CN114213573B - Acrylic ester microemulsion wood modifier and preparation method and application thereof - Google Patents
Acrylic ester microemulsion wood modifier and preparation method and application thereof Download PDFInfo
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- CN114213573B CN114213573B CN202111556778.7A CN202111556778A CN114213573B CN 114213573 B CN114213573 B CN 114213573B CN 202111556778 A CN202111556778 A CN 202111556778A CN 114213573 B CN114213573 B CN 114213573B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/02—Processes; Apparatus
- B27K3/08—Impregnating by pressure, e.g. vacuum impregnation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K3/00—Impregnating wood, e.g. impregnation pretreatment, for example puncturing; Wood impregnation aids not directly involved in the impregnation process
- B27K3/52—Impregnating agents containing mixtures of inorganic and organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K5/00—Treating of wood not provided for in groups B27K1/00, B27K3/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27K—PROCESSES, APPARATUS OR SELECTION OF SUBSTANCES FOR IMPREGNATING, STAINING, DYEING, BLEACHING OF WOOD OR SIMILAR MATERIALS, OR TREATING OF WOOD OR SIMILAR MATERIALS WITH PERMEANT LIQUIDS, NOT OTHERWISE PROVIDED FOR; CHEMICAL OR PHYSICAL TREATMENT OF CORK, CANE, REED, STRAW OR SIMILAR MATERIALS
- B27K2240/00—Purpose of the treatment
- B27K2240/30—Fireproofing
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Abstract
The invention relates to the technical field of wood modifiers, and discloses an acrylic ester microemulsion wood modifier and a preparation method and application thereof, wherein the acrylic ester microemulsion wood modifier comprises, by weight, 10-20 parts of soft monomers, 10-20 parts of monomers A, 1-5 parts of emulsifying agents, 0.3-1 part of initiating agents, 0.5-1 part of pH regulators, 0.5-2 parts of chain transfer agents, 0.5-3 parts of polymerization inhibitors, 5-10 parts of flame retardants and 100-150 parts of deionized water; the acrylate microemulsion wood modifier provided by the invention is an aldehyde-free multifunctional wood impregnation modifier, the density, the dimensional stability and the mechanical strength of the wood treated by the wood modifier are greatly improved, meanwhile, the wood treated by the wood modifier has a flame retardant effect, the problem of wood cracking is solved, and the modified wood can be applied to the aspects of indoor furniture, wooden doors and windows, floors and the like.
Description
Technical Field
The invention relates to the technical field of wood modifiers, in particular to an acrylic ester microemulsion wood modifier and a preparation method and application thereof.
Background
Wood is a natural renewable porous polymer material, is a green environment-friendly material, is popular with people, and is widely used for building, furniture, musical instruments, vehicles, boats and the like. In recent years, because the natural forest is forbidden, the artificial forest timber is efficiently modified and utilized with high value, and the artificial forest timber becomes one of effective ways for relieving the contradiction between wood supply and demand in China.
Chemical modification of wood is one of the important methods for modifying wood, and chemical reactants and hydroxyl groups of chemical components of the cell wall of the wood are mainly used for carrying out chemical reaction to form covalent bonds, so that the properties of the wood are improved. Wherein, the resin impregnation modification is an effective way for obviously improving the physical and mechanical properties of wood such as density, dimensional stability, strength and the like.
In recent years, with the strengthening of the national environment-friendly requirement on indoor and outdoor wood materials, the realization of formaldehyde-free environment-friendly modification of artificial woods becomes an urgent requirement for industry development. The water-based polyacrylate emulsion is a high molecular polymer, uses water as a dispersion medium, and is a homopolymer or a copolymer formed by acrylate or methacrylate through free radical polymerization reaction and other vinyl monomers, and has good water resistance, weather resistance and alkali resistance, and the adhesive film has good flexibility.
In the prior art, the water-based polyacrylate emulsion has large molecular weight, and is difficult to uniformly penetrate into wood and penetrate into the cell wall of the wood. Therefore, the scholars utilize the acrylic ester monomer to dip into the wood and then perform in-situ polymerization, so that the dimensional stability of the wood is improved; also, it is known to synthesize aqueous polyacrylate and then impregnate wood flour to react with hydroxyl groups on the surface of wood by transesterification to form a dense hydrophobic film. Therefore, to achieve the impregnation modification of solid wood and allow polyacrylate to enter the interior of the wood, a water-based acrylate microemulsion with small particle size and low viscosity, which is suitable for the impregnation modification of wood, needs to be developed.
Disclosure of Invention
The invention aims to provide an acrylic ester microemulsion wood modifier which can realize modification of wood.
The invention is realized in such a way that the acrylate microemulsion wood modifier comprises, by weight, 10-20 parts of soft monomers, 10-20 parts of hard monomers, 1-5 parts of emulsifiers, 0.3-1 part of initiators, 0.5-1 part of pH regulators, 0.5-2 parts of chain transfer agents, 0.5-3 parts of polymerization inhibitors, 5-10 parts of flame retardants and 100-150 parts of deionized water.
Further, the soft monomer is one or more of methyl acrylate, ethyl acrylate and butyl acrylate.
