CN106905656A - A kind of wab board modified phenolic foam composite and preparation method thereof - Google Patents
A kind of wab board modified phenolic foam composite and preparation method thereof Download PDFInfo
- Publication number
- CN106905656A CN106905656A CN201710229835.8A CN201710229835A CN106905656A CN 106905656 A CN106905656 A CN 106905656A CN 201710229835 A CN201710229835 A CN 201710229835A CN 106905656 A CN106905656 A CN 106905656A
- Authority
- CN
- China
- Prior art keywords
- modified
- weight
- parts
- ratio
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/14—Applications used for foams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Laminated Bodies (AREA)
Abstract
A kind of wab board modified phenolic foam composite and preparation method thereof, after composite is impregnated by paper honeycomb in phenolic resin as matrix resin, pressing mold, solidification are formed after mixing with toughness-increasing modified material；The raw material of toughness-increasing modified material is constituted：13 parts of 30 45 parts of phenolic resin as matrix resin, 12 18 parts of modified polyurethane prepolymer, 7 10 parts of polymethyl siloxane, 8 13 parts of reinforcing agent, 46 parts of composite fibre, 36 parts of foaming agent, 68 parts of surfactant, 6 10 parts of curing agent and antioxidant, are additionally added the additive that weight accounts for toughness-increasing modified material raw material gross weight 6 8%.Wab board modified phenolic foam composite of the invention obtained, is prevented from the brittle fracture and efflorescence of material, and can eliminate the electrostatic of material surface, makes the more hommization of worth wab board.
Description
Technical field
The present invention relates to sports apparatus technical field, and in particular to a kind of wab board with modified phenolic foam composite and
Its preparation method.
Background technology
Wab board is board for lying on back, be body-building, thin abdomen, with sit-ups, receive it is unlucky move, the lift training function such as leg of lying on the back
Sports apparatus.The material of existing wab board is generally steel, because its comfort level is intersected, need to be in its outer wrap plastics.And phenolic aldehyde
Foamed plastics has density low, lightweight, and thermal conductivity factor is low, temperature in use model with big, the characteristics of good stability of the dimension, Er Qiexiang
Than in polyvinyl chloride foam, polyethylene, polyurethane foam, phenol formaldehyde foam has excellent fire retardant, self-extinguishment, low smog, resistance to
The advantage that flame runs through.Therefore, in recent years, phenolic foam has been obtained extensively in fields such as ship, air material, sports equipments
General application.
But because the rigid aromatic ring of molecular structure methylene connection is closely piled up, phenolic hydroxyl group and the easy oxygen of methylene
Change so that oxidative resistance is bad in itself for phenolic foam, and mechanical property is poor, especially fragility are big, easy efflorescence, this defect
Significantly limit its application, the application on particularly outdoor sports equipment.In sports equipment field, to make phenolic foam
With the performance such as wear-resisting, buffering, shockproof, and meet strength demand, activeness and quietness must be carried out to it and is modified, while also to meet
Light weight, it is fire-retardant and with low cost the advantages of.
The content of the invention
It is an object of the invention to provide a kind of wab board modified phenolic foam composite and preparation method thereof, so as to change
Phenolic foam after property can be applied on outdoor sports equipment.
The technical scheme that is used to achieve the above object of the present invention for：A kind of wab board modified phenolic foam composite wood
Material, after being impregnated in phenolic resin as matrix resin by paper honeycomb, pressing mold, solidification are formed after mixing with toughness-increasing modified material, by weight
Number meter, the raw material of toughness-increasing modified material constitutes and is：Phenolic resin as matrix resin 30-45 parts, modified polyurethane prepolymer 12-18 parts, it is poly-
Methylsiloxane 7-10 parts, reinforcing agent 8-13 parts, composite fibre 4-6 parts, foaming agent 3-6 parts, surfactant 6-8 parts, solidification
Agent 6-10 parts and antioxidant 1-3 parts, it is additionally added the additive that weight accounts for toughness-increasing modified material raw material gross weight 6-8%；Its
In, the reinforcing agent by alumina powder, white mica powder, sodium carboxymethylcellulose and modified meerschaum suede, successively according to weight
Compare 4-5：8-9：2-3：The ratio of 1-1.2 is mixed；The composite fibre is by carbon nano-fiber, polyacrylonitrile fibre and hexichol
Formic acid diethylene glycol (DEG) ester, is successively 1-2 according to weight ratio：2-3：The ratio of 8-10 is mixed.
Wherein, surfactant is 1 by weight ratio：2 Tween-80 and water-soluble silicon oil composition.
Wherein, foaming agent is 2 by weight ratio：1 pentane and n-hexane composition.
Wherein, curing agent is 2 by weight ratio：1：1：2 p-methyl benzenesulfonic acid, phosphoric acid, boric acid and water composition.
