined polyether
The average hydroxyl number of the conjugate polyether is 328 and the average functionality is 3.85, wherein the polyether polyol Ia: polyether polyol Ib: the mass parts of the polyether polyol ic are respectively 25 parts, 50 parts and 25 parts.
Wherein: (1) polyether polyol Ia: taking glycerin as an initiator, carrying out ring-opening polymerization on propylene oxide, sealing the end of the propylene oxide, and obtaining the number average molecular weight of 2000; (2) polyether polyol Ib: taking a mixture of sucrose and diethylene glycol with a molar ratio of 3.7:6.3 as an initiator, carrying out ring-opening polymerization on propylene oxide, and capping the propylene oxide with a number average molecular weight of 550; (3) polyether polyol ic: sorbitol and toluenediamine mixture initiator, propylene oxide ring-opening polymerization, functionality of 4, number average molecular weight 600;
(2) catalyst: catalyst iva of guangzhou yourun synthesis materials ltd: RM-301 is 1 part, catalyst IVb from Beijing Yintaidech technologies, Inc.: 0.5 part of SA-1;
(3) surfactant (b): selecting a surfactant IIa of German winning company: b8870;
(4) foaming agent: water was chosen as the blowing agent.
(II) B material
Polymeric MDI (fully-known as polyphenyl methane diisocyanate and polymer thereof) is selected, the NCO (isocyanate group) content of the polymeric MDI is 32-32.5%, and the average functionality is 2.5-2.8.
(III) reinforcing fiber
Tex9600 continuous glass fiber is selected.
(IV) flame retardant
The flame retardant is prepared by mixing two flame retardants: (1) flame retardant IIIa: tetrakis (2-chloroethyl) diethylene ether diphosphate; (2) flame retardant IIIb: the expandable graphite is 80 meshes. The mass part ratio of the flame retardant IIIa to the flame retardant IIIb is 1:1.
Secondly, preparing raw materials
Examples 1-4 materials a, B, flame retardant and continuous glass fibers were prepared according to the formulation of table 1.
| Raw material names (parts by mass) | Example 1 | Example 2 | Example 3 | Example 4 |
| Material A | 100 | 100 | 100 | 100 |
| B material | 120 | 120 | 120 | 120 |
| Continuous glass fiber | 220 | 55 | 94.2 | 94.2 |
| Flame retardant | 30 | 30 | 30 | 0 |
Preparation of materials
Referring to fig. 1 and 2, in the infiltration tool 5, the upper end of the infiltration groove 51 is open, and referring to fig. 1, the left end is a wide opening and the right end is a narrow opening. A vibration frame 53 which crosses the infiltration tank 51 is arranged along the width direction of the infiltration tank 51, the vibration frame 53 is in an n shape, the vibration frame 53 is connected with the output end of the eccentric mechanism 52 and can do transverse digging reciprocating motion and vertical reciprocating motion under the driving of the eccentric mechanism 52, the middle of the vibration frame 53 is connected with an oscillator 54 through a hanging rod, and the oscillator 54 can oscillate when being started. The connection mode of the whole production line is as follows: the A material barrel 1 and the B material barrel 2 are respectively connected with a feed inlet of a polyurethane glue injection machine 3, a discharge outlet of the polyurethane glue injection machine 3 is connected with a liquid inlet of an infiltration tool 5, a yarn outlet end of a creel 4 is opposite to a wide opening of an infiltration groove 51 of the infiltration tool 5, a narrow opening of the infiltration groove 51 is connected with a feed inlet of a laminating machine 6, an outlet of the laminating machine 6 is connected with a cutting machine 7
The test pieces of example 1, example 2, example 3, and example 4 were prepared according to the following procedure:
1. creel
According to the density of the glass fibers and the size of the composite material, the number of the needed glass fibers is calculated, the continuous glass fibers penetrate out of the creel 4, are uniformly distributed according to the cross section of the product, penetrate through the soaking tool 5 and are continuously pulled.
2. Glue injection
Adding the material A and the flame retardant into the material barrel A1, uniformly mixing, adding the material B into the material barrel B2, and feeding the raw materials in the material barrel A1 and the raw materials in the material barrel B2 into the polyurethane glue injection machine 3 for mixing under glue injection pressures of 11.0-11.5 MPa and 10.0-10.5 MPa respectively.
The temperature of the polyurethane glue injection machine 3 is controlled to be 20-30 ℃, the deblocking temperature of the catalyst is not reached to 50-60 ℃, the material A and the material B undergo slow chemical reaction, and the flame retardant does not undergo chemical reaction with the material A and the material B.
3. Infiltration of
The polyurethane glue injection machine 3 injects the mixed polyurethane raw material into the soaking tank 51 of the soaking tool 5, firstly sprays the mixed polyurethane raw material on the surface of the glass fiber in the soaking tank 51 uniformly, and then the glass fiber is extruded by the left and right continuous vibration and extrusion of the vibration frame 53 (the glass fiber is extruded by the vertical reciprocating motion of the vibration frame 53), and the oscillator 56 also performs vibration and knocking motion to soak the glass fiber and the polyurethane raw material uniformly. In the link from glue injection to infiltration, the starting time of the polyurethane foam is more than or equal to 2min, and the infiltration effect is fully ensured.