Further, the hard monomer is one or more of acrylic acid, methacrylic acid, methyl methacrylate and acrylonitrile.
Further, the emulsifier adopts a composite system of an anionic emulsifier and a nonionic emulsifier, wherein the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dialkyl-2-sulfosuccinate; the nonionic emulsifier is one or more of alkylphenol ethoxylates.
Furthermore, the initiator is water-soluble persulfate.
Further, the pH regulator is ammonia water or sodium bicarbonate.
Further, the flame retardant is one or more than two of boric acid, borax, sodium silicate, ammonium phosphate, diammonium hydrogen phosphate, monoammonium phosphate and ammonium pyrophosphate.
The invention also provides a preparation method of the acrylic ester microemulsion wood modifier, which comprises the following preparation steps:
1) Preparing two persulfate initiator solutions, and preparing the two persulfate initiator solutions into a first initiator solution with mass fractions of 1% -3% and a second initiator solution with mass fractions of 4% -6% respectively; respectively dissolving two parts of nonionic emulsifier in deionized water according to a mass ratio of 1 (2-5), sequentially marking as a first part of emulsifier solution and a second part of emulsifier solution, adding 50% -80% of soft monomer and 30% -50% of hard monomer into the first part of emulsifier solution, respectively adding the rest soft monomer and hard monomer into the second part of emulsifier solution, and respectively preparing a first part of monomer pre-emulsion and a second part of monomer pre-emulsion by reacting for 0.5-1 hour at a stirring speed of 180-240 r/min;
2) Adding all pH regulator, chain transfer agent, anionic emulsifier and quantitative deionized water into a reactor, stirring at a stirring speed of 180-250r/min, adding a first part of initiator solution when the reaction temperature reaches 55-65 ℃, slowly dropwise adding a first part of monomer pre-emulsion at the same time, after 1.5-2 hours, and continuously reacting for 0.5-1 hour to obtain seed emulsion;
3) Adding a polymerization inhibitor into the seed emulsion, dropwise adding a second part of monomer pre-emulsion and a second part of initiator solution into the seed emulsion, controlling the dropwise adding speed to be within 2 hours, then raising the temperature to 70-90 ℃, reacting for 1-3 hours, and reducing the temperature to 40-50 ℃;
4) Adding flame-retardant functional auxiliary agent into the emulsion, and stirring for 30-60 minutes to obtain the acrylic ester microemulsion wood modifier.
Further, the reactor comprises an inner sleeve device and an outer sleeve device with stirring cavities, wherein the outer sleeve device is sleeved on the periphery of the inner sleeve device, a spaced interlayer space is formed between the inner sleeve device and the outer sleeve device, electric wires are arranged in the interlayer space, and the electric wires are wound on the periphery of the inner sleeve device;
a rotating shaft which is longitudinally arranged is arranged in the stirring cavity, a plurality of stirring shafts which are transversely arranged are arranged on the rotating shaft, the stirring shafts extend along the axial direction of the rotating shaft, and adjacent stirring shafts are arranged in a staggered manner along the circumferential direction of the rotating shaft;
the rotary shaft is internally provided with an air blowing channel, the air blowing channel extends and is arranged along the axial direction of the rotary shaft, a plurality of air blowing holes are formed in the side wall of the rotary shaft, the air blowing holes are arranged at intervals along the axial direction of the rotary shaft, the top of the air blowing channel is connected with an air compressor through an air blowing pipeline, the air compressor blows high-pressure air into the air blowing channel through the air blowing pipeline, and the high-pressure air is blown out through the air blowing holes;
the rotary shaft is internally provided with an air suction channel, the air suction channel is arranged along the axial extension of the rotary shaft, the periphery of the lower part of the rotary shaft is provided with an air suction ring, the air suction ring is provided with a downward lower end face, the lower end face of the air suction ring is provided with a ring-shaped suction inlet, the suction inlet is arranged along the circumferential extension of the air suction ring, and the suction inlet is communicated with the bottom of the air suction channel; the side wall of the rotating shaft is provided with a plurality of air suction holes which are arranged at intervals along the axial direction of the rotating shaft and are respectively communicated with the air suction channels; the top of the air suction channel is connected with the negative pressure device through an air suction pipeline, the air suction pipeline is communicated with a buffer container, and the buffer container is communicated with the top of the stirring cavity of the reactor.
The invention also provides application of the acrylate microemulsion wood modifier in wood.
Compared with the prior art, the acrylate microemulsion wood modifier provided by the invention is an aldehyde-free multifunctional wood impregnation modifier, the density, the dimensional stability and the mechanical strength of the wood treated by the wood modifier are greatly improved, meanwhile, the wood treated by the wood modifier has a flame retardant effect, the problem of wood cracking is solved, and the modified wood can be applied to the aspects of indoor furniture, wood doors and windows, floors and the like.
Drawings
FIG. 1 is a schematic front view of a reactor provided by the present invention;
FIG. 2 is a schematic diagram of the structure of the connection of the stirring shaft and the moving block;
fig. 3 is an internal schematic view of the rotating shaft provided by the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The implementation of the present invention will be described in detail below with reference to specific embodiments.