A kind of wab board method of modified phenolic foam composite as described above is prepared, is comprised the following steps：
Step one, the uncured paper honeycomb for choosing target size as needed, are soaked in 3h in phenolic resin as matrix resin, so
After take out paper honeycomb, pull open and be laid on flat board foaming mould, be put into after fixing in 140 DEG C of baking oven and heat 1.5h, finally will
Paper honeycomb takes out, and is cooled to room temperature, stand-by；
Step 2, according to above-mentioned parts by weight, phenolic resin as matrix resin is preheated to 40 DEG C in water-bath first, be subsequently adding
Modified polyurethane prepolymer, 20-30min is stirred under the rotating speed of 450-500r/min；Then reinforcing agent, compound fibre are sequentially added
Peacekeeping polymethyl siloxane, 20-30min is stirred under the rotating speed of 550-600r/min；Sequentially add surfactant, foaming
Agent, antioxidant and additive, 15-20min is stirred under the rotating speed of 550-600r/min；Curing agent is subsequently adding, in 650-
Mixed solution is obtained after 5-10min is stirred under the rotating speed of 700r/min, mixed solution is poured into and is scribbled releasing agent and is preheated to 40
DEG C mould in, paper honeycomb prepared by press-in step one, closed die, and mould is moved to solidify 2h in 75 DEG C of baking oven, most
After be cooled to the room temperature demoulding, obtain modified phenolic foam composite.
Further, the preparation method of modified polyurethane prepolymer is：
（1）, sequentially add in Ludox account for the silicon powder of Ludox weight 2-3%, Ludox weight 1-2% potassium hexatitanate it is brilliant
1-2h then must be stirred under the conditions of 70-80 DEG C with the sodium acetate of Ludox weight 0.8-1%, modified silicasol is obtained, it is standby；
（2）, will be added in nano titanium oxide and account for the surface modifier I of nano titanium oxide weight 3-5%, stirring is obtained modified
Nano titanium oxide, it is standby；Wherein, surface modifier I, by barium hydroxide, sodium carbonate and KH570, is successively 3- according to weight ratio
4：1-2：30 ratio is mixed；
（3）, take MDI Type Polyurethane Prepolymers, add modified filler mix and modified polyurethane prepolymer；Wherein, change
Property filler and MDI Type Polyurethane Prepolymers weight ratio be 7：6；Modified filler is by di-n-octyl phthalate, acetone, step
（1）Obtained modified silicasol and step（2）Obtained modified nano-titanium dioxide, is successively 2 according to weight ratio：3：1：1
Ratio is mixed.
Further, the preparation method of reinforcing agent is：
（1）, sepiolite cashmere is mixed with the surface modifier II for accounting for its weight 3-5% after, stand 1-2h after filtering dry be obtained change
Property sepiolite cashmere；Wherein, surface modifier II compares 3-4 according to weight successively by KH550, ethanol, acetone and barium hydroxide：80：
2-3：The ratio of 1-2 is mixed；
（2）, according to weight compare 4-5：8-9：2-3：The ratio of 1-1.2, takes alumina powder, white mica powder, carboxymethyl fine successively
The plain sodium of dimension and step（1）Obtained modified meerschaum suede is well mixed, and reinforcing agent is obtained.
Further, the preparation method of additive is：According to weight ratio, tetraethyl orthosilicate is taken with deionized water according to 1：8-
10 ratio mixing, then sequentially add 1-2 parts of sepiolite cashmere thereto, account for the glacial acetic acid of tetraethyl orthosilicate weight 10% and account for just
The conductive black of silester weight 5% is well mixed to be reacted, and in course of reaction, is applied in reaction system every 20min
The ultrasonic wave 1min of frequency 250-270kHz, question response carries out ultrafiltration and obtains solid powder after terminating to reaction system, finally will
Solid powder abundant calcination under aerobic conditions removes carbon dust, that is, obtain additive.
In the present invention, it is the nomex paper honeycombs of 0.5-0.1mm that paper honeycomb uses thickness, and the cell length of side is 1.8-4.5mm,
Nominal unit weight is 30-48kg/m3。
In the present invention, it is preferred that conductive black specific surface area is 700-850m2/ g, average grain diameter is 20nm, and resistance is less than
0.6 Ω·m；Carbon nano-fiber, average diameter is 15-100 nm, and length is 20-50 μm, and specific surface area is 15-20 m2/g；
Antioxidant is phosphite ester kind antioxidant.
The present invention uses and treatment, modified polyurethane prepolymer and phenolic resin is modified to MDI Type Polyurethane Prepolymers
Methylol reaction in matrix, showing as introducing a small amount of base polyurethane prepolymer for use as can just play good toughening effect；Course of reaction
In, the isocyano that modification is crossed in polyurethane prepolymer is crosslinked with the methylol in phenolic resin, forms IPN net
Network shape structure, improves the intensity and toughness of foamed plastics, so as to reduce fragility, is not pulverized easily；Meanwhile, nano-titania particle
Surface contain a number of oxygen-containing functional group, be easy to titanium dioxide and remaining material occur at high temperature chemical bonding or
Physical bond, in the case where being acted on by external impacts, nano-titania particle can absorb more work of deformation, and produce " nail
Prick-climb up and over " effect, the increase crackle resistance suffered in extension, so that its toughness increases.
In the present invention, modified meerschaum suede, nano aluminium oxide micro mist are contained in reinforcing agent, both materials can be in carboxylic first
Under the auxiliary of base sodium cellulosate knead when it is dispersed in the plastic, on the one hand, modified meerschaum suede have very big inner surface
Product, the external force effect that the microcellular structure having can effectively be cut down and absorb；On the other hand, modified meerschaum is made in modifying process
The surfaces externally and internally of suede is grafted substantial amounts of silicone hydroxyl, and with matrix be connected modified meerschaum suede by chemical reaction by these groups
Come, it is ensured that the two has good interface binding power.
