CN107379692A - A kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite and preparation method thereof - Google Patents
A kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/021—Fibrous or filamentary layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
- B32B2260/025—Particulate layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/04—Impregnation, embedding, or binder material
- B32B2260/046—Synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2266/00—Composition of foam
- B32B2266/02—Organic
- B32B2266/0214—Materials belonging to B32B27/00
- B32B2266/0285—Condensation resins of aldehydes, e.g. with phenols, ureas, melamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/302—Conductive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
- B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
Abstract
The present invention provides a kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite and preparation method thereof, lignin is replaced part phenol to prepare liquid resol-type phenolic resin by the present invention, again respectively to adding carbon chopped fiber in the mixture of liquid A step phenolic resin type phenolic resin and polyurethane and performed polymer, hollow silicon dioxide microballoon and metal hydroxide-modified prepare a variety of phenolic resin composites, surface layer is used as using metal hydroxide-modified phenolic resin composite again, the phenolic resin composite microsphere modified using carbon chopped fiber and hollow silicon dioxide is used as intermediate layer, polyurethane-modified flexible multi-layered foamed phenolic resin composite is obtained through paved in multi-layers drying foaming.Polyurethane-modified flexible multi-layered foamed phenolic resin composite prepared by the present invention is remaining original insulation, low-quality, fire-retardant high-quality performance, reduces production cost, improves acid resistance, intensity and toughness, excellent combination property.
Description
Technical field
The invention belongs to foamed phenolic resin technical field of composite materials, and in particular to a kind of polyurethane-modified flexibility is more
Layer foamed phenolic resin composite and preparation method thereof.
Background technology
Phenolic resin, also referred to as phenol formaldehyde resin, it is prepared by formaldehyde and benzoic acid or the reaction of cruel analog derivative,
Product structure depends on the soda acid bad border of phenol derivatives, the stoichiometric proportion of phenol and formaldehyde and reaction, at present phenolic resin
Large-scale application is in plastics and adhesive, with the continuous improvement to phenolic resin performance, phenolic resin by add boron, phosphorus or
The compound modified anti-flammability and oxidation resistent susceptibility that can improve phenolic resin of person's silicon etc., phenolaldehyde moulding compound, refractory material,
Foundry Coated Sand, friction material, grinding tool material, rubber for tire, Electric/electronic Materials, wood binder, phenolic resin base are compound
Material and phenol formaldehyde foam etc. are applied.
Expansion type phenolic resin is substantially resol type phenol resin, has many excellent heat insulating abilities, anti-flammability, thermostabilization
Property, insulating properties, low smoke density and low smoke toxicity, and melt phenomenon characteristic with flame without dripping off in combustion, have very high
Chemicals-resistant and chemical solvent feature, compared with Ju vinyl chlorides Pao Droplets materials and Polyoxyethylene este Pao Droplets materials, fire resistance is more
Add excellent, there are more preferable potentiality.Foaminess resol-type phenolic resin disclosed in Chinese patent CN101189289B
Moulding material and phenol resin foam, it is non-anti- that the moulding material contains liquid A step phenolic resin type phenolic resin, organic system
Answer type foaming agent, foam stabilizer, nitrogenous cross-linking type cyclic compound additive, acid as curing agent and aluminium hydroxide and/or calcium carbonate without
Machine filler is formed, and wherein liquid A step phenolic resin type phenolic resin is 1 by mol ratio:1.5-1.0：3 ratio make phenol with
Formaldehyde is reacted to obtain, and the foaminess resol-type phenolic resin molding material of preparation has excellent intensity, changed
Kind fragility and good corrosion resistance.A kind of layered distribution short fiber reinforced is more disclosed in Chinese patent CN105086348B
Hole phenolic composite and preparation method thereof, liquid phenolic resin, solvent, curing agent and surface modifier are mixed to obtain
Phenol resin solution, chopped fiber stirring will be added in phenol resin solution, vacuumizing and defoaming obtains slurry, and last injection molding solidification is cold
But, layered distribution short fiber reinforced porous phenolic composite is obtained, it is in composite prepared by this method that chopped fiber is uniform
It is distributed in the phenolic resin of a large amount of nanometers or micrometer grade hole, has that density is low, and thermal conductivity is low and the high characteristic of compressive strength.