The glass fiber is mainly longitudinally distributed (similar to the longitudinal lines of the tree growth) parallel to the continuous traction direction; in addition, due to the action of the left and right transverse movement of the self-made soaking tool 5, the glass fiber part presents an angle or is perpendicular to the continuous traction direction, the glass fiber part presents transverse distribution, a large amount of disordered long fibers also exist in the glass fiber, and the disordered angular distribution (similar to transverse grains in wood) of the part of the fiber along the traction direction is presented under the vibration and extrusion action of the soaking tool 5. The wood grain is mainly provided with longitudinal grains and partially provided with disordered transverse grains with angle distribution, and the wood grain is combined to form unique solid wood texture.
4. Curing and forming
The polyurethane fully soaked with the glass fiber enters a laminating machine 6, the temperature in the laminating machine 6 is controlled at 60 ℃, the deblocking temperature of the catalyst is reached, the material A and the material B are foamed and molded, and the curing time is less than or equal to 40 min.
5. Cutting of
And cutting the cured and molded polyurethane material into polyurethane material test pieces with the same size by a cutting machine 7. Finally, example 1, example 2, example 3, and example 4 were manufactured into test pieces 1, 2,3, and 4, respectively.
Third, test and detection
Preparing a pine block with the same size as the polyurethane material test piece, and carrying out experimental detection on the test piece 1, the test piece 2, the test piece 3 and the pine, wherein the results are as follows:
from the test results, it is noted that:
(1) material density: the density of the test pieces 1, 2,3 and 4 was 498Kg/m 3 、395Kg/m 3 、 403Kg/m 3 、407Kg/m 3 Are all 300-500Kg/m 3 Within the range. The density of pine wood is 410Kg/m 3 The density of the test pieces 1-4 is very close to that of pine, and the test pieces can be machined in a mode of cutting, sawing, planing and the like.
(2) Bending strength, shear strength, shore hardness: the bending strength of the test pieces 1, 2,3 and 4 is 105MPa, 65MPa, 87MPa and 90MPa respectively, and the bending strength of the pine is 55 MPa; the shear strength of the test pieces 1, 2,3 and 4 was 21.2MPa, 12.5MPa, 17.3MPa and 18.5MP, respectively, and the shear strength of pine was 7.5 MPa. The shore hardness of the test pieces 1, 2,3 and 4 are respectively 80HA, 65HA, 75HA and 78HA, and the hardness of the pine is 60 HA.
Therefore, the shear resistance, bending resistance and the like of the test pieces 1-4 are higher than those of natural wood, the hardness of the test pieces is higher than that of the natural solid wood, and the test pieces have the characteristics of light weight and high strength, and the mechanical properties of the test pieces cannot be lost even being exposed in the air for a long time, so that the test pieces can completely replace the natural wood (or anticorrosive wood) on the market in terms of performance and can be widely applied to the fields of door and window furniture, tourist properties, building energy conservation and the like.
(3) Water absorption: the water absorption rates of the test pieces 1, 2,3 and 4 are respectively 1.2%, 2.2% and 1.7% and 1.5%, the water absorption rate of the pine is 19.3%, and the water absorption rates of the test pieces 1 to 4 and natural solid wood are greatly different, so that the water absorption is not easy, and the waterproof and moistureproof performances are more excellent.
(4) Coefficient of thermal conductivity: the heat conduction coefficients of the test pieces 1, 2,3 and 4 are respectively 0.02W/(m.K), 0.04W/(m.K), 0.03W/(m.K), and the heat conduction coefficient of the pine is 0.08W/(m.K), so that the heat conduction performances of the test pieces 1 to 4 are equivalent to those of the pine (the heat insulation material is generally 0.03 to 0.17W/(m.K)), and the heat insulation performance is close to that of natural solid wood;
(5) dimensional stability, linear thermal expansion coefficient: the dimensional stability of test pieces 1, 2,3 and 4 was 0.3%, 0.8%, 0.5% and 0.5%, respectively, and the pine content was 5.6%; the linear expansion coefficients of test pieces 1, 2,3 and 4 were 0.3 × 10 -5 (1/℃)、0.7×10 -5 (1/℃)、0.5×10 -5 (1/℃)、0.5×10 -5 (1/deg.C), 7.9 × 10 of pine -5 (1/. degree. C.), therebyTherefore, compared with pine, the test pieces 1-4 have lower linear expansion coefficient, higher dimensional stability, low deformation rate, stability in extreme temperature change and strong cracking resistance.
(2) Acid and alkali resistance: the test pieces 1, 2,3, 4 and pine were tested according to the method in the above table, and the pine was slightly swollen, partially fluffy, discolored, and the appearances of the 4 test pieces were not changed. Therefore, the test pieces 1 to 4 are stable in acid and alkaline environments, and the acid and alkali resistance is higher than that of natural solid wood.