In the present invention, polymethyl siloxane can to a certain extent lift the toughness of foamed plastics, while improving enhancing
The compatibility of agent, composite fibre and phenolic resin as matrix resin；And composite fibre can not only be cross-linked with each other in mixing, so that anti-
The dibenzoic diglycol laurate for only containing in the brittle fracture and efflorescence, and composite fibre of material, can further enhance material
The plasticity and toughness of material, can more make fiber be combined closely with matrix material.
The present invention is combined using inorganic acid and organic acid, so both guaranteed efficiencies, and whole hair can be preferably controlled again
Bubble technical process.Additionally, conductive black and carbon nano-fiber also have certain contribution to the mechanical property of phenolic foam material, more
Importantly, the two forms three-dimensional conductive network structure in phenolic foam material, to there is phenolic foam certain
Electric conductivity, eliminates the electrostatic of material surface, makes the more hommization of worth wab board.
Specific embodiment
With reference to specific embodiment, the invention will be further described, so that those skilled in the art can be more preferable
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
A kind of wab board modified phenolic foam composite, after being impregnated in phenolic resin as matrix resin by paper honeycomb, with increasing
Pressing mold, solidification are formed after tough material modified mixing, are counted by weight, and the raw material composition of toughness-increasing modified material is：Phenolic resin
Matrix 30-45 parts, modified polyurethane prepolymer 12-18 parts, polymethyl siloxane 7-10 parts, reinforcing agent 8-13 parts, composite fibre
4-6 parts, foaming agent 3-6 parts, surfactant 6-8 parts, curing agent 6-10 parts and antioxidant 1-3 parts, weight has been additionally added it and has accounted for
The additive of toughness-increasing modified material raw material gross weight 6-8%；Wherein, the reinforcing agent is by alumina powder, white mica powder, carboxylic first
Base sodium cellulosate and modified meerschaum suede, compare 4-5 according to weight successively：8-9：2-3：The ratio of 1-1.2 is mixed；It is described multiple
Condensating fiber, by carbon nano-fiber, polyacrylonitrile fibre and dibenzoic diglycol laurate, is successively 1-2 according to weight ratio：2-3：8-
10 ratio is mixed.
Embodiment 1
A kind of wab board preparation method of modified phenolic foam composite, comprises the following steps：
Step one, sequentially add in Ludox account for the silicon powder of Ludox weight 3%, Ludox weight 1% potassium hexatitanate it is brilliant
1h then must be stirred under the conditions of 80 DEG C with the sodium acetate of Ludox weight 0.9%, modified silicasol is obtained, it is standby；
Step 2, will be added in nano titanium oxide and account for the surface modifier I of nano titanium oxide weight 5%, stirring will be obtained modified
Nano titanium oxide, it is standby；Wherein, surface modifier I, by barium hydroxide, sodium carbonate and KH570, is successively 4 according to weight ratio：
1：30 ratio is mixed；
Step 3, take MDI Type Polyurethane Prepolymers, add modified filler mix and modified polyurethane prepolymer；Wherein,
Modified filler is 7 with the weight ratio of MDI Type Polyurethane Prepolymers：6；Modified filler is by di-n-octyl phthalate, acetone, step
Modified silicasol obtained in rapid one and modified nano-titanium dioxide obtained in step 2, are successively 2 according to weight ratio：3：1：1
Ratio is mixed；
Step 4, sepiolite cashmere is mixed with the surface modifier II for accounting for its weight 3-5% after, stand 1-2h after filter the system of drying
Obtain modified meerschaum suede；Wherein, surface modifier II compares 4 according to weight successively by KH550, ethanol, acetone and barium hydroxide：
80：2：1 ratio is mixed；
Step 5, compare 5 according to weight：8：3：1 ratio, take successively alumina powder, white mica powder, sodium carboxymethylcellulose and
Modified meerschaum suede obtained in step 4 is well mixed, and reinforcing agent is obtained；
Step 6：According to weight ratio, tetraethyl orthosilicate is taken with deionized water according to 1：8 ratio mixing, then add successively thereto
Enter 2 parts of sepiolite cashmeres, account for tetraethyl orthosilicate weight 10% glacial acetic acid and account for tetraethyl orthosilicate weight 5% conductive black mixing it is equal
It is even to be reacted, in course of reaction, every 20min to the ultrasonic wave 1min for applying frequency 260kHz in reaction system, question response
Ultrafiltration is carried out to reaction system after end and obtains solid powder, finally abundant calcination removes carbon elimination under aerobic conditions by solid powder
Powder, that is, obtain additive, standby；
Step 7, the uncured paper honeycomb for choosing target size as needed, are soaked in 3h in phenolic resin as matrix resin, so
After take out paper honeycomb, pull open and be laid on flat board foaming mould, be put into after fixing in 140 DEG C of baking oven and heat 1.5h, finally will
Paper honeycomb takes out, and is cooled to room temperature, stand-by；
Step 8, count by weight, take 45 parts of phenolic resin as matrix resin, 15 parts of modified polyurethane prepolymer obtained in step 3,
It is 7 parts of polymethyl siloxane, 8 parts of reinforcing agent obtained in step 5,4 parts of composite fibre, 5 parts of foaming agent, 6 parts of surfactant, solid
8 parts of agent, 2 parts of antioxidant and 7 parts of additive obtained in step 6, it is standby；Wherein, composite fibre by carbon nano-fiber,
Polyacrylonitrile fibre and dibenzoic diglycol laurate, are successively 1 according to weight ratio：1：4 ratio is mixed；Surfactant
It is 1 by weight ratio：2 Tween-80 and water-soluble silicon oil composition；Foaming agent is 2 by weight ratio：1 pentane and n-hexane group
Into；Curing agent is 2 by weight ratio：1：1：2 p-methyl benzenesulfonic acid, phosphoric acid, boric acid and water composition；
Phenolic resin as matrix resin is preheated to 40 DEG C in water-bath first, modified polyurethane prepolymer is subsequently adding, in 450r/
20min is stirred under the rotating speed of min；Then reinforcing agent, composite fibre and polymethyl siloxane are sequentially added, in turning for 550r/min
The lower stirring 20min of speed；Surfactant, foaming agent, antioxidant and additive are sequentially added, under the rotating speed of 550r/min
Stirring 15min；Curing agent is subsequently adding, mixed solution is obtained after stirring 5min under the rotating speed of 650r/min, by mixed solution
Pour into and scribble releasing agent and be preheated in 40 DEG C of mould, paper honeycomb prepared by press-in step 7, closed die, and mould is moved
Solidify 2h into 75 DEG C of baking ovens, be finally cooled to the room temperature demoulding, obtain modified phenolic foam composite.