But the mechanical performance of expansion type phenolic resin is still without obtaining larger improvement at present.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of polyurethane-modified flexible multi-layered foamed phenolic resin is compound
Lignin is replaced part phenol to prepare liquid resol-type phenolic resin by material and preparation method thereof, the present invention, then
Respectively to adding carbon chopped fiber, hollow two in the mixture of liquid A step phenolic resin type phenolic resin and polyurethane and performed polymer
Silicon oxide microsphere and it is metal hydroxide-modified prepare a variety of phenolic resin composites, then obtain through paved in multi-layers multi-functional
Flexible multi-layered foamed phenolic resin composite.
In order to solve the above technical problems, the technical scheme is that：
A kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite, it is described polyurethane-modified flexible multi-layered
Foamed phenolic resin composite include acidproof foamed phenolic resin surface layer, hollow ball be modified foamed phenolic resin intermediate layer and
The foamed phenolic resin intermediate layer that chopped fiber is modified, what the acidproof foamed phenolic resin surface layer, hollow ball and chopped fiber were modified
All contain polyurethane foam resin in foamed phenolic resin intermediate layer, the chopped fiber is carbon chopped fiber.
As the preferred of above-mentioned technical proposal, the polyurethane-modified flexible multi-layered foamed phenolic resin composite
Structure is followed successively by：The hair that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
Steep phenolic resin intermediate layer, the foamed phenolic resin intermediate layer that hollow ball is modified and acidproof foamed phenolic resin surface layer.
As the preferred of above-mentioned technical proposal, the polyurethane-modified flexible multi-layered foamed phenolic resin composite
Structure is followed successively by：The hair that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
Steep phenolic resin intermediate layer and acidproof foamed phenolic resin surface layer.
The present invention also provides a kind of preparation method of polyurethane-modified flexible multi-layered foamed phenolic resin composite, wraps
Include following steps：
(1) biological lignin is added in the strong basic ion aqueous solution and hydrolyzed, after centrifugation removes insoluble matter, add 1%
Sulfuric acid solution, separate out lignin, wash to neutrality, vacuum drying obtains micro/nano level biology lignin；
(2) micro/nano level biology lignin mixing prepared by step (1) is added after phenol is melted, is stirred at 80-90 DEG C
Mix uniformly, add first paraformaldehyde, regulation pH to alkalescence, continue to react 30-60min, be cooled to 60 DEG C, add second
Paraformaldehyde is criticized, regulation pH to alkalescence, 70-80 DEG C is warming up to and continues to react 30-60min, be cooled to 60 DEG C, add the 3rd batch
Paraformaldehyde, regulation pH to alkalescence, it is warming up to 70-80 DEG C and continues to react 30-60min, be cooled to room temperature, obtain liquid first rank phenol
Urea formaldehyde type phenolic resin；
(3) carbon chopped fiber, emulsifying agent and hair are added in the liquid A step phenolic resin type phenolic resin for preparing step (2)
Infusion and base polyurethane prepolymer for use as stir, and adjust pH value to 2-3 with compound acid as curing agent, stir, obtain phenolic resin
Composite A, hollow silica ball, emulsification will be added in the liquid A step phenolic resin type phenolic resin of step (2) preparation
Agent and foaming agent and base polyurethane prepolymer for use as stir, and adjust pH value to 2-3 with compound acid as curing agent, it is compound to obtain phenolic resin
Material B；Metal hydroxides, emulsifying agent and hair are added in liquid A step phenolic resin type phenolic resin prepared by step (2)
Infusion and base polyurethane prepolymer for use as stir, and adjust pH value to 2-3 with compound acid as curing agent, obtain phenolic resin composite C；
(4) phenolic resin composite C, phenolic resin composite B and the phenolic resin composite wood for preparing step (2)
Material A is added in template, is transferred in 70 DEG C of baking ovens and is handled 30-60min, and taking-up obtains polyurethane-modified flexible multi-layered foaming
Phenolic resin composite.
As the preferred of above-mentioned technical proposal, in the step (1), the temperature of hydrolysis is 90-100 DEG C, time 10-
30min。
As the preferred of above-mentioned technical proposal, in the step (2), the amount of the middle material of formaldehyde Pyrogentisinic Acid and lignin
Than for 1.5-1.8, the lignin and the ratio of the amount of phenol material are 3-5:5-7.
As the preferred of above-mentioned technical proposal, in the step (2), first paraformaldehyde, second batch paraformaldehyde and
The mass ratio of 3rd batch of paraformaldehyde is 5:3:2.
As the preferred of above-mentioned technical proposal, in the step (3), carbon chopped fiber contains in phenolic resin composite A
Measure as 10-15%, the content of hollow silicon dioxide microsphere is 8-16% in phenolic resin composite B, phenolic resin composite wood
The content for expecting metal hydroxides in C is 5-10%.