The same or similar reference numerals in the drawings of the present embodiment correspond to the same or similar components; in the description of the present invention, it should be understood that, if there is an azimuth or positional relationship indicated by terms such as "upper", "lower", "left", "right", etc., based on the azimuth or positional relationship shown in the drawings, it is only for convenience of describing the present invention and simplifying the description, but it is not indicated or implied that the apparatus or element referred to must have a specific azimuth, be constructed and operated in a specific azimuth, and thus terms describing the positional relationship in the drawings are merely illustrative and should not be construed as limitations of the present patent, and specific meanings of the terms described above may be understood by those skilled in the art according to specific circumstances.
Referring to fig. 1-3, a preferred embodiment of the present invention is provided.
The acrylate microemulsion wood modifier comprises, by weight, 10-20 parts of soft monomers, 10-20 parts of hard monomers, 1-5 parts of emulsifiers, 0.3-1 part of initiators, 0.5-1 part of pH regulators, 0.5-2 parts of chain transfer agents, 0.5-3 parts of polymerization inhibitors, 5-10 parts of flame retardants and 100-150 parts of deionized water.
The acrylate microemulsion wood modifier is an aldehyde-free multifunctional wood impregnation modifier, the density, the dimensional stability and the mechanical strength of the wood treated by the wood modifier are greatly improved, meanwhile, the wood treated by the wood modifier has a flame retardant effect, the problem of wood cracking is solved, and the modified wood can be applied to indoor furniture, wood doors and windows, floors and the like.
The soft monomer is one or more of methyl acrylate, ethyl acrylate and butyl acrylate.
The hard monomer is one or more of acrylic acid, methacrylic acid, methyl methacrylate and acrylonitrile.
The emulsifier adopts a composite system of an anionic emulsifier and a nonionic emulsifier, and the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dialkyl-2-sulfosuccinate; the nonionic emulsifier is one or more of alkylphenol ethoxylates (OP, NP and TX).
The initiator is water-soluble persulfate. The pH regulator is ammonia water or sodium bicarbonate. The flame retardant is one or more of boric acid, borax, sodium silicate, ammonium phosphate, diammonium phosphate, monoammonium phosphate and ammonium pyrophosphate.
The embodiment also provides a preparation method of the acrylic ester microemulsion wood modifier, which comprises the following preparation steps:
1) Preparing two persulfate initiator solutions, and preparing the two persulfate initiator solutions into initiator solutions with mass fractions of 1% -4% and 2% -6% respectively; dissolving two parts of nonionic emulsifier in quantitative deionized water according to the proportion of 1 (2-5), sequentially marking as a first part of emulsifier solution and a second part of emulsifier solution, adding 50% -80% of soft monomer and 30% -50% of hard monomer into the first part of emulsifier solution, respectively adding the rest soft monomer and hard monomer into the second part of emulsifier solution, and preparing two parts of monomer pre-emulsion by reacting for 0.5-1 hour at the stirring speed of 180-240 r/min;
2) Adding all pH regulator, chain transfer agent, anionic emulsifier and quantitative deionized water into a reactor, stirring at a stirring speed of 180-250r/min, adding a first part of initiator solution according to mass fraction when the reaction temperature reaches 55-65 ℃, slowly dropwise adding a first part of monomer pre-emulsion at the same time, after 1.5-2 hours, continuously reacting for 0.5-1 hour to obtain seed emulsion;
3) Adding a polymerization inhibitor into the seed emulsion, dropwise adding a second part of monomer pre-emulsion and a second part of initiator solution into the seed emulsion, controlling the dropwise adding speed to be within 2 hours, then raising the temperature to 70-90 ℃, reacting for 1-3 hours, and reducing the temperature to 40-50 ℃;
4) Adding flame-retardant functional auxiliary agent into the emulsion, and stirring for 30-60 minutes to obtain the acrylic ester microemulsion wood modifier.
In this embodiment, the reactor includes an inner liner 102 and an outer liner 100 sleeved outside the inner liner 102, a space interlayer space 101 is formed between the inner liner 102 and the outer liner 100, a stirring cavity 103 is provided in the inner liner 102, and an electric wire is provided in the interlayer space 101 and wound around the outer circumference of the inner liner 102, so that the inner liner 102 can be heated by energizing the electric wire.
The stirring cavity 103 of the inner sleeve device 102 is internally provided with a rotating shaft 400 which is longitudinally arranged, the rotating shaft 400 is provided with a plurality of stirring shafts 300 which are transversely arranged, the stirring shafts 300 are arranged along the axial direction of the rotating shaft 400 in an extending mode, and the adjacent stirring shafts 300 are arranged in a staggered mode along the circumferential direction of the rotating shaft 400, so that when substances in the reactor are required to be stirred, the rotating shaft 400 rotates to drive the stirring shafts 300 to axially rotate, and the stirring effect is achieved.
