CN106625947A - Composite modifying agent added with oxide graphene modified emulsion for fast growing wood - Google Patents

Abstract

The invention discloses a composite modifying agent added with oxide graphene modified emulsion for fast growing wood. The composite modifying agent is prepared by the following raw materials in parts by weight: 3-3.5 of formaldehyde, 2-3 of urea, 1.5-2 of hexamine, 0.02-0.03 of maleic anhydride, a proper amount of acetic acid, a proper amount of ammonia water, a proper amount of de-ionized water, 20-23 of dihydroxymethyl dihydroxyl ethylene urea with the solid content of 42 wt%, 1.5-2 of hexahydrate magnesium chloride, 10-11 of silicon sol, 3-4 of oxide graphene, 7-8 of methyl methacrylate, 3-4 of butyl acrylate, 0.8-1 of nonyl phenol polyvinyl oxide ether, 1.5-2 of gioia sodium phosphate, and 0.1-0.12 of potassium persulfate. The wood modified by the composite modifying agent is high in hardness and strength and excellent in wear resistance, meanwhile, reduces the water absorption, can stop external water from entering the wood to cause corrosion, is more suitable for producing outdoor furniture and devices, reduces the production cost, and meanwhile, widens the application range of the fast growing wood.

Description

A kind of composite modifier of the addition graphene oxide modified emulsion for fast growing wood

Technical field

The present invention relates to Wood Property Improvement field, more particularly to a kind of addition graphene oxide for fast growing wood changes The composite modifier of property emulsion.

Background technology

Timber and wood materials as social and economic construction in the important means of production, be not only widely used in daily life In every field, be also widely used for traffic, building and the industrial circle such as space flight.As the forest reserves are increasingly in world wide Shortage, particularly precious timber quantity increasingly falls sharply, and in recent years the substantial amounts of quick growing species of trees is widely cultivated and meets in global range Wood supply.Compared with natural forest, by growth year is short etc., factor is limited the quick growing species of trees, causes early late wood's difference very Greatly, material is loose, and mechanical property is poor, so not being difficult to be used in the economic height such as Furniture manufacture by processing artificial fast-growing forest timber Added value field.Because timber is a kind of natural with porous macromolecular material, by the little, shapes of different fire and different company The tubular units of understanding and considerate condition are cross-linked and form, and with fluid-pervious, its distinctive vesicular texture is carried for Wooden modifying Basis is supplied.Physically or chemically modification is carried out to fast-growing forest, the economic value added of fast-growing forest is not only increased, also Serve the effect of protection rare tree resource.Wooden modifying is referred to using methods such as physics, chemistry and machineries to logs of wood Manufacturability process is carried out, makes physico-mechanical propertieses such as density of wood, hardness, intensity and dimensional stability etc. obtain good changing It is kind.Chemical modification is the modified Main Means of fast-growing forest, the selection of the chemical impregnation liquid wherein in modifying process and dipping The drying process of material is the research emphasis of Chinese scholars.But the increasing of the raising and environmental consciousness with living standards of the people By force, to human health angle, the residual for how reducing chemical impregnation liquid in modified material is chemical modification fast-growing forest Urgent problem, therefore how to be towards environmental protection and functionalization by fast-growing forest functionalization improvement Study on Integration The modified new direction of this paper and from now on fast-growing forest.

《Composite modifier is to quick growth poplar wood and Chinese toon wood Modification effect and study mechanism》By independently synthesizing low point in one text The modified nitrogen footpath methyl performed polymer of son is combined with hydroxymethyl-2 dihydroxy-ethylene urea, and by adding plurality of stable agent many work(are made Energy type chemical modifier, has carried out Primary Study, by impregnation drying to the timber physicochemical property and mechanism of modification after before modified Substantially, heat endurance is improved the main mechanical strength improving effect of the modified material after process, while modifying agent is impregnated into wood During material inside, self-condensation can occur and act on forming tridimensional network, it is higher that modifying agent serves as intensity in wood internal Filler, it is especially more obvious to dimensional stability and mechanical property improvement result.Although modified fast growing wood is in mechanics Increase in performance, but because it has not enough significantly affected fast growing wood furniture, open air out of doors to absorptive reduction The application of wooden clothing arts, needs further to be modified its composite modifier, it is also desirable to can have other additional properties To meet the demand to fast growing wood such as outdoor furniture.

The content of the invention

The object of the invention is exactly to make up the defect of prior art, there is provided a kind of addition for fast growing wood aoxidizes stone The composite modifier of black alkene modified emulsion.