As the preferred of above-mentioned technical proposal, in the step (3), phenolic resin composite A, phenolic resin is compound
The content of base polyurethane prepolymer for use as is 10-20% in material B and phenolic resin composite C.
As the preferred of above-mentioned technical proposal, in the step (4), phenolic resin composite C is as surface layer, phenolic aldehyde tree
Resin composite material A and phenolic resin composite B are as intermediate layer.
Compared with prior art, the invention has the advantages that：
(1) main material of polyurethane-modified flexible multi-layered foamed phenolic resin composite prepared by the present invention is wood
The phenolic resin that quality is modified, replaces phenol, substitution rate reaches 30-50%, can not only reduce life with the lignin of micro/nano level
Cost is produced, improves porosity, and the content of free formaldehyde and phenol is low, and bonding strength is moderate, the foam phenolic aldehyde tree of preparation
The compressive strength of fat also slightly improves, and heat conductivility and fire resistance are more preferable, and by the phenolic resin of lignin modification and poly- ammonia
Ester performed polymer is combined, and flexible using polyurethane improves the toughness of foamed phenolic resin, and do not interfere with foaming structure.
(2) respectively to phenolic aldehyde tree in polyurethane-modified flexible multi-layered foamed phenolic resin composite prepared by the present invention
Fat carries out carbon chopped fiber, hollow silicon dioxide and metal hydroxide-modified processing, carbon chopped fiber can in phenolic resin shape
Into network of fibers, the toughness and internal bond strength of phenolic resin are improved, hollow silicon dioxide microballoon can be attached to the table of hole
Face, the compactness of phenolic resin is improved, metal hydroxides can improve the acid resistance of phenolic resin, utilize these features
Material improves the compressive strength and toughness of phenolic resin, and does not interfere with foaming structure, and passes through a variety of phenolic resin materials
Stratiform laying, can according to product need to adjust each layer phenolic resin material raw material composition and porosity, be allowed to meet
The needs in various fields.
(3) free formaldehyde of polyurethane-modified flexible multi-layered foamed phenolic resin composite prepared by the present invention and trip
Low from phenol content, security is good, and heat endurance is good, and thermal conductivity factor is big, good heat preservation performance, good flame resistance, has good pressure-resistant
Contracting and stretch resistance energy, excellent combination property, and composite prepared by the present invention is sandwich construction, the controllability of product is good,
The needs in various fields can be met.
Embodiment
The present invention is described in detail below in conjunction with specific embodiment, herein illustrative examples and explanation of the invention
For explaining the present invention, but it is not as a limitation of the invention.
Embodiment 1：
(1) biological lignin is added in the strong basic ion aqueous solution, 10min is hydrolyzed at 90 DEG C, centrifugation removes not
After molten thing, 1% sulfuric acid solution is added, separates out lignin, washed to neutrality, it is wooden that vacuum drying obtains micro/nano level biology
Element.
(2) it is 1.5 according to the ratio of formaldehyde Pyrogentisinic Acid and the amount of the middle material of lignin, lignin and the amount of phenol material
Than for 3:7, the mass ratio of first paraformaldehyde, second batch paraformaldehyde and the 3rd batch of paraformaldehyde is 5:3:2, phenol is melted
The mixing of micro/nano level biology lignin is added after change, is stirred at 80 DEG C, adds first paraformaldehyde, regulation pH to alkali
Property, continue to react 30min, be cooled to 60 DEG C, add second batch paraformaldehyde, pH is to alkalescence for regulation, is warming up to 70 DEG C of continuation
30min is reacted, is cooled to 60 DEG C, adds the 3rd batch of paraformaldehyde, pH is to alkalescence for regulation, is warming up to 70 DEG C and continues to react
30min, room temperature is cooled to, obtains liquid A step phenolic resin type phenolic resin.
(3) by weight, it is 0.5-5mm by length is added in 100 parts of liquid A step phenolic resin type phenolic resin
Carbon chopped fiber, 6 parts of tween emulsifier, 10 parts of pentamethylene foaming agent and 10 parts of base polyurethane prepolymer for use as stir, use
Compound acid as curing agent adjusts pH value to 2, stirs, obtains phenolic resin composite A, wherein, phenolic resin composite A
The content of middle carbon chopped fiber is 10%.
By being added in 100 parts of liquid A step phenolic resin type phenolic resin, the silica that particle diameter is 100-1000nm is empty
Bulbus cordis, 6 parts of tween emulsifier, 10 parts of pentamethylene foaming agent and 10 parts of base polyurethane prepolymer for use as stir, and use Compound-acid
Curing agent adjusts pH value to 2, obtains phenolic resin composite B, wherein, hollow silicon dioxide in phenolic resin composite B
The content of microballoon is 8%.