In this embodiment, the air blowing channel 600 is disposed in the rotating shaft 400, the air blowing channel 600 extends along the axial direction of the rotating shaft 400, a plurality of air blowing holes 601 are formed in the side wall of the rotating shaft 400, and the plurality of air blowing holes 601 are disposed at intervals along the axial direction of the rotating shaft 400, so that the top of the air blowing channel 600 is connected with the air compressor through the air blowing pipeline, the air compressor blows high-pressure air into the air blowing channel 600 through the air blowing pipeline, blows the high-pressure air along the air blowing channel 600, blows the high-pressure air out through the air blowing holes 601, can play a role of gas stirring with substances in the stirring cavity 103, and cooperates with the stirring role of the stirring shaft 300 to realize double-layer stirring.
The plurality of air blowing holes 601 are arranged in a spiral shape along the axial direction of the rotation shaft 400, so that when the rotation shaft 400 rotates, a wider range of air blowing of the air blowing holes 601 toward the outer circumference can be achieved.
In the present embodiment, the air intake duct 500 is provided in the rotation shaft 400, the air intake duct 500 is arranged to extend in the axial direction of the rotation shaft 400, the air intake ring 401 is provided on the outer periphery of the lower portion of the rotation shaft 400, the air intake ring 401 has a downward lower end surface, the ring-shaped air intake port 402 is provided on the lower end surface of the air intake ring 401, the air intake port 402 is arranged to extend in the circumferential direction of the air intake ring 401, and the air intake port 402 communicates with the bottom of the air intake duct 500.
In the side wall of the rotation shaft 400, a plurality of suction holes 501 are formed, and the plurality of suction holes 501 are arranged at intervals along the axial direction of the rotation shaft 400 and communicate with the suction passages 500, respectively. The top of the air suction channel 500 is connected with the negative pressure device through an air suction pipeline, the air suction pipeline is communicated with a buffer container, and the buffer container is communicated with the top of the stirring cavity 103 of the reactor.
In this way, in the process of stirring the substances, the stirring shaft 300 has the function of sucking and stirring the substances in the stirring cavity 103 through the suction pipeline by the negative pressure device, and part of the substances sucked into the buffer container are returned to the stirrer for stirring, so that the stirring uniformity is ensured.
The above-mentioned reactor that provides, it not only plays the rotation stirring through the rotation of (mixing) shaft 300 to the material in the stirring chamber 103 to, through the cooperation of blowing air flue 600 and suction air flue 500, play the effect of gaseous mixing stirring to the material in the stirring chamber 103, avoid waiting to stir the material caking, and can break up big granule, the stirring is more even.
The plurality of air suction holes 501 are arranged in a spiral along the axial direction of the rotation shaft 400, and the spiral direction of the plurality of air suction holes 501 is opposite to the spiral direction of the plurality of air blowing holes 601.
The inner end of the stirring shaft 300 is connected to the rotating shaft 400, the outer end of the stirring shaft 300 extends outwards and transversely, in this embodiment, a rail groove 301 extending transversely is provided on the stirring shaft 300, a moving block 303 is provided on the stirring shaft 300, a bump 303 is provided on the lower portion of the moving block 303, the bump 303 is movably embedded in the rail groove 301, and the moving block 303 can move along the rail groove 301 of the stirring shaft 300.
The rail groove 301 is provided with two springs 302, the two springs 302 are respectively arranged at two sides of the protruding block 303, one end of each spring 302 is fixedly connected with the end of the rail groove 301, and the other end of each spring 302 is fixedly connected with the protruding block 303, so that when the stress of the two springs 302 is inconsistent, the moving block 303 can move on the rail groove 301 until the stress at two sides of the moving block 303 is balanced.
In practice, when the stirring shaft 300 rotates to stir, the moving block 303 can move back and forth along the rail groove 301 of the stirring shaft 300 along with the change of the stirring speed, so that the same rotation phenomenon of the liquid rotation can be destroyed, and more uniform stirring of the stirring shaft 300 can be realized.
The embodiment also provides application of the prepared acrylic ester microemulsion wood modifier in wood, wherein the wood can be poplar, fir, pine, eucalyptus, rubber wood and the like, and the specific application steps are as follows:
1) The acrylic ester microemulsion wood modifier is prepared into a wood modifier with 5-15% of solid content;
2) Firstly, drying wood, and controlling the water content to be 8-10%; carrying out wood modification treatment in a vacuum pressurizing impregnation mode, putting the wood into an impregnation tank, vacuumizing the impregnation tank to-0.1 MPa, and keeping the impregnation tank for 0.5-1 hour; under the condition of maintaining vacuum, introducing wood modifier into the impregnating tank until the wood is completely immersed in the wood modifying agent, pressurizing for 1.0-1.5MPa, holding for 4-6 hr, discharging impregnating solution, and taking out the wood.
3) And drying the modified wood taken out of the impregnation tank at the temperature of 60-100 ℃ until the water content of the modified wood is 8-12%, thereby finishing the modification of the wood.
Three specific examples are provided below
Example 1
The raw materials for preparing the acrylic ester microemulsion wood modifier comprise: methyl acrylate, ethyl acrylate, methyl methacrylate, acrylonitrile, sodium dodecyl sulfate, NP-10, ammonium persulfate, ammonia water, sodium bicarbonate, hydroquinone, n-dodecyl mercaptan, deionized water, boric acid, and borax.