The present invention is achieved by the following technical solutions：

A kind of composite modifier of the addition graphene oxide modified emulsion for fast growing wood, by the raw material system of following weight portion Prepare into：Formaldehyde 3-3.5, urea 2-3, hexa 1.5-2, maleic anhydride 0.02-0.03, appropriate acetic acid, ammoniacal liquor are fitted Amount, appropriate deionized water, solid content are hydroxymethyl-2 dihydroxy-ethylene urea 20-23, Magnesium dichloride hexahydrate 1.5-2, the silicon of 42wt% Poly- ten oxyethylene group of colloidal sol 10-11, graphene oxide 3-4, methyl methacrylate 7-8, butyl acrylate 3-4, nonyl phenol Ether 0.8-1, pyrophosphorous acid sodium 1.5-2, potassium peroxydisulfate 0.1-0.12.

The composite modifier of a kind of addition graphene oxide modified emulsion for fast growing wood, by walking in detail below Suddenly make：

（1）Formaldehyde, urea, hexa are put into reactor, maleic anhydride is added, are heated to while stirring completely molten Solution, the deionized water for adding total amount 1.5-2 times to measure, is heated to 70-80 DEG C, is adjusted with acetic acid and ammoniacal liquor after stirring reaction 3-4 hour Section pH value is 7, terminates reaction；

（2）The poly- ten oxyethylene groups ether of nonyl phenol is dissolved in the 30-40 times of deionized water measured, heating water bath to 40-50 DEG C, Pyrophosphorous acid sodium is continuously added, is stirred to after being completely dissolved and is added the methyl methacrylate of half amount to mix with butyl acrylate Thing, to be warming up to 70-80 DEG C after 600-800 turn/part speed stirring 20-30 minutes, is slowly added dropwise potassium peroxydisulfate, adds remainder Methyl methacrylate and butyl acrylate mixture, insulated and stirred reaction 90-120 minutes it is stand-by；By graphene oxide plus In entering the 2-3 times of deionized water measured, ultrasonic disperse 30-40 minutes form and add after suspension in above-mentioned reaction system, with 800- 1000 revs/min of speed stirring 20-30 minutes, obtain complex emulsions；

（3）Hydroxymethyl-2 dihydroxy-ethylene urea of the solid content for 42wt% is mixed with Ludox, with 500-600 rev/min of speed Step is added after stirring 10-15 minutes（1）Step（2）The product for obtaining and remaining residual components, continue ultrasonic disperse 15-20 Minute, obtain final product.

It is an advantage of the invention that：Formaldehyde, urea, hexa are carried out reaction life by the present invention by certain technique Into performed polymer, then by being compounded with hydroxymethyl-2 dihydroxy-ethylene urea, Ludox, magnesium chloride, can after ultrasonically treated To form colloidal sol type composite modifier, wherein Si-0-Si skeleton structures play stabilization to modifier system, by timber Impregnation process is carried out, timber pickling degree of modification can be significantly improved, improve the rate of body weight gain of timber；Composite modifier can be in wood The cell membrane microcellular structure of timber is scattered in material dipping process well, with Wood chemical composition in subsequent heat drying In cellulose, hemicellulose, lignin etc. there is situ-gel polymerisation, chemical reaction finally makes the sense between them Group can connect to form covalent bond, and covalent bond is very firm, thus the bending strength of modified fast growing wood, Deflection Modulus of Elasticity and Parallel-to-grain compressive strength all improves a lot；Simultaneously composite modifier can with the main chemical compositions cellulose of timber, half There is etherification reaction in cellulose and lignin, such reaction can reduce hydrophilic hydroxy group in timber, so as to significantly reduce wood Material hygroscopicity.

The present invention is prepared for polyacrylate dispersion by blending, and then adding graphene oxide carries out compounding and answered Emulsion is closed, coordinates the addition of the compositions such as Ludox, make product of the present invention, modifying agent uniform quality of the present invention, stable in properties, appearance Easily storage, for the modified of fast growing wood, can equably penetrate into wood internal and dispersion by dipping slurry active ingredient In wood surface, improve that fast growing wood compression strength is low, easy abrasion shortcoming so that modified timber has high hard Degree, high intensity, splendid wearability, while water absorption rate is reduced, can stop the corruption that outside moisture carries out wood internal and causes Lose, be especially suitable for, with this timber manufacture outdoor furniture, equipment, production cost being reduced, while having widened the use of fast growing wood Scope.

Specific embodiment

A kind of composite modifier of the addition graphene oxide modified emulsion for fast growing wood, by following weight portion（It is public Jin）Raw material make：Formaldehyde 3, urea 2, hexa 1.5, maleic anhydride 0.02, appropriate acetic acid, appropriate ammoniacal liquor, Appropriate deionized water, solid content are the hydroxymethyl-2 dihydroxy-ethylene urea 20 of 42wt%, Magnesium dichloride hexahydrate 1.5, Ludox 10, The poly- ten oxyethylene groups ether 0.8 of graphene oxide 3, methyl methacrylate 7, butyl acrylate 3, nonyl phenol, pyrophosphorous acid sodium 1.5th, potassium peroxydisulfate 0.1.