Aluminium hydroxide, 6 parts of tween emulsifier, 10 will be added in 100 parts of liquid A step phenolic resin type phenolic resin
The pentamethylene foaming agent and 10 parts of base polyurethane prepolymer for use as of part stir, and adjust pH value to 2 with compound acid as curing agent, obtain phenol
Urea formaldehyde composite C, wherein, the content of metal hydroxides is 5% in phenolic resin composite C.
(4) make phenolic resin composite C as surface layer, phenolic resin composite A and phenolic resin composite B
It is added to for intermediate layer in template, is transferred in 70 DEG C of baking ovens and handles 30min, taking-up obtains polyurethane-modified flexible multi-layered hair
Phenolic resin composite is steeped, wherein, the structure of polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：
The foamed phenolic resin that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
The foamed phenolic resin intermediate layer and acidproof foamed phenolic resin surface layer that intermediate layer, hollow ball are modified.
Embodiment 2：
(1) biological lignin is added in the strong basic ion aqueous solution, 30min is hydrolyzed at 100 DEG C, centrifugation removes not
After molten thing, 1% sulfuric acid solution is added, separates out lignin, washed to neutrality, it is wooden that vacuum drying obtains micro/nano level biology
Element.
(2) it is 1.8 according to the ratio of formaldehyde Pyrogentisinic Acid and the amount of the middle material of lignin, lignin and the amount of phenol material
Than for 5:5, the mass ratio of first paraformaldehyde, second batch paraformaldehyde and the 3rd batch of paraformaldehyde is 5:3:2, phenol is melted
The mixing of micro/nano level biology lignin is added after change, is stirred at 90 DEG C, adds first paraformaldehyde, regulation pH to alkali
Property, continue to react 60min, be cooled to 60 DEG C, add second batch paraformaldehyde, pH is to alkalescence for regulation, is warming up to 80 DEG C of continuation
60min is reacted, is cooled to 60 DEG C, adds the 3rd batch of paraformaldehyde, pH is to alkalescence for regulation, is warming up to 80 DEG C and continues to react
60min, room temperature is cooled to, obtains liquid A step phenolic resin type phenolic resin.
(3) by weight, it is 0.5-5mm by length is added in 100 parts of liquid A step phenolic resin type phenolic resin
Carbon chopped fiber, 10 parts of tween emulsifier, 20 parts of pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as stir, use
Compound acid as curing agent adjusts pH value to 3, stirs, obtains phenolic resin composite A, wherein, phenolic resin composite A
The content of middle carbon chopped fiber is 15%.
The silicon dioxide hollow that particle diameter is 1000nm will be added in 100 parts of liquid A step phenolic resin type phenolic resin
Ball, 10 parts of tween emulsifier, 20 parts of pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as stir, and are consolidated with Compound-acid
Agent adjusts pH value to 3, obtains phenolic resin composite B, wherein, hollow silicon dioxide is micro- in phenolic resin composite B
The content of ball is 16%.
Magnesium hydroxide, 10 parts of tween emulsifier, 20 will be added in 100 parts of liquid A step phenolic resin type phenolic resin
The pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as of part stir, and adjust pH value to 3 with compound acid as curing agent, obtain phenol
Urea formaldehyde composite C, wherein, the content of metal hydroxides is 10% in phenolic resin composite C.
(4) make phenolic resin composite C as surface layer, phenolic resin composite A and phenolic resin composite B
It is added to for intermediate layer in template, is transferred in 70 DEG C of baking ovens and handles 60min, taking-up obtains polyurethane-modified flexible multi-layered hair
Phenolic resin composite is steeped, wherein, the structure of polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：
The foamed phenolic resin that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
Intermediate layer and acidproof foamed phenolic resin surface layer.
Embodiment 3：
(1) biological lignin is added in the strong basic ion aqueous solution, 15min is hydrolyzed at 95 DEG C, centrifugation removes not
After molten thing, 1% sulfuric acid solution is added, separates out lignin, washed to neutrality, it is wooden that vacuum drying obtains micro/nano level biology
Element.