The preparation process of the acrylate microemulsion wood modifier comprises the following steps:
preparing 3% and 5% of initiator solution by mass of ammonium persulfate respectively; 1g of NP-10 is firstly dissolved in 75g of deionized water, then 20g of methyl acrylate, 10g of ethyl acrylate, 15g of methyl methacrylate and 5g of acrylonitrile are added, and the first monomer pre-emulsion is prepared by reacting for 30min at the stirring speed of 180 r/min; then, the remaining 2g NP-10 was dissolved in 85g of deionized water, 10g of methyl acrylate, 10g of ethyl acrylate, 15g of methyl methacrylate and 10g of acrylonitrile were added, and the reaction was carried out at a stirring speed of 180r/min for 30 minutes to prepare a second monomer pre-emulsion.
1.5g of sodium bicarbonate, 4.0g of n-dodecyl mercaptan, 3.0g of sodium dodecyl sulfate and 300g of deionized water are added into a reactor, stirring is carried out at a stirring speed of 200r/min, when the reaction temperature reaches 55 ℃, 3% of initiator solution by mass fraction is added, meanwhile, a first part of monomer pre-emulsion is slowly added dropwise, after 1.5 hours of dropwise addition, the reaction is continued for 0.5 hour, and a seed emulsion is obtained.
5.0g of hydroquinone is added into the seed emulsion, simultaneously, a second part of monomer pre-emulsion and an initiator solution with the mass fraction of 5% are added dropwise, the dripping speed is controlled to be within 2 hours, the temperature is increased to 80 ℃ and the reaction is carried out for 2 hours, the temperature is reduced to 45 ℃, 15g of boric acid and borax are added, and the mixture is stirred for 30 minutes, so that the acrylic ester microemulsion wood modifier with the solid content of 15.3% is obtained.
The operations of impregnating and modifying the wood in the acrylate microemulsion wood modifier are as follows:
placing poplar with water content of 10% in an impregnation tank, vacuumizing to-0.1 MPa, and keeping for 0.5 hours; under the condition of maintaining vacuum, introducing an acrylic ester micro-solution modifier with the solid content of 8%, fully immersing the wood in the acrylic ester micro-solution modifier, pressurizing for 1.2MPa, maintaining for 4 hours, discharging the impregnating solution after the completion, taking out the wood, and air-drying for 5 days. Then, step drying was performed at 60 ℃, 80 ℃ and 100 ℃ to a moisture content of 10% of the modified wood.
Example 2
The raw materials for preparing the acrylic ester microemulsion wood modifier comprise: methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid, sodium dodecyl sulfate, OP-10, ammonium persulfate, ammonia water, sodium bicarbonate, hydroquinone, n-dodecyl mercaptan, deionized water, boric acid and borax.
The preparation process of the acrylate microemulsion wood modifier comprises the following steps:
preparing initiator solutions with mass fractions of 2% and 4% respectively from ammonium persulfate; 1.5g OP-10 is firstly taken and dissolved in 60g deionized water, then 20g methyl acrylate, 12g ethyl acrylate, 15g methyl methacrylate and 10g acrylic acid are added, and the first monomer pre-emulsion is prepared by the reaction for 30min at the stirring speed of 180 r/min; then, the remaining 3g OP-10 was dissolved in 85g deionized water, 10g methyl acrylate, 13g ethyl acrylate, 15g methyl methacrylate and 10g acrylic acid were added, and the reaction was carried out for 30 minutes at a stirring speed of 180r/min to prepare a second monomer pre-emulsion.
2g of sodium bicarbonate, 4.5g of n-dodecyl mercaptan, 4.0g of sodium dodecyl sulfate and 200g of deionized water are added into a reactor, stirring is carried out at a stirring speed of 250r/min, when the reaction temperature reaches 55 ℃, 2% of initiator solution by mass fraction is added, meanwhile, a first part of monomer pre-emulsion is slowly added dropwise, after 1.5 hours of dropwise addition, the reaction is continued for 1 hour, and a seed emulsion is obtained.
6.0g of hydroquinone is added into the seed emulsion, simultaneously, a second part of monomer pre-emulsion and an initiator solution with the mass fraction of 4% are added dropwise, the dripping speed is controlled to be over 2 hours, and then the temperature is raised to 80 ℃ for reaction for 3 hours. Then cooling to 45 ℃, adding 20g of boric acid and borax, and stirring for 30 minutes to obtain the acrylic ester microemulsion wood modifier with the solid content of 21.5 percent.
The operations of impregnating and modifying the wood in the acrylate microemulsion wood modifier are as follows:
placing poplar with water content of 10% in an impregnation tank, vacuumizing to-0.1 MPa, and keeping for 0.5 hours; under the vacuum condition, introducing an acrylic ester micro-solution modifier with the solid content of 10 percent, immersing the wood into the modifying agent, pressurizing for 1.2MPa, keeping for 4 hours, discharging the impregnating solution after the completion, taking out the wood, and air-drying for 5 days. Then, step drying was performed at 60 ℃, 80 ℃ and 100 ℃ to a moisture content of 10% of the modified wood.