The composite modifier of a kind of addition graphene oxide modified emulsion for fast growing wood, by walking in detail below Suddenly make：

（1）Formaldehyde, urea, hexa are put into reactor, maleic anhydride is added, are heated to while stirring completely molten Solution, adds the deionized water of 1.5 times of amounts of total amount, is heated to 70 DEG C, and stirring reaction adjusts pH value and is after 3 hours with acetic acid and ammoniacal liquor 7, terminate reaction；

（2）The poly- ten oxyethylene groups ether of nonyl phenol is dissolved in the deionized water of 30 times of amounts, heating water bath continues to add to 40 DEG C Enter pyrophosphorous acid sodium, stir to after being completely dissolved and add the methyl methacrylate and butyl acrylate mixture of half amount, with 600 turn/part speed are warming up to 70 DEG C after stirring 20 minutes, are slowly added dropwise potassium peroxydisulfate, add remaining methyl methacrylate Ester and butyl acrylate mixture, insulated and stirred react 90 minutes it is stand-by；Add graphene oxide into the deionized water of 2 times of amounts In, ultrasonic disperse is formed and added in above-mentioned reaction system after suspension for 30 minutes, is stirred 20 minutes with 800 revs/min of speed, is obtained To complex emulsions；

（3）Hydroxymethyl-2 dihydroxy-ethylene urea of the solid content for 42wt% is mixed with Ludox, is stirred with 500 revs/min of speed Step is added after 10 minutes（1）Step（2）The product for obtaining and remaining residual components, continue ultrasonic disperse 15 minutes, obtain final product.

Fast growing wood is processed into the veneer of certain specification, it is 6-10% to be dried to moisture content, is put into vacuum pressure impregnation In tank, after being evacuated to -0.01MPa, kept for 30-40 minutes, be then rapidly injected modifying agent of the present invention, continue to keep 40-50 Minute, 0.89-0.9 MPa are forced into afterwards is kept for 15-20 minutes；After sheet material is taken out, environment gas disposed within is done to aqueous Rate is less than 30%, is then placed in baking oven, and 6-8 hours are first dried at 80-90 DEG C, then solidifies 4-5 hours at 120-130 DEG C, cold But afterwards discharging obtains modified fast growing wood.Modified fast growing wood is compared with unmodified timber, Absolute Dry Density 65.4% is improve, bending strength improves 63.3%, and parallel-to-grain compressive strength improves 16.6%, and whole water absorption rate reduces 34.7%.

Claims (2)

1. it is a kind of for fast growing wood addition graphene oxide modified emulsion composite modifier, it is characterised in that by following The raw material of weight portion is made：Formaldehyde 3-3.5, urea 2-3, hexa 1.5-2, maleic anhydride 0.02-0.03, vinegar Hydroxymethyl-2 dihydroxy-ethylene urea 20-23, six hydrations of sour appropriate, appropriate ammoniacal liquor, appropriate deionized water, solid content for 42wt% Magnesium chloride 1.5-2, Ludox 10-11, graphene oxide 3-4, methyl methacrylate 7-8, butyl acrylate 3-4, nonyl phenol Poly- ten oxyethylene groups ether 0.8-1, pyrophosphorous acid sodium 1.5-2, potassium peroxydisulfate 0.1-0.12.

2. according to claim 1 it is a kind of for fast growing wood addition graphene oxide modified emulsion composite modifier, Characterized in that, being made up of step in detail below：

（1）Formaldehyde, urea, hexa are put into reactor, maleic anhydride is added, are heated to while stirring completely molten Solution, the deionized water for adding total amount 1.5-2 times to measure, is heated to 70-80 DEG C, is adjusted with acetic acid and ammoniacal liquor after stirring reaction 3-4 hour Section pH value is 7, terminates reaction；

（2）The poly- ten oxyethylene groups ether of nonyl phenol is dissolved in the 30-40 times of deionized water measured, heating water bath to 40-50 DEG C, Pyrophosphorous acid sodium is continuously added, is stirred to after being completely dissolved and is added the methyl methacrylate of half amount to mix with butyl acrylate Thing, to be warming up to 70-80 DEG C after 600-800 turn/part speed stirring 20-30 minutes, is slowly added dropwise potassium peroxydisulfate, adds remainder Methyl methacrylate and butyl acrylate mixture, insulated and stirred reaction 90-120 minutes it is stand-by；By graphene oxide plus In entering the 2-3 times of deionized water measured, ultrasonic disperse 30-40 minutes form and add after suspension in above-mentioned reaction system, with 800- 1000 revs/min of speed stirring 20-30 minutes, obtain complex emulsions；

（3）Hydroxymethyl-2 dihydroxy-ethylene urea of the solid content for 42wt% is mixed with Ludox, with 500-600 rev/min of speed Step is added after stirring 10-15 minutes（1）Step（2）The product for obtaining and remaining residual components, continue ultrasonic disperse 15-20 Minute, obtain final product.