(2) it is 1.6 according to the ratio of formaldehyde Pyrogentisinic Acid and the amount of the middle material of lignin, lignin and the amount of phenol material
Than for 4:6, the mass ratio of first paraformaldehyde, second batch paraformaldehyde and the 3rd batch of paraformaldehyde is 5:3:2, phenol is melted
The mixing of micro/nano level biology lignin is added after change, is stirred at 85 DEG C, adds first paraformaldehyde, regulation pH to alkali
Property, continue to react 40min, be cooled to 60 DEG C, add second batch paraformaldehyde, pH is to alkalescence for regulation, is warming up to 80 DEG C of continuation
40min is reacted, is cooled to 60 DEG C, adds the 3rd batch of paraformaldehyde, pH is to alkalescence for regulation, is warming up to 80 DEG C and continues to react
40min, room temperature is cooled to, obtains liquid A step phenolic resin type phenolic resin.
(3) by weight, it is 0.5-5mm by length is added in 100 parts of liquid A step phenolic resin type phenolic resin
Carbon chopped fiber, 8 parts of tween emulsifier, 15 parts of pentamethylene foaming agent and 13 parts of base polyurethane prepolymer for use as stir, use
Compound acid as curing agent adjusts pH value to 2.5, stirs, obtains phenolic resin composite A, wherein, phenolic resin composite wood
The content for expecting carbon chopped fiber in A is 11%.
By being added in 100 parts of liquid A step phenolic resin type phenolic resin, the silica that particle diameter is 100-1000nm is empty
Bulbus cordis, 7 parts of tween emulsifier, 17 parts of pentamethylene foaming agent and 18 parts of base polyurethane prepolymer for use as stir, and use Compound-acid
Curing agent adjusts pH value to 2.4, obtains phenolic resin composite B, wherein, hollow titanium dioxide in phenolic resin composite B
The content of silicon microballoon is 10%.
Aluminium hydroxide, 8 parts of tween emulsifier, 13 will be added in 100 parts of liquid A step phenolic resin type phenolic resin
The pentamethylene foaming agent and 14 parts of base polyurethane prepolymer for use as of part stir, and adjust pH value to 3 with compound acid as curing agent, obtain phenol
Urea formaldehyde composite C, wherein, the content of metal hydroxides is 7% in phenolic resin composite C.
(4) make phenolic resin composite C as surface layer, phenolic resin composite A and phenolic resin composite B
It is added to for intermediate layer in template, is transferred in 70 DEG C of baking ovens and handles 40min, taking-up obtains polyurethane-modified flexible multi-layered hair
Phenolic resin composite is steeped, wherein, the structure of polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：
The foamed phenolic resin that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
The foamed phenolic resin intermediate layer and acidproof foamed phenolic resin surface layer that intermediate layer, hollow ball are modified.
Embodiment 4：
(1) biological lignin is added in the strong basic ion aqueous solution, 25min is hydrolyzed at 95 DEG C, centrifugation removes not
After molten thing, 1% sulfuric acid solution is added, separates out lignin, washed to neutrality, it is wooden that vacuum drying obtains micro/nano level biology
Element.
(2) it is 1.7 according to the ratio of formaldehyde Pyrogentisinic Acid and the amount of the middle material of lignin, lignin and the amount of phenol material
Than for 5:5, the mass ratio of first paraformaldehyde, second batch paraformaldehyde and the 3rd batch of paraformaldehyde is 5:3:2, phenol is melted
The mixing of micro/nano level biology lignin is added after change, is stirred at 85 DEG C, adds first paraformaldehyde, regulation pH to alkali
Property, continue to react 50min, be cooled to 60 DEG C, add second batch paraformaldehyde, pH is to alkalescence for regulation, is warming up to 75 DEG C of continuation
40min is reacted, is cooled to 60 DEG C, adds the 3rd batch of paraformaldehyde, pH is to alkalescence for regulation, is warming up to 75 DEG C and continues to react
45min, room temperature is cooled to, obtains liquid A step phenolic resin type phenolic resin.
(3) by weight, it is 0.5-5mm by length is added in 100 parts of liquid A step phenolic resin type phenolic resin
Carbon chopped fiber, 7 parts of tween emulsifier, 12 parts of pentamethylene foaming agent and 16 parts of base polyurethane prepolymer for use as stir, use
Compound acid as curing agent adjusts pH value to 2.3, stirs, obtains phenolic resin composite A, wherein, phenolic resin composite wood
The content for expecting carbon chopped fiber in A is 13%.
By being added in 100 parts of liquid A step phenolic resin type phenolic resin, the silica that particle diameter is 100-1000nm is empty
Bulbus cordis, 8 parts of tween emulsifier, 17 parts of pentamethylene foaming agent and 13 parts of base polyurethane prepolymer for use as stir, and use Compound-acid
Curing agent adjusts pH value to 2.6, obtains phenolic resin composite B, wherein, hollow titanium dioxide in phenolic resin composite B
The content of silicon microballoon is 12%.