Embodiment 2
A kind of wab board preparation method of modified phenolic foam composite, comprises the following steps：
Step one, sequentially add in Ludox account for the silicon powder of Ludox weight 2%, Ludox weight 2% potassium hexatitanate it is brilliant
1h then must be stirred under the conditions of 70 DEG C with the sodium acetate of Ludox weight 1%, modified silicasol is obtained, it is standby；
Step 2, will be added in nano titanium oxide and account for the surface modifier I of nano titanium oxide weight 3%, stirring will be obtained modified
Nano titanium oxide, it is standby；Wherein, surface modifier I, by barium hydroxide, sodium carbonate and KH570, is successively 3 according to weight ratio：
1：30 ratio is mixed；
Step 3, take MDI Type Polyurethane Prepolymers, add modified filler mix and modified polyurethane prepolymer；Wherein,
Modified filler is 7 with the weight ratio of MDI Type Polyurethane Prepolymers：6；Modified filler is by di-n-octyl phthalate, acetone, step
Modified silicasol obtained in rapid one and modified nano-titanium dioxide obtained in step 2, are successively 2 according to weight ratio：3：1：1
Ratio is mixed；
Step 4, sepiolite cashmere is mixed with the surface modifier II for accounting for its weight 3-5% after, stand 1-2h after filter the system of drying
Obtain modified meerschaum suede；Wherein, surface modifier II compares 3 according to weight successively by KH550, ethanol, acetone and barium hydroxide：
80：3：2 ratio is mixed；
Step 5, compare 4 according to weight：9：2：1.2 ratio, takes alumina powder, white mica powder, sodium carboxymethylcellulose successively
It is well mixed with modified meerschaum suede obtained in step 4, reinforcing agent is obtained；
Step 6：According to weight ratio, tetraethyl orthosilicate is taken with deionized water according to 1：10 ratio mixing, then add successively thereto
Enter 1 part of sepiolite cashmere, account for tetraethyl orthosilicate weight 10% glacial acetic acid and account for tetraethyl orthosilicate weight 5% conductive black mixing it is equal
It is even to be reacted, in course of reaction, every 20min to the ultrasonic wave 1min for applying frequency 270kHz in reaction system, question response
Ultrafiltration is carried out to reaction system after end and obtains solid powder, finally abundant calcination removes carbon elimination under aerobic conditions by solid powder
Powder, that is, obtain additive, standby；
Step 7, the uncured paper honeycomb for choosing target size as needed, are soaked in 3h in phenolic resin as matrix resin, so
After take out paper honeycomb, pull open and be laid on flat board foaming mould, be put into after fixing in 140 DEG C of baking oven and heat 1.5h, finally will
Paper honeycomb takes out, and is cooled to room temperature, stand-by；
Step 8, count by weight, take 30 parts of phenolic resin as matrix resin, 18 parts of modified polyurethane prepolymer obtained in step 3,
It is 8 parts of polymethyl siloxane, 13 parts of reinforcing agent obtained in step 5,5 parts of composite fibre, 3 parts of foaming agent, 8 parts of surfactant, solid
6 parts of agent, 1 part of antioxidant and 5.52 parts of additive obtained in step 6, it is standby；Wherein, composite fibre is by carbon Nanowire
Dimension, polyacrylonitrile fibre and dibenzoic diglycol laurate, are successively 1 according to weight ratio：3：10 ratio is mixed；Live on surface
Property agent by weight ratio be 1：2 Tween-80 and water-soluble silicon oil composition；Foaming agent is 2 by weight ratio：1 pentane and just oneself
Alkane is constituted；Curing agent is 2 by weight ratio：1：1：2 p-methyl benzenesulfonic acid, phosphoric acid, boric acid and water composition；
Phenolic resin as matrix resin is preheated to 40 DEG C in water-bath first, modified polyurethane prepolymer is subsequently adding, in 500r/
25min is stirred under the rotating speed of min；Then reinforcing agent, composite fibre and polymethyl siloxane are sequentially added, in turning for 600r/min
The lower stirring 25min of speed；Surfactant, foaming agent, antioxidant and additive are sequentially added, under the rotating speed of 600r/min
Stirring 18min；Curing agent is subsequently adding, mixed solution is obtained after stirring 6min under the rotating speed of 700r/min, by mixed solution
Pour into and scribble releasing agent and be preheated in 40 DEG C of mould, paper honeycomb prepared by press-in step 7, closed die, and mould is moved
Solidify 2h into 75 DEG C of baking ovens, be finally cooled to the room temperature demoulding, obtain modified phenolic foam composite.
