CN109369950A - A kind of supercritical carbon dioxide foaming phenol formaldehyde foam and preparation method thereof - Google Patents

A kind of supercritical carbon dioxide foaming phenol formaldehyde foam and preparation method thereof Download PDF

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CN109369950A
CN109369950A CN201811311388.1A CN201811311388A CN109369950A CN 109369950 A CN109369950 A CN 109369950A CN 201811311388 A CN201811311388 A CN 201811311388A CN 109369950 A CN109369950 A CN 109369950A
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phenol
supercritical
foam
carbon dioxide
foaming
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钟东南
孙志武
张威
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Shandong Tianyang New Materials Co Ltd
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Shandong Tianyang New Materials Co Ltd
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    • 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
    • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
    • 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
    • C08J2203/06—CO2, N2 or noble gases
    • 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
    • C08J2203/08—Supercritical fluid
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • 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
    • C08J2203/20—Ternary blends of expanding agents
    • C08J2203/202—Ternary blends of expanding agents of physical blowing agents
    • 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
    • C08J2361/14—Modified phenol-aldehyde condensates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a kind of supercritical carbon dioxide foaming phenol formaldehyde foams, belong to phenolic aldehyde technical field, it is made after being mixed by phenolic resin masterbatch with curing agent, the mass ratio of the phenolic resin masterbatch and curing agent is 1: 0.2~0.6, the phenolic resin masterbatch is made of phenol-formaldehyde resin modified, foam stabilizer, foaming agent, it is in terms of 100 parts by phenolic resin masterbatch gross mass, the mass parts of the foaming agent are 3~10 parts, and foaming agent is supercritical CO2Or Traditional blowing agents and supercritical CO2Mixture, Traditional blowing agents and supercritical CO2Mixing ratio it is any；The mass fraction of the foam stabilizer is 3~8 parts.This method is by liquid CO2Phenolic resin masterbatch is prepared with supercriticality, and then carries out acid solidification and prepares the phenol formaldehyde foam, preparation method is simple and reliable, is suitable for practical promote and apply.