Magnesium hydroxide, 7 parts of tween emulsifier, 14 will be added in 100 parts of liquid A step phenolic resin type phenolic resin
The pentamethylene foaming agent and 17 parts of base polyurethane prepolymer for use as of part stir, and adjust pH value to 2.5 with compound acid as curing agent, obtain
Phenolic resin composite C, wherein, the content of metal hydroxides is 8% in phenolic resin composite C.
(4) make phenolic resin composite C as surface layer, phenolic resin composite A and phenolic resin composite B
It is added to for intermediate layer in template, is transferred in 70 DEG C of baking ovens and handles 40min, taking-up obtains polyurethane-modified flexible multi-layered hair
Phenolic resin composite is steeped, wherein, the structure of polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：
The foamed phenolic resin that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
Intermediate layer and acidproof foamed phenolic resin surface layer.
Embodiment 5：
(1) biological lignin is added in the strong basic ion aqueous solution, 10min is hydrolyzed at 100 DEG C, centrifugation removes not
After molten thing, 1% sulfuric acid solution is added, separates out lignin, washed to neutrality, it is wooden that vacuum drying obtains micro/nano level biology
Element.
(2) it is 1.8 according to the ratio of formaldehyde Pyrogentisinic Acid and the amount of the middle material of lignin, lignin and the amount of phenol material
Than for 3:7, the mass ratio of first paraformaldehyde, second batch paraformaldehyde and the 3rd batch of paraformaldehyde is 5:3:2, phenol is melted
The mixing of micro/nano level biology lignin is added after change, is stirred at 90 DEG C, adds first paraformaldehyde, regulation pH to alkali
Property, continue to react 30min, be cooled to 60 DEG C, add second batch paraformaldehyde, pH is to alkalescence for regulation, is warming up to 80 DEG C of continuation
30min is reacted, is cooled to 60 DEG C, adds the 3rd batch of paraformaldehyde, pH is to alkalescence for regulation, is warming up to 80 DEG C and continues to react
30min, room temperature is cooled to, obtains liquid A step phenolic resin type phenolic resin.
(3) by weight, it is 0.5-5mm by length is added in 100 parts of liquid A step phenolic resin type phenolic resin
Carbon chopped fiber, 6 parts of tween emulsifier, 20 parts of pentamethylene foaming agent and 10 parts of base polyurethane prepolymer for use as stir, use
Compound acid as curing agent adjusts pH value to 3, stirs, obtains phenolic resin composite A, wherein, phenolic resin composite A
The content of middle carbon chopped fiber is 14%.
By being added in 100 parts of liquid A step phenolic resin type phenolic resin, the silica that particle diameter is 100-1000nm is empty
Bulbus cordis, 10 parts of tween emulsifier, 10 parts of pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as stir, and use Compound-acid
Curing agent adjusts pH value to 2, obtains phenolic resin composite B, wherein, hollow silicon dioxide in phenolic resin composite B
The content of microballoon is 14%.
Aluminium hydroxide, 6 parts of tween emulsifier, 20 will be added in 100 parts of liquid A step phenolic resin type phenolic resin
The pentamethylene foaming agent and 10 parts of base polyurethane prepolymer for use as of part stir, and adjust pH value to 3 with compound acid as curing agent, obtain phenol
Urea formaldehyde composite C, wherein, the content of metal hydroxides is 9% in phenolic resin composite C.
(4) make phenolic resin composite C as surface layer, phenolic resin composite A and phenolic resin composite B
It is added to for intermediate layer in template, is transferred in 70 DEG C of baking ovens and handles 60min, taking-up obtains polyurethane-modified flexible multi-layered hair
Phenolic resin composite is steeped, wherein, the structure of polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：
The foamed phenolic resin that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
The foamed phenolic resin intermediate layer and acidproof foamed phenolic resin surface layer that intermediate layer, hollow ball are modified.
Embodiment 6：
(1) biological lignin is added in the strong basic ion aqueous solution, 30min is hydrolyzed at 90 DEG C, centrifugation removes not
After molten thing, 1% sulfuric acid solution is added, separates out lignin, washed to neutrality, it is wooden that vacuum drying obtains micro/nano level biology
Element.