Embodiment 3
A kind of wab board preparation method of modified phenolic foam composite, comprises the following steps：
Step one, silicon powder, six metatitanic acids of Ludox weight 1.5% for accounting for Ludox weight 2.5% are sequentially added in Ludox
The sodium acetate of potassium whisker and Ludox weight 0.8%, then stirs 2h under the conditions of 75 DEG C, and modified silicasol is obtained, standby；
Step 2, will be added in nano titanium oxide and account for the surface modifier I of nano titanium oxide weight 3-5%, stirring will be obtained and changes
Property nano titanium oxide, it is standby；Wherein, surface modifier I is successively according to weight ratio by barium hydroxide, sodium carbonate and KH570
3：2：30 ratio is mixed；
Step 3, take MDI Type Polyurethane Prepolymers, add modified filler mix and modified polyurethane prepolymer；Wherein,
Modified filler is 7 with the weight ratio of MDI Type Polyurethane Prepolymers：6；Modified filler is by di-n-octyl phthalate, acetone, step
Modified silicasol obtained in rapid one and modified nano-titanium dioxide obtained in step 2, are successively 2 according to weight ratio：3：1：1
Ratio is mixed；
Step 4, sepiolite cashmere is mixed with the surface modifier II for accounting for its weight 3-5% after, stand 1-2h after filter the system of drying
Obtain modified meerschaum suede；Wherein, surface modifier II compares 3 according to weight successively by KH550, ethanol, acetone and barium hydroxide：
80：2：1 ratio is mixed；
Step 5, compare 4.5 according to weight：8.5：2：1 ratio, takes alumina powder, white mica powder, carboxymethylcellulose calcium successively
Modified meerschaum suede obtained in sodium and step 4 is well mixed, and reinforcing agent is obtained；
Step 6：According to weight ratio, tetraethyl orthosilicate is taken with deionized water according to 1：9 ratio mixing, then add successively thereto
Enter 1.5 parts of sepiolite cashmeres, account for the glacial acetic acid of tetraethyl orthosilicate weight 10% and account for the conductive black mixing of tetraethyl orthosilicate weight 5%
Uniformly reacted, in course of reaction, every 20min to the ultrasonic wave 1min for applying frequency 250kHz in reaction system, treated anti-
Ultrafiltration is carried out to reaction system after should terminating and obtains solid powder, finally abundant calcination is removed under aerobic conditions by solid powder
Carbon dust, that is, obtain additive, standby；
Step 7, the uncured paper honeycomb for choosing target size as needed, are soaked in 3h in phenolic resin as matrix resin, so
After take out paper honeycomb, pull open and be laid on flat board foaming mould, be put into after fixing in 140 DEG C of baking oven and heat 1.5h, finally will
Paper honeycomb takes out, and is cooled to room temperature, stand-by；
Step 8, count by weight, take 40 parts of phenolic resin as matrix resin, 12 parts of modified polyurethane prepolymer obtained in step 3,
10 parts of polymethyl siloxane, 10 parts of reinforcing agent obtained in step 5,6 parts of composite fibre, 6 parts of foaming agent, 7 parts of surfactant,
10 parts of curing agent, 3 parts of antioxidant and 8.32 parts of additive obtained in step 6, it is standby；Wherein, composite fibre is by carbon nanometer
Fiber, polyacrylonitrile fibre and dibenzoic diglycol laurate, are successively 1 according to weight ratio：3：9 ratio is mixed；Surface
Activating agent is 1 by weight ratio：2 Tween-80 and water-soluble silicon oil composition；Foaming agent is 2 by weight ratio：1 pentane and just
Hexane is constituted；Curing agent is 2 by weight ratio：1：1：2 p-methyl benzenesulfonic acid, phosphoric acid, boric acid and water composition；
Phenolic resin as matrix resin is preheated to 40 DEG C in water-bath first, modified polyurethane prepolymer is subsequently adding, in 480r/
30min is stirred under the rotating speed of min；Then reinforcing agent, composite fibre and polymethyl siloxane are sequentially added, in turning for 580r/min
The lower stirring 30min of speed；Surfactant, foaming agent, antioxidant and additive are sequentially added, under the rotating speed of 580r/min
Stirring 20min；Curing agent is subsequently adding, mixed solution is obtained after stirring 10min under the rotating speed of 680r/min, by mixed solution
Pour into and scribble releasing agent and be preheated in 40 DEG C of mould, paper honeycomb prepared by press-in step 7, closed die, and mould is moved
Solidify 2h into 75 DEG C of baking ovens, be finally cooled to the room temperature demoulding, obtain modified phenolic foam composite.