Example 3
The raw materials for preparing the acrylic ester microemulsion wood modifier comprise: methyl acrylate, butyl acrylate, methyl methacrylate, acrylic acid, sodium dodecyl sulfate, NP-10, potassium persulfate, sodium bicarbonate, hydroquinone, n-dodecyl mercaptan, deionized water, and sodium silicate.
The preparation process of the acrylate microemulsion wood modifier comprises the following steps:
preparing 3% and 4% of initiator solution by mass of ammonium persulfate respectively; 1g of NP-10 is firstly dissolved in 40g of deionized water, then 20g of methyl acrylate, 15g of butyl acrylate, 15g of methyl methacrylate and 10g of acrylic acid are added, and the first monomer pre-emulsion is prepared by reacting for 30min at the stirring speed of 180 r/min; then, the remaining 3g of NP-10 was dissolved in 50g of deionized water, 10g of methyl acrylate, 15g of butyl acrylate, 15g of methyl methacrylate and 10g of acrylic acid were added, and the reaction was carried out for 30 minutes at a stirring speed of 180r/min to prepare a second monomer pre-emulsion.
2g of sodium bicarbonate, 4.5g of n-dodecyl mercaptan, 4.0g of sodium dodecyl sulfate and 90g of deionized water are added into a reactor, stirring is carried out at a stirring speed of 250r/min, when the reaction temperature reaches 60 ℃, 3% of initiator solution by mass fraction is added, meanwhile, a first part of monomer pre-emulsion is slowly added dropwise, after 1.5 hours of dropwise addition, the reaction is continued for 1 hour, and a seed emulsion is obtained.
6.0g of hydroquinone is added into the seed emulsion, simultaneously, a second part of monomer pre-emulsion and an initiator solution with the mass fraction of 4% are added dropwise, the dripping speed is controlled to be over 2 hours, and then the temperature is raised to 80 ℃ for reaction for 3 hours. Then cooling to 45 ℃, adding 25g of sodium silicate, and stirring for 45 minutes to obtain the acrylic ester microemulsion wood modifier with the solid content of 32.4%.
The operations of impregnating and modifying the wood in the acrylate microemulsion wood modifier are as follows:
placing poplar with water content of 10% in an impregnation tank, vacuumizing to-0.1 MPa, and keeping for 0.5 hours; under the vacuum condition, introducing an acrylic ester micro-solution modifier with the solid content of 15 percent, immersing the wood into the modifying agent, pressurizing for 1.2MPa, keeping for 4 hours, discharging the impregnating solution after the completion, taking out the wood, and air-drying for 5 days. Then, step drying was performed at 60 ℃, 80 ℃ and 100 ℃ to a moisture content of 10% of the modified wood.
Comparative example 1
The following performance test comparisons were made for examples 1, 2, 3, the wood to be modified being poplar.
First, the performance of the acrylate microemulsion wood modifier was tested as follows:
the acrylic acid ester microemulsion wood modifiers of examples 1-3 were tested for five aspects of appearance, solids content, viscosity, storage stability, and water miscibility, and the results are shown in Table 1.
The method for measuring the solid content comprises the following steps: and (3) taking 1-1.5g of each acrylic ester microemulsion wood modifier in examples 1-3 respectively, putting into a baking oven at 102 ℃ to bake to constant weight, and calculating the mass percent of the rest part accounting for the total amount after baking to obtain the solid content.
The viscosity was measured using a paint-4 cup.
The average particle size was measured using a DelsaNano C-type laser particle sizer.
TABLE 1 results of Performance test of acrylate microemulsion Wood modifier
The detection results show that the examples 1-3 are all bluish light slightly yellowish semitransparent emulsion, the main distribution range of the particle size is 50-100nm, the viscosity value is 8-11s, the storage stability is good, and the emulsion can be mutually dissolved with water in any proportion.
The physical and mechanical properties of the modified wood are determined as follows:
the modified materials of examples 1 to 3 and the comparative materials were tested for dimensional stability, absolute density, flexural strength (MOR) and modulus of elasticity (MOE) with reference to national standards GB/T1934.2-2009, "method for determination of wet expansion of Wood", GB/T1933-2009, "method for determination of Density of Wood", GB/T1936.1-2009, "method for experiment of flexural Strength of Wood", and GB/T1936.2-2009 "method for determination of flexural modulus of elasticity of Wood", and part 2 of combustion behavior was determined with reference to GB/T2406.2-2009 "oxygen index method for plastics: the oxygen index was measured in room temperature test, and the results are shown in Table 2.
The results show that the modified materials of examples 1-3 have improved absolute dry density, dimensional stability, flexural strength (MOR) and modulus of elasticity (MOE) compared with the material of comparative example 1, indicating that the acrylate microemulsion modifier can enter wood, has physical filling and bonding effects with chemical components of the wood, and the dimensional stability and mechanical properties of the wood are improved significantly after the resin is cured, and has flame retardant properties.