(2) it is 1.8 according to the ratio of formaldehyde Pyrogentisinic Acid and the amount of the middle material of lignin, lignin and the amount of phenol material
Than for 5:5, the mass ratio of first paraformaldehyde, second batch paraformaldehyde and the 3rd batch of paraformaldehyde is 5:3:2, phenol is melted
The mixing of micro/nano level biology lignin is added after change, is stirred at 80 DEG C, adds first paraformaldehyde, regulation pH to alkali
Property, continue to react 60min, be cooled to 60 DEG C, add second batch paraformaldehyde, pH is to alkalescence for regulation, is warming up to 70 DEG C of continuation
60min is reacted, is cooled to 60 DEG C, adds the 3rd batch of paraformaldehyde, pH is to alkalescence for regulation, is warming up to 70 DEG C and continues to react
30min, room temperature is cooled to, obtains liquid A step phenolic resin type phenolic resin.
(3) by weight, it is 0.5-5mm by length is added in 100 parts of liquid A step phenolic resin type phenolic resin
Carbon chopped fiber, 8 parts of tween emulsifier, 20 parts of pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as stir, use
Compound acid as curing agent adjusts pH value to 2, stirs, obtains phenolic resin composite A, wherein, phenolic resin composite A
The content of middle carbon chopped fiber is 11%.
By being added in 100 parts of liquid A step phenolic resin type phenolic resin, the silica that particle diameter is 100-1000nm is empty
Bulbus cordis, 6 parts of tween emulsifier, 10 parts of pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as stir, and use Compound-acid
Curing agent adjusts pH value to 2, obtains phenolic resin composite B, wherein, hollow silicon dioxide in phenolic resin composite B
The content of microballoon is 12%.
Magnesium hydroxide, 9 parts of tween emulsifier, 15 will be added in 100 parts of liquid A step phenolic resin type phenolic resin
The pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as of part stir, and adjust pH value to 2 with compound acid as curing agent, obtain phenol
Urea formaldehyde composite C, wherein, the content of metal hydroxides is 7% in phenolic resin composite C.
(4) make phenolic resin composite C as surface layer, phenolic resin composite A and phenolic resin composite B
It is added to for intermediate layer in template, is transferred in 70 DEG C of baking ovens and handles 60min, taking-up obtains polyurethane-modified flexible multi-layered hair
Phenolic resin composite is steeped, wherein, the structure of polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：
The foamed phenolic resin that acidproof foamed phenolic resin surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, chopped fiber are modified
Intermediate layer and acidproof foamed phenolic resin surface layer.
Comparative example：
2 parts of aluminium hydroxides, 5 parts of carbon chopped fibers, 1 part of sky are added in 100 parts of liquid A step phenolic resin type phenolic resin
Heart silica, 9 parts of tween emulsifier, 15 parts of pentamethylene foaming agent and 20 parts of base polyurethane prepolymer for use as stir, and add
Enter into template, be transferred in 70 DEG C of baking ovens and handle 60min, taking-up obtains polyurethane-modified foamed phenolic resin composite wood
Material.
After testing, the polyurethane-modified flexible multi-layered foamed phenolic resin composite that prepared by embodiment 1-6 and contrast
The result of the environment-friendly type flame-retardant of polyurethane-modified foamed phenolic resin composite, heat resistance and mechanical performance prepared by example
It is as follows：
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Comparative example | |
| The content (%) of free formaldehyde | 0 | 0.3 | 0.1 | 0.1 | 0 | 0.2 | 3.5 |
| Pyrolysis temperature (DEG C) | 234 | 246 | 230 | 231 | 245 | 237 | 226 |
| Quality remnants (%) after heat treatment | 70 | 73 | 70 | 71 | 72 | 70 | 64 |
| Compressive strength (MPa) | 0.16 | 0.21 | 0.19 | 0.20 | 0.17 | 0.19 | 0.13 |
| Tensile strength (MPa) | 0.09 | 0.08 | 0.09 | 0.07 | 0.08 | 0.09 | 0.03 |
As seen from the above table, the polyurethane-modified flexible multi-layered foamed phenolic resin composite that prepared by the present invention, which uses, to be divided
Rotating fields, interlayer do not have obvious boundary line, and heat resistance, fire resistance and mechanical performance are all significantly improved.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
- A kind of 1. polyurethane-modified flexible multi-layered foamed phenolic resin composite, it is characterised in that：It is described polyurethane-modified Flexible multi-layered foamed phenolic resin composite include acidproof foamed phenolic resin surface layer, hollow ball be modified foamable phenolic tree The foamed phenolic resin intermediate layer that fat intermediate layer and chopped fiber are modified, the acidproof foamed phenolic resin surface layer, hollow ball and short All contain polyurethane foam resin in the foamed phenolic resin intermediate layer of fibre modification, the chopped fiber is carbon chopped fiber.