Embodiment 4：Count by weight, take 42 parts of phenolic resin as matrix resin, 14 parts of modified polyurethane prepolymer, poly- methyl silicon
9 parts of oxygen alkane, 12 parts of reinforcing agent, 5.5 parts of composite fibre, 4 parts of foaming agent, 6.5 parts of surfactant, 7 parts of curing agent, antioxidant
2.5 parts and 7.7 parts of additive, these raw materials are mixed according to the operating procedure of step 8 in embodiment, and and paper wasp
Nest carries out pressing mold, and modified phenolic foam composite is obtained.
Performance test, result of the test such as following table institute are carried out to phenolic foam composite material obtained in aforementioned four embodiment
Show：
Control of the curing agent to the cell size in foamed plastics, structure and porosity, plays an important role.Phenolic resin makes
During with inorganic acid as catalyst, the carrying out of polycondensation reaction between molecular resin is promoted, so that emulsifying resins expand, accelerate foaming
Solidification, but the viscosity increase of resin is very fast, and foaming process is difficult to control, and residual acid has strong corruption in the phenolic foams being made
Corrosion；Organic acid makees curing agent, although be relatively easy to control and without corrosivity, but its expansion rate is slower, influences production efficiency.This
Invention is solidified by the way of inorganic acid and organic acid are combined, both guaranteed efficiency, and whole hair can be preferably controlled again
Bubble technical process.
The present invention using acetone to MDI Type Polyurethane Prepolymers treatment, institute reaction prepolymer and phenolic resin in hydroxyl
Methyl reacts, and then excessive MDI reacts with the methylol in phenolic resin, shows as introducing a small amount of base polyurethane prepolymer for use as with regard to energy
Play good toughening effect.In course of reaction, in isocyano and phenolic resin that modification is crossed in polyurethane prepolymer
Methylol crosslink, form interpenetrating networks shape structure, a large amount of flexible carbamic acids well are introduced in phenolic resin
Ester segment, changes the rigid structure of phenolic resin, raises phenol formaldehyde foam compressive strength, toughness enhancing, so that fragility is reduced,
It is not pulverized easily.
The Nomex paper honeycombs that the present invention is selected are impregnated with phenolic resin as matrix resin first shapes, during follow-up pressing mold, leaching
Paper honeycomb after stain can be effectively combined with resin matrix, make phenol formaldehyde foam and Nomex paper honeycombs as an entirety
Material, the destruction of common resistance external force, improves material overall mechanical properties；Furthermore, Nomex paper honeycombs rise to integral foam materials
To a skeleton function, further reduce the pulverization rate of material；Additionally, modified phenol formaldehyde foam has class alveolate texture,
Similar to Nomex paper honeycombs, the cellular phenol formaldehyde foam of class that material shows as small-bore is nested in the Nomex paper honeycombs of large aperture
In, have the effect of improving to the mechanical property of material.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
Member, on the premise of the inventive method is not departed from, can also make some improvement and supplement, and these are improved and supplement also should be regarded as
Protection scope of the present invention.
Claims (9)
1. a kind of wab board modified phenolic foam composite, after being impregnated in phenolic resin as matrix resin by paper honeycomb, then with increasing
Pressing mold, solidification are formed after tough material modified mixing, it is characterised in that：Count by weight, the raw material composition of toughness-increasing modified material
For：Phenolic resin as matrix resin 30-45 parts, modified polyurethane prepolymer 12-18 parts, polymethyl siloxane 7-10 parts, reinforcing agent 8-13
Part, composite fibre 4-6 part, foaming agent 3-6 parts, surfactant 6-8 parts, curing agent 6-10 parts and antioxidant 1-3 parts, also add
Enter to have weight to account for the additive of toughness-increasing modified material raw material gross weight 6-8%；
Wherein, the reinforcing agent is pressed successively by alumina powder, white mica powder, sodium carboxymethylcellulose and modified meerschaum suede
Compare 4-5 according to weight：8-9：2-3：The ratio of 1-1.2 is mixed；
The composite fibre is successively according to weight ratio by carbon nano-fiber, polyacrylonitrile fibre and dibenzoic diglycol laurate
1-2：2-3：The ratio of 8-10 is mixed.
2. a kind of wab board modified phenolic foam composite as claimed in claim 1, it is characterised in that：Described surface
Activating agent is 1 by weight ratio：2 Tween-80 and water-soluble silicon oil composition.
3. a kind of wab board modified phenolic foam composite as claimed in claim 1, it is characterised in that：Described foaming
Agent is 2 by weight ratio：1 pentane and n-hexane composition.
4. a kind of wab board modified phenolic foam composite as claimed in claim 1, it is characterised in that：Described solidification
Agent is 2 by weight ratio：1：1：2 p-methyl benzenesulfonic acid, phosphoric acid, boric acid and water composition.