TABLE 2 physical and mechanical Properties of modified Material and Sucun
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. The preparation method of the acrylic ester microemulsion wood modifier is characterized by comprising, by weight, 10-20 parts of soft monomer, 10-20 parts of monomer A, 1-5 parts of emulsifier, 0.3-1 part of initiator, 0.5-1 part of pH regulator, 0.5-2 parts of chain transfer agent, 0.5-3 parts of polymerization inhibitor, 5-10 parts of flame retardant and 100-150 parts of deionized water; the soft monomer is one or more of methyl acrylate, ethyl acrylate and butyl acrylate; the monomer A is acrylic acid and methyl methacrylate or methyl methacrylate and acrylonitrile; the emulsifier adopts an anionic emulsifier and nonionic emulsifier composite system; the initiator is water-soluble persulfate; the flame retardant is one or the combination of more than two of boric acid, borax, sodium silicate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium pyrophosphate; the emulsion particle size of the acrylic ester microemulsion wood modifier is mainly distributed in the range of 50-100 nm;
the preparation method comprises the following preparation steps:
1) Preparing two persulfate initiator solutions, namely preparing a first initiator solution with mass fractions of 1% -3% and a second initiator solution with mass fractions of 4% -6% respectively from the two persulfate initiator solutions; respectively dissolving two parts of nonionic emulsifier in deionized water according to a mass ratio of 1 (2-5), sequentially marking as a first part of emulsifier solution and a second part of emulsifier solution, adding 50% -80% of soft monomer and 30% -50% of monomer A into the first part of emulsifier solution, respectively adding the rest soft monomer and monomer A into the second part of emulsifier solution, and respectively preparing a first part of monomer pre-emulsion and a second part of monomer pre-emulsion at a stirring speed of 180-240r/min and a reaction time of 0.5-1 hour;
2) Adding all pH regulator, chain transfer agent, anionic emulsifier and quantitative deionized water into a reactor, stirring at a stirring speed of 180-250r/min, adding a first part of initiator solution when the reaction temperature reaches 55-65 ℃, slowly dropwise adding a first part of monomer pre-emulsion at the same time, after 1.5-2 hours, and continuously reacting for 0.5-1 hour to obtain seed emulsion;
3) Adding a polymerization inhibitor into the seed emulsion, dropwise adding a second part of monomer pre-emulsion and a second part of initiator solution into the seed emulsion, controlling the dropwise adding speed to be within 2 hours, then raising the temperature to 70-90 ℃, reacting for 1-3 hours, and reducing the temperature to 40-50 ℃;
4) Adding a flame retardant into the emulsion, and stirring for 30-60 minutes to obtain the acrylic ester microemulsion wood modifier.
2. The method for preparing the acrylic ester microemulsion wood modifier according to claim 1, wherein the anionic emulsifier is one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dialkyl-2-sulfosuccinate; the nonionic emulsifier is one or more of alkylphenol ethoxylates.
3. The method for preparing an acrylic acid ester microemulsion wood modifier according to claim 1, wherein said pH regulator is ammonia water or sodium bicarbonate.
4. A method of preparing an acrylic acid ester microemulsion wood modifier according to any one of claims 1 to 3, wherein said reactor comprises an inner sleeve having a stirring chamber and an outer sleeve, said outer sleeve being fitted around the outer periphery of said inner sleeve, a space being formed between said inner sleeve and said outer sleeve, said space being provided with an electric wire, said electric wire being wound around the outer periphery of said inner sleeve;
a rotating shaft which is longitudinally arranged is arranged in the stirring cavity, a plurality of stirring shafts which are transversely arranged are arranged on the rotating shaft, the stirring shafts extend along the axial direction of the rotating shaft, and adjacent stirring shafts are arranged in a staggered manner along the circumferential direction of the rotating shaft;
the rotary shaft is internally provided with an air blowing channel, the air blowing channel extends and is arranged along the axial direction of the rotary shaft, a plurality of air blowing holes are formed in the side wall of the rotary shaft, the air blowing holes are arranged at intervals along the axial direction of the rotary shaft, the top of the air blowing channel is connected with an air compressor through an air blowing pipeline, the air compressor blows high-pressure air into the air blowing channel through the air blowing pipeline, and the high-pressure air is blown out through the air blowing holes;
the rotary shaft is internally provided with an air suction channel, the air suction channel is arranged along the axial extension of the rotary shaft, the periphery of the lower part of the rotary shaft is provided with an air suction ring, the air suction ring is provided with a downward lower end face, the lower end face of the air suction ring is provided with a ring-shaped suction inlet, the suction inlet is arranged along the circumferential extension of the air suction ring, and the suction inlet is communicated with the bottom of the air suction channel; the side wall of the rotating shaft is provided with a plurality of air suction holes which are arranged at intervals along the axial direction of the rotating shaft and are respectively communicated with the air suction channels; the top of the air suction channel is connected with the negative pressure device through an air suction pipeline, the air suction pipeline is communicated with a buffer container, and the buffer container is communicated with the top of the stirring cavity of the reactor.