- 2. a kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 1, its feature It is：The structure of the polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：Acidproof foamable phenolic tree Fat surface layer, the foamed phenolic resin intermediate layer of hollow ball modification, the foamed phenolic resin intermediate layer of chopped fiber modification, hollow ball change The foamed phenolic resin intermediate layer of property and acidproof foamed phenolic resin surface layer.
- 3. a kind of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 1, its feature It is：The structure of the polyurethane-modified flexible multi-layered foamed phenolic resin composite is followed successively by：Acidproof foamable phenolic tree Foamed phenolic resin intermediate layer, the foamed phenolic resin intermediate layer of chopped fiber modification and the acidproof hair that fat surface layer, hollow ball are modified Steep phenolic resin surface layer.
- A kind of 4. preparation method of polyurethane-modified flexible multi-layered foamed phenolic resin composite, it is characterised in that including Following steps：(1) biological lignin is added in the strong basic ion aqueous solution and hydrolyzed, after centrifugation removes insoluble matter, add 1% sulphur Acid solution, lignin is separated out, wash to neutrality, vacuum drying and obtain micro/nano level biology lignin；(2) micro/nano level biology lignin mixing prepared by step (1) is added after phenol is melted, is stirred at 80-90 DEG C equal It is even, first paraformaldehyde is added, regulation pH to alkalescence, continues to react 30-60min, is cooled to 60 DEG C, it is more to add second batch Polyformaldehyde, regulation pH to alkalescence, it is warming up to 70-80 DEG C and continues to react 30-60min, be cooled to 60 DEG C, add the 3rd batch of poly Formaldehyde, regulation pH to alkalescence, it is warming up to 70-80 DEG C and continues to react 30-60min, be cooled to room temperature, obtain liquid first rank phenolic aldehyde tree Epoxy-type phenolic resin；(3) carbon chopped fiber, emulsifying agent and foaming agent are added in the liquid A step phenolic resin type phenolic resin for preparing step (2) Stirred with base polyurethane prepolymer for use as, adjust pH value to 2-3 with compound acid as curing agent, stir, it is compound to obtain phenolic resin Materials A, will step (2) prepare liquid A step phenolic resin type phenolic resin in add hollow silica ball, emulsifying agent and Foaming agent and base polyurethane prepolymer for use as stir, and adjust pH value to 2-3 with compound acid as curing agent, obtain phenolic resin composite B；Metal hydroxides, emulsifying agent and foaming agent are added in liquid A step phenolic resin type phenolic resin prepared by step (2) Stirred with base polyurethane prepolymer for use as, adjust pH value to 2-3 with compound acid as curing agent, obtain phenolic resin composite C；(4) phenolic resin composite C, phenolic resin composite B and the phenolic resin composite A for preparing step (2) It is added in template, is transferred in 70 DEG C of baking ovens and handles 30-60min, taking-up obtains polyurethane-modified flexible multi-layered foaming phenol Urea formaldehyde composite.
- A kind of 5. preparation side of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 4 Method, it is characterised in that：In the step (1), the temperature of hydrolysis is 90-100 DEG C, time 10-30min.
- A kind of 6. preparation side of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 4 Method, it is characterised in that：In the step (2), the ratio of the amount of the middle material of formaldehyde Pyrogentisinic Acid and lignin is 1.5-1.8, described Lignin and the ratio of the amount of phenol material are 3-5:5-7.
- A kind of 7. preparation side of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 4 Method, it is characterised in that：In the step (2), the matter of first paraformaldehyde, second batch paraformaldehyde and the 3rd batch of paraformaldehyde Amount is than being 5:3:2.
- A kind of 8. preparation side of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 4 Method, it is characterised in that：In the step (3), the content of carbon chopped fiber is 10-15% in phenolic resin composite A, phenolic aldehyde tree The content of hollow silicon dioxide microsphere is 8-16% in resin composite material B, metal hydroxides in phenolic resin composite C Content is 5-10%.
- A kind of 9. preparation side of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 4 Method, it is characterised in that：In the step (3), phenolic resin composite A, phenolic resin composite B and phenolic resin are compound The content of base polyurethane prepolymer for use as is 10-20% in material C.
- A kind of 10. preparation of polyurethane-modified flexible multi-layered foamed phenolic resin composite according to claim 4 Method, it is characterised in that：In the step (4), phenolic resin composite C is as surface layer, phenolic resin composite A and phenol Urea formaldehyde composite B is as intermediate layer.
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