Description

A kind of supercritical carbon dioxide foaming phenol formaldehyde foam and preparation method thereof
Technical field
The invention belongs to phenolic aldehyde technical fields, and in particular to a kind of supercritical carbon dioxide foaming phenol formaldehyde foam and its preparation Method.
Background technique
Phenol formaldehyde foam is foamed using low-boiling foaming agent pentane, pentamethylene.This kind of low-boiling compound absorbing phenolic resin The heat released is reacted with curing agent and is gasified, and achievees the purpose that foaming.But belong to inflammable explosive article, the high requirements on the equipment, And there are certain security risks for production.
CO2It is that one kind has with ODP value is 0, GWP value is extremely low, bubbling efficiency is high, the excellent characteristic such as non-ignitable, nontoxic The inexpensive foaming agent of broad prospect of application.Other than low-boiling foaming agent pentane, pentamethylene foaming, due to CO2Boiling point is extremely low, Highly volatile in air, so needing to explore viable process and its preparation side for carrying out phenolic foam using liquid carbon dioxide Method.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of supercritical carbon dioxide foaming phenol formaldehyde foam and its preparation side Method, phenol formaldehyde foam of the invention use low-boiling liquid CO2Or liquid CO2With other foaming agent certain proportion mixed foaming systems It is standby, and special formula system is used, so that phenol formaldehyde foam of the invention is had good intensity, heat-insulating property and dimensionally stable Property, in addition the present invention also while providing the mating preparation method of the phenol formaldehyde foam, and this method is by liquid CO2With supercriticality Phenolic resin masterbatch is prepared, and then carries out acid solidification and prepares the phenol formaldehyde foam, preparation method is simple and reliable, is suitable for practical promote Using.
The present invention is achieved by the following technical solutions:
A kind of supercritical carbon dioxide foaming phenol formaldehyde foam is made, the phenolic aldehyde after being mixed by phenolic resin masterbatch with curing agent The mass ratio of resin concentrates and curing agent is 1: 0.2~0.6, and the phenolic resin masterbatch is by phenol-formaldehyde resin modified, foam stabilizer, hair Infusion composition is in terms of 100 parts by phenolic resin masterbatch gross mass, and the mass parts of the foaming agent are 3~10 parts, and foaming agent is super Critical CO2Or Traditional blowing agents and supercritical CO2Mixture, Traditional blowing agents and supercritical CO2Mixing ratio it is any；Institute The mass fraction for stating foam stabilizer is 3~8 parts.
Preferably, the Traditional blowing agents be selected from one of pentane and pentamethylene or more than one.
Preferably, the phenolic resin is basic raw material by using phenol, liquid formaldehyde or paraformaldehyde, synthesized Cheng Caiyong modifying agent methylolurea carries out graft modification, obtains phenol-formaldehyde resin modified.
Preferably, the foam stabilizer be selected from one of TWEEN Series, siloxane series, ionic series or it is a kind of with On.
It is highly preferred that the group of the foam stabilizer becomes one kind or one kind of silicone oil AK158, polysorbas20, polysorbate40, Tween 80 More than.
Preferably, the curing agent in sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid and acetic acid one Kind or more than one.
Supercritical carbon dioxide foaming phenol formaldehyde foam preparation method described above, comprising the following steps:
Step 1, phenol-formaldehyde resin modified, foam stabilizer, foaming agent are subjected to physics mixture；
Step 2, the liquid CO that high pressure is canned2It is changed into supercritical state by decompression gasification and the increased pressure liquefied mode that cools down State；
Step 3, the supercritical CO in proportion obtained step 22The mixture obtained with step 1 is sufficiently mixed, and becomes phenolic aldehyde tree Rouge masterbatch；
Step 4, under certain temperature of charge and environment temperature, by phenolic resin masterbatch described in curing agent and step 3 through high pressure Pump foams after being delivered to mixing pipette tips mixing；
Step 5, after certain curing time, supercritical CO is obtained2Foamable phenolic foam.
Preferably, the temperature of charge in the step 4 is 55~65 DEG C, and the environment temperature in the step 4 is -10~35 ℃。
Preferably, the curing time in the step 5 is 4~8min.
Beneficial effect
1, phenol formaldehyde foam of the invention uses low-boiling liquid CO2Or liquid CO2Hair is mixed with other foaming agent certain proportions It is brewed standby, it can single foaming agent, it can also be with mixed foaming agent；
2, using pure phenolic resin foaming system, toughening, heat-resisting, impact resistance of other Related products etc. is not needed and is modified again；
3, using special Phenolic Formulations preparation system, phenol formaldehyde foam of the invention is made to have good intensity, heat-insulating property And dimensional stability；
4, nontoxic and pollution-free using the green-blowing agent of zero odp, comply with the requirement of international environmental convention；
5, construction environment tolerance of the invention is high, can meet low-temperature construction environment, have a wide range of application, and modification method for preparing is to setting Standby is of less demanding, and preparation method is simple and reliable.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.
Different formulations ratio supercritical CO2Foaming agent prepare phenol formaldehyde foam method and comparison example it is as follows:
1) phenol-formaldehyde resin modified, foam stabilizer, foaming agent (foaming agent can be not added) are subjected to physics mixture；
2) the phenolic resin masterbatch after mixture is delivered in foaming machine equipment tank by mentioning material pump and delivery pipe, while curing agent is logical It crosses to mention and expects that pump and delivery pipe are delivered in equipment tank；
3) liquid CO2By decompression gasification, cool down it is increased pressure liquefied after be delivered in phenolic resin masterbatch equipment tank with constant ratio, It is sufficiently mixed in the supercritical state with phenolic resin masterbatch；
4) in the case where temperature of charge is 55~65 DEG C and environment temperature is -10~35 DEG C, foaming machine is by phenolic resin masterbatch and admittedly Agent is delivered to premix spray gun with fixed proportion, sprays after mixing；
5) pass through certain curing time, obtain phenol formaldehyde foam.
Liquid CO in comparative example and embodiment2It is added with supercriticality, due to phenolic resin masterbatch and curing agent Mass ratio at 1: 0.2~0.6, foaming properties be not in conspicuousness difference, so in comparative example and implementation of the invention The mass ratio of phenolic resin masterbatch and curing agent is set as representative 1: 0.5 in example.
Comparative example 1
Phenol-formaldehyde resin modified A(methylolurea is modified), catalyst A is sodium hydroxide catalyzed preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentane, pentamethylene, mass ratio 2:1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Comparative example 2
Phenol-formaldehyde resin modified A, catalyst A preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentane, mass ratio 1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Comparative example 3
Phenol-formaldehyde resin modified A, catalyst A preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentamethylene, mass ratio 1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Comparative example 4
Phenol-formaldehyde resin modified A, catalyst A preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Comparative example 5
Phenol-formaldehyde resin modified B(methylolurea is modified), catalyst B is barium hydroxide catalysis preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentane, pentamethylene, mass ratio 2:1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Comparative example 6
Phenol-formaldehyde resin modified B, catalyst B preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentane, mass ratio 1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Comparative example 7
Phenol-formaldehyde resin modified B, catalyst B preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentamethylene, mass ratio 1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Comparative example 8
Phenol-formaldehyde resin modified B, catalyst B preparation；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Embodiment 1
Phenol-formaldehyde resin modified A, phenol-formaldehyde resin modified B；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentane, pentamethylene, mass ratio 2:1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Embodiment 2
Phenol-formaldehyde resin modified A, phenol-formaldehyde resin modified B；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentane, mass ratio 1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Embodiment 3
Phenol-formaldehyde resin modified A, phenol-formaldehyde resin modified B；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2, pentamethylene, mass ratio 1:1；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
Embodiment 4
Phenol-formaldehyde resin modified A, phenol-formaldehyde resin modified B；
Compound foam stabilizer filters out from the foam stabilizers such as TWEEN Series, siloxane series, ionic series and is suitable for formula system Compound foam stabilizer, the foam stabilizer silicone oil AK158, Tween 80 mass ratio be 1:0.8；
Foaming agent is supercritical CO2；
Curing agent is filtered out again by resin activity from sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid, acetic acid etc. Close curing agent, p-methyl benzenesulfonic acid, xylene monosulfonic acid mass ratio be 1:0.4；
Foaming formulation and technique are shown in Table 1.
By comparative example 1 to 4,5 to 8, illustrate within the scope of the present disclosure, ideal super face has been prepared Boundary CO2Foamable phenolic foam.By embodiment 1 to 4, illustrate supercritical CO2Foamable phenolic foam has original foaming system substantially Apparent technical indicator.
The hard polyurethane foams performance that each comparative example of table 2 and embodiment obtain
Each comparative example and the obtained foaming properties of embodiment are shown in Table 2, and from the data in the table, foam of the invention has lower Thermal coefficient, higher compressive strength.
With supercritical CO2As foaming agent, by liquid CO2It is directly appended in system after being converted into supercriticality, low boiling The CO of point2As foaming agent addition after can gasify rapidly, effectively improve phenolic resin curing generation starting it is slow, foam is crisp, The low deficiency with poor dimensional stability of intensity, while liquid CO2Part reaction heat can be taken away when volatilization, avoided foaming and easily burnt core The problem of；Due to liquid CO2Boiling point is far below room temperature, and foaming process is the foaming of foam shape, the mechanical property and heat-insulating property of foam It increases, so high temperature and when ultra low temperature state keep preferable dimensional stability to product at lower densities.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies Within, then the present invention is also intended to include these modifications and variations.