5. Use of an acrylate microemulsion wood modifier prepared by the preparation method based on any one of claims 1-4 in wood impregnation modification.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002018812A (en) * | 2000-07-02 | 2002-01-22 | Misao Kadoi | Timber modifying agent and method for manufacturing modified timber using the same |
| CN1644334A (en) * | 2005-02-07 | 2005-07-27 | 陈万利 | Wooden modifying composition, production and use thereof |
| CN1764696A (en) * | 2003-06-05 | 2006-04-26 | 氦克逊特种化学品公司 | Emulsions for lignocellulosic products, methods of their manufacture, improved lignocellulosic products and methods for their manufacture |
| RU2007122234A (en) * | 2007-06-13 | 2008-12-20 | Государственное образовательное учреждение Высшего профессионального образования "Тамбовский государственный технический университет" (ГОУ ВПО "ТГТУ") (RU) | Emucril Modified Wood (M or C) |
| CN103963124A (en) * | 2014-04-21 | 2014-08-06 | 北京林业大学 | Paraffin emulsion-borate compound modifier, as well as preparation method and application thereof |
| CN107599093A (en) * | 2017-08-31 | 2018-01-19 | 宜华生活科技股份有限公司 | A kind of water ballast functional form Wood modifier and its processing method |
| CN110655620A (en) * | 2019-09-20 | 2020-01-07 | 中国林业科学研究院木材工业研究所 | Aqueous hyperbranched polyacrylate emulsion, preparation method and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2427867A (en) * | 2005-07-01 | 2007-01-10 | Mohsen Zakikhani | Flame retardant polymer emulsion |
| CN107033271B (en) * | 2016-02-03 | 2019-11-12 | 山东坤瀚新材料科技有限公司 | A kind of woodcare paint environmental-protection flame-retardant lotion and preparation method thereof |
| CN106040041A (en) * | 2016-06-23 | 2016-10-26 | 徐州工程学院 | Horizontal powder material mixing machine with spraying and blowing device and work method thereof |
| CN106811052A (en) * | 2017-01-18 | 2017-06-09 | 广东达志环保科技股份有限公司 | A kind of color inhibition Waterborne Polyurethane Emulsion with Multiple Modification and preparation method thereof |
| CN206566829U (en) * | 2017-02-22 | 2017-10-20 | 南京金帅环保建筑材料有限公司 | A kind of coating agitator |
| CN107379167A (en) * | 2017-07-28 | 2017-11-24 | 阜南县中信柳木工艺品有限公司 | A kind of processing method for preventing bamboo product from ftractureing |
| CN108995064A (en) * | 2018-07-26 | 2018-12-14 | 陈洪滔 | A kind of flame retardant plastics process equipment |
| CN209304795U (en) * | 2018-11-14 | 2019-08-27 | 东莞市润大胶粘科技有限公司 | A kind of Particle mixer |
| CN111607309B (en) * | 2020-06-05 | 2021-11-30 | 福建南烽防火科技有限公司 | Acrylic acid expansion type fireproof coating material |
-
2021
- 2021-12-17 CN CN202111556778.7A patent/CN114213573B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002018812A (en) * | 2000-07-02 | 2002-01-22 | Misao Kadoi | Timber modifying agent and method for manufacturing modified timber using the same |
| CN1764696A (en) * | 2003-06-05 | 2006-04-26 | 氦克逊特种化学品公司 | Emulsions for lignocellulosic products, methods of their manufacture, improved lignocellulosic products and methods for their manufacture |
| CN1644334A (en) * | 2005-02-07 | 2005-07-27 | 陈万利 | Wooden modifying composition, production and use thereof |
| RU2007122234A (en) * | 2007-06-13 | 2008-12-20 | Государственное образовательное учреждение Высшего профессионального образования "Тамбовский государственный технический университет" (ГОУ ВПО "ТГТУ") (RU) | Emucril Modified Wood (M or C) |
| CN103963124A (en) * | 2014-04-21 | 2014-08-06 | 北京林业大学 | Paraffin emulsion-borate compound modifier, as well as preparation method and application thereof |
| CN107599093A (en) * | 2017-08-31 | 2018-01-19 | 宜华生活科技股份有限公司 | A kind of water ballast functional form Wood modifier and its processing method |
| CN110655620A (en) * | 2019-09-20 | 2020-01-07 | 中国林业科学研究院木材工业研究所 | Aqueous hyperbranched polyacrylate emulsion, preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| MECHANICAL PROPERTIES OF WOOD MODIFIED BY MONTMORILLONITE/POLY(ETHYL GLYCOL)/HYPERBRANCHED POLYACRYLATE EMULSION;LIU RU ET AL.;JOURNAL OF BEIJING FORESTRY UNIVERSITY;第42卷(第12期);135-141 * |
| 有机 /无机复合浸渍液对杨木的改性处理;谭惠芬等;木材工业;第23卷(第4期);40-42 * |
| 有机/无机复合浸渍液对杨木的改性处理;谭惠芬;郭红霞;杜万里;王群;;木材工业(第04期);19-21 * |
| 树脂型硅酸盐改性剂及改性材的制备工艺与性能分析;王飞;柴宇博;刘君良;;木材加工机械(第04期);33-36 * |
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