5. the method for preparing a kind of wab board modified phenolic foam composite as claimed in claim 1, it is characterised in that
Comprise the following steps：
Step one, the uncured paper honeycomb for choosing target size as needed, are soaked in 3h in phenolic resin as matrix resin, so
After take out paper honeycomb, pull open and be laid on flat board foaming mould, be put into after fixing in 140 DEG C of baking oven and heat 1.5h, finally will
Paper honeycomb takes out, and is cooled to room temperature, stand-by；
Step 2, according to the parts by weight described in claim 1, phenolic resin as matrix resin is preheated to 40 in water-bath first
DEG C, modified polyurethane prepolymer is subsequently adding, stir 20-30min under the rotating speed of 450-500r/min；Then increasing is sequentially added
Strong agent, composite fibre and polymethyl siloxane, 20-30min is stirred under the rotating speed of 550-600r/min；Sequentially add surface
Activating agent, foaming agent, antioxidant and additive, 15-20min is stirred under the rotating speed of 550-600r/min；It is subsequently adding solid
Agent, mixed solution is obtained after stirring 5-10min under the rotating speed of 650-700r/min, mixed solution is poured into and scribbles releasing agent
And be preheated in 40 DEG C of mould, paper honeycomb prepared by press-in step one, closed die, and mould is moved into 75 DEG C of baking oven
Solidification 2h, is finally cooled to the room temperature demoulding, obtains modified phenolic foam composite.
6. a kind of method of wab board modified phenolic foam composite is prepared as claimed in claim 5, it is characterised in that
The preparation method of modified polyurethane prepolymer is：
（1）, sequentially add in Ludox account for the silicon powder of Ludox weight 2-3%, Ludox weight 1-2% potassium hexatitanate it is brilliant
1-2h then must be stirred under the conditions of 70-80 DEG C with the sodium acetate of Ludox weight 0.8-1%, modified silicasol is obtained, it is standby；
（2）, will be added in nano titanium oxide and account for the surface modifier I of nano titanium oxide weight 3-5%, stirring is obtained modified
Nano titanium oxide, it is standby；Wherein, surface modifier I, by barium hydroxide, sodium carbonate and KH570, is successively 3- according to weight ratio
4：1-2：30 ratio is mixed；
（3）, take MDI Type Polyurethane Prepolymers, add modified filler mix and modified polyurethane prepolymer；Wherein, change
Property filler and MDI Type Polyurethane Prepolymers weight ratio be 7：6；Modified filler is by di-n-octyl phthalate, acetone, step
（1）Obtained modified silicasol and step（2）Obtained modified nano-titanium dioxide, is successively 2 according to weight ratio：3：1：1
Ratio is mixed.
7. a kind of method of wab board modified phenolic foam composite is prepared as claimed in claim 5, it is characterised in that
The preparation method of reinforcing agent is：
（1）, sepiolite cashmere is mixed with the surface modifier II for accounting for its weight 3-5% after, stand 1-2h after filtering dry be obtained change
Property sepiolite cashmere；Wherein, surface modifier II compares 3-4 according to weight successively by KH550, ethanol, acetone and barium hydroxide：80：
2-3：The ratio of 1-2 is mixed；
（2）, according to weight compare 4-5：8-9：2-3：The ratio of 1-1.2, takes alumina powder, white mica powder, carboxymethyl fine successively
The plain sodium of dimension and step（1）Obtained modified meerschaum suede is well mixed, and reinforcing agent is obtained.
8. a kind of method of wab board modified phenolic foam composite is prepared as claimed in claim 5, it is characterised in that
The preparation method of additive is：According to weight ratio, tetraethyl orthosilicate is taken with deionized water according to 1：The ratio mixing of 8-10, then to
1-2 parts of sepiolite cashmere is wherein sequentially added, the glacial acetic acid of tetraethyl orthosilicate weight 10% is accounted for and is accounted for leading for tetraethyl orthosilicate weight 5%
Electric carbon black is well mixed to be reacted, in course of reaction, every 20min to applying the super of frequency 250-270kHz in reaction system
Sound wave 1min, question response carries out ultrafiltration and obtains solid powder after terminating to reaction system, finally by solid powder in aerobic conditions
Abundant calcination down removes carbon dust, that is, obtain additive.