(3) Nail-holding power: the nail holding power of the test piece 1, the test piece 2, the test piece 3 and the test piece 4 is 835N, 580N, 731N and 740N respectively, the nail holding power of the pine is 498N, the nail holding power of the composite material is larger than or close to natural solid wood, after the nail enters the plate, the nail hole is easily fixed by the nail and is not easy to loosen and fall off, the nail hole can be recycled, and vice versa.
In conclusion, the composite material has the advantages of light weight, high strength, strong mechanical properties (shear resistance, hardness and the like), heat preservation, heat insulation, acid and alkali resistance, corrosion resistance, moisture resistance and good dimensional stability, is more comprehensive in performance compared with natural woods such as pine, does not use chemical agents to enhance the corrosion resistance, is more environment-friendly and nontoxic compared with anticorrosive woods, and is more suitable for the aspects of doors and windows, filling, external decoration and the like.
The foregoing is merely an example of the present invention and common general knowledge in the art of designing and/or characterizing particular aspects and/or features is not described in any greater detail herein. It should be noted that, for those skilled in the art, without departing from the technical solution of the present invention, several variations and modifications can be made, which should also be regarded as the protection scope of the present invention, and these will not affect the effect of the implementation of the present invention and the practicability of the patent. The scope of the claims of the present application shall be determined by the contents of the claims, and the description of the embodiments and the like in the specification shall be used to explain the contents of the claims.
Claims (16)
1. A fiber reinforced polyurethane composite characterized by: the composite material contains hard polyurethane foam and reinforcing fiber, and the density of the material is 300-500Kg/m 3 (ii) a The composite material HAs water absorption rate not more than 5%, Shore hardness not less than 60HA, bending strength not less than 50MPa, shear strength not less than 10MPa, and dimensional stability not more than 1.5%, and HAs no change in appearance after being soaked in acid solution or alkali solution for 30 days, heat conduction coefficient not more than 0.05W/(m.K), and linear thermal expansion coefficient not more than 1 × 10 (1/deg.C) -5 。
2. The fiber reinforced polyurethane composite of claim 1, wherein: the density of the hard polyurethane foam is 100-300 Kg/m 3 The density of the reinforcing fiber is 1 to 2.7g/cm 3 (ii) a The mass part ratio of the hard polyurethane foam to the reinforcing fiber is 1: 1-4: 1.
3. The fiber reinforced polyurethane composite of claim 1 or 2, wherein: the nail-holding power of the composite material is more than or equal to 500N.
4. The fiber reinforced polyurethane composite of claim 3, wherein: the reinforced fiber is one or a mixture of several of continuous glass fiber, glass fiber felt, bamboo fiber and polymer fiber.
5. The fiber reinforced polyurethane composite of claim 4, wherein: the raw materials of the rigid polyurethane foam comprise a material A and a material B, wherein the mass part ratio of the material A to the material B is 1: 0.9-1: 1.2.
6. The fiber reinforced polyurethane composite of claim 5, wherein: the material B is isocyanate or modified isocyanate, and the material A comprises the following raw materials in parts by mass:
100 parts of combined polyether;
0.5-1.5 parts of a catalyst;
1.0-3 parts of a surfactant;
0.6-1 part of foaming agent.
7. The fiber reinforced polyurethane composite of claim 6, wherein: the hydroxyl value of the combined polyether is 30-500 mg KOH/g, and the average functionality is 2-6.
8. The fiber reinforced polyurethane composite of claim 7, wherein: the average functionality of the combined polyether is 3-4.5.
9. The fiber reinforced polyurethane composite of claim 8, wherein: the isocyanate or modified isocyanate is an aliphatic, cycloaliphatic, araliphatic, aromatic isocyanate or a combination thereof.
10. The fiber reinforced polyurethane composite of claim 9, wherein: the catalyst is a heat-sensitive delayed action catalyst.
11. The fiber reinforced polyurethane composite of claim 10, wherein: the foaming agent is water.
12. The fiber reinforced polyurethane composite of claim 11, wherein: the composite material is added with a flame retardant grade of more than B1, and the mass part ratio of the composite material to the flame retardant is 10: 1-10: 4.
13. The fiber reinforced polyurethane composite of claim 12, wherein: the flame retardant is an inorganic filler flame retardant.
14. The fiber reinforced polyurethane composite of claim 13, wherein: the inorganic filler flame retardant is one or a mixture of more of phosphorus, nitrogen, expanded graphite, magnesium hydroxide and montmorillonite.
15. The preparation method of the fiber reinforced polyurethane composite material according to any one of claims 1 to 14, comprising the steps of creel yarn arrangement, glue injection, infiltration, curing and forming and cutting, and is characterized in that: in the soaking step, the glue dipping tool adopts a semi-closed vibration glue dipping mode, firstly, a polyurethane high-pressure glue injecting machine uniformly sprays polyurethane raw materials on the surfaces of the fibers, and then, the reinforcing fibers and the polyurethane raw materials are uniformly soaked in a mode of continuous vibration and extrusion from left to right of the tool.
16. Use of a fibre reinforced polyurethane composite according to any one of claims 1 to 14, wherein: the composite material can be used as a heat-insulating filling material on wall bodies and door and window core materials.
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