Claims (9)

1. a kind of supercritical carbon dioxide foaming phenol formaldehyde foam is made, the phenol after being mixed by phenolic resin masterbatch with curing agent The mass ratio of urea formaldehyde masterbatch and curing agent be 1: 0.2~0.6, the phenolic resin masterbatch by phenol-formaldehyde resin modified, foam stabilizer, Foaming agent composition, it is characterised in that: by phenolic resin masterbatch gross mass be in terms of 100 parts, the mass parts of the foaming agent are 3~10 Part, foaming agent is supercritical CO2Or Traditional blowing agents and supercritical CO2Mixture, Traditional blowing agents and supercritical CO2's Mixing ratio is any；The mass fraction of the foam stabilizer is 3~8 parts.
2. supercritical carbon dioxide foaming phenol formaldehyde foam according to claim 1, it is characterised in that: the Traditional blowing agents Selected from one of pentane and pentamethylene or more than one.
3. supercritical carbon dioxide foaming phenol formaldehyde foam according to claim 1, it is characterised in that: the phenolic resin, It is basic raw material by using phenol, liquid formaldehyde or paraformaldehyde, synthesis process carries out graft modification using methylolurea, obtains To phenol-formaldehyde resin modified.
4. supercritical carbon dioxide foaming phenol formaldehyde foam according to claim 1, it is characterised in that: the foam stabilizer is selected from One of TWEEN Series, siloxane series, ionic series or more than one.
5. supercritical carbon dioxide foaming phenol formaldehyde foam according to claim 1, it is characterised in that: the group of the foam stabilizer One or more as silicone oil AK158, polysorbas20, polysorbate40, Tween 80.
6. supercritical carbon dioxide foaming phenol formaldehyde foam according to claim 1, it is characterised in that: the curing agent is selected from One of sulfuric acid, phosphoric acid, p-methyl benzenesulfonic acid, phenol sulfonic acid, methane sulfonic acid and acetic acid or more than one.
7. supercritical carbon dioxide foaming phenol formaldehyde foam preparation method described in -6 according to claim 1, it is characterised in that: including Following steps:
Step 1, phenol-formaldehyde resin modified, foam stabilizer, foaming agent are subjected to physics mixture；
Step 2, the liquid CO that high pressure is canned2It is changed into supercriticality by decompression gasification and the increased pressure liquefied mode that cools down；
Step 3, the supercritical CO in proportion obtained step 22The mixture obtained with step 1 is sufficiently mixed, and becomes phenolic resin Masterbatch；
Step 4, under certain temperature of charge and environment temperature, by phenolic resin masterbatch described in curing agent and step 3 through high pressure Pump foams after being delivered to mixing pipette tips mixing；
Step 5, after certain curing time, supercritical CO is obtained2Foamable phenolic foam.
8. supercritical carbon dioxide foaming phenol formaldehyde foam preparation method according to claim 7, it is characterised in that: the step Temperature of charge in rapid 4 is 55~65 DEG C, and the environment temperature in the step 4 is -10~35 DEG C.
9. supercritical carbon dioxide foaming phenol formaldehyde foam preparation method according to claim 7, it is characterised in that: the step Curing time in rapid 5 is 4~8min.
CN201811311388.1A 2018-11-06 2018-11-06 A kind of supercritical carbon dioxide foaming phenol formaldehyde foam and preparation method thereof Pending CN109369950A (en)

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CN114395406A (en) * 2022-02-15 2022-04-26 辽宁工程技术