9. a kind of method of wab board modified phenolic foam composite is prepared as claimed in claim 8, it is characterised in that：
It is the nomex paper honeycombs of 0.5-0.1mm that paper honeycomb uses thickness, and the cell length of side is 1.8-4.5mm, and nominal unit weight is 30-48kg/
m3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710229835.8A CN106905656A (en) | 2017-04-10 | 2017-04-10 | A kind of wab board modified phenolic foam composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710229835.8A CN106905656A (en) | 2017-04-10 | 2017-04-10 | A kind of wab board modified phenolic foam composite and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106905656A true CN106905656A (en) | 2017-06-30 |
Family
ID=59195037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710229835.8A Pending CN106905656A (en) | 2017-04-10 | 2017-04-10 | A kind of wab board modified phenolic foam composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106905656A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189342A (en) * | 2017-07-12 | 2017-09-22 | 合肥轻风飏电气科技有限责任公司 | A kind of wear-resisting antistatic Yoga mat and preparation method thereof |
| CN107236246A (en) * | 2017-08-01 | 2017-10-10 | 合肥康之恒机械科技有限公司 | A kind of wab board nano antibacterial composite and preparation method thereof |
| CN107383767A (en) * | 2017-09-14 | 2017-11-24 | 江苏攸途健身器材有限公司 | A kind of preparation method of wab board modified phenolic foam composite |
| CN107573640A (en) * | 2017-09-14 | 2018-01-12 | 江苏攸途健身器材有限公司 | A kind of wab board modified phenolic foam composite |
| CN114274567A (en) * | 2021-12-31 | 2022-04-05 | 北京奥星雅博科技发展有限责任公司 | Phenolic filling aramid fiber honeycomb structure and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838770A (en) * | 2012-09-10 | 2012-12-26 | 山东圣泉化工股份有限公司 | Preparation method of phenolic foam boards |
| CN103788570A (en) * | 2012-10-31 | 2014-05-14 | 合肥杰事杰新材料股份有限公司 | Modified phenolic foam and preparation method thereof |
| CN106280231A (en) * | 2016-08-12 | 2017-01-04 | 河南科技大学 | A kind of sports equipment toughening modifying phenolic foam and preparation method thereof |
| CN106481947A (en) * | 2016-11-09 | 2017-03-08 | 李强 | A kind of surveying instrument manufacture method of field quakeproof bracket and Shockproof base |
| CN106519309A (en) * | 2016-11-29 | 2017-03-22 | 洛阳理工学院 | Auxiliary tool for English learning of children |
-
2017
- 2017-04-10 CN CN201710229835.8A patent/CN106905656A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102838770A (en) * | 2012-09-10 | 2012-12-26 | 山东圣泉化工股份有限公司 | Preparation method of phenolic foam boards |
| CN103788570A (en) * | 2012-10-31 | 2014-05-14 | 合肥杰事杰新材料股份有限公司 | Modified phenolic foam and preparation method thereof |
| CN106280231A (en) * | 2016-08-12 | 2017-01-04 | 河南科技大学 | A kind of sports equipment toughening modifying phenolic foam and preparation method thereof |
| CN106481947A (en) * | 2016-11-09 | 2017-03-08 | 李强 | A kind of surveying instrument manufacture method of field quakeproof bracket and Shockproof base |
| CN106519309A (en) * | 2016-11-29 | 2017-03-22 | 洛阳理工学院 | Auxiliary tool for English learning of children |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107189342A (en) * | 2017-07-12 | 2017-09-22 | 合肥轻风飏电气科技有限责任公司 | A kind of wear-resisting antistatic Yoga mat and preparation method thereof |
| CN107236246A (en) * | 2017-08-01 | 2017-10-10 | 合肥康之恒机械科技有限公司 | A kind of wab board nano antibacterial composite and preparation method thereof |
| CN107383767A (en) * | 2017-09-14 | 2017-11-24 | 江苏攸途健身器材有限公司 | A kind of preparation method of wab board modified phenolic foam composite |
| CN107573640A (en) * | 2017-09-14 | 2018-01-12 | 江苏攸途健身器材有限公司 | A kind of wab board modified phenolic foam composite |
| CN114274567A (en) * | 2021-12-31 | 2022-04-05 | 北京奥星雅博科技发展有限责任公司 | Phenolic filling aramid fiber honeycomb structure and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106905656A (en) | A kind of wab board modified phenolic foam composite and preparation method thereof | |
| CN101717514B (en) | Modified phenolic resin, foamed material thereof and method for preparing same | |
| CN107363963B (en) | Manufacturing method of ultrahigh-density ultrahigh-strength plant fiber board | |
| CN115302885B (en) | High-heat-resistance high-heat-conductivity copper-clad plate and preparation method thereof | |
| CN102877366B (en) | Method for preparing wet curtain paper | |
| CN104877157B (en) | A kind of efficient fast-curing resin base light composite material and preparation method thereof | |
| CN108192054B (en) | Preparation method of phenolic resin polyol for polyurethane foam | |
| CN109279811A (en) | A kind of preparation method of building heat preservation heat-insulation composite material | |
| CN107216608A (en) | A kind of compositions of thermosetting resin of highly corrosion resistant and its application | |
| CN107189342A (en) | A kind of wear-resisting antistatic Yoga mat and preparation method thereof | |
| CN105462163B (en) | A kind of preparation method of biomass foam core composite partition material | |
| TW202000460A (en) | Resin laminate and method of manufacturing resin laminate | |
| CN106751530B (en) | A kind of composite material sandwich structure co-curable lightweight high rigidity core material and its preparation method and application | |
| AU2021104560A4 (en) | Preparation method of biomass-based foam sandwich board material for partition wall | |
| CN114940005A (en) | High-heat-insulation heat-preservation composite board and production process thereof | |
| CN114806134A (en) | Thermoplastic/thermoset polymer blend foam and method of making same | |
| JPS6139901B2 (en) | ||
| EP3165569B1 (en) | Prepreg and fibre-reinforced composite foam material | |
| CN101067016A (en) | Synthesis and usage of fast curing phenolic resin | |
| CN107379692A (en) | A kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite and preparation method thereof | |
| CN104017385B (en) | Resin combination, prepreg, composite board and its preparation method and application | |
| CN1044881C (en) | Artificial straw board and its manufacturing technology | |
| CN107236246A (en) | A kind of wab board nano antibacterial composite and preparation method thereof | |
| CN106118571A (en) | Wind electricity blade graphene-containing structural adhesive and preparation method thereof | |
| CN109438916A (en) | Heat-resisting antistatic polyether-ether-ketone composite material of one kind and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170630 |
|
| RJ01 | Rejection of invention patent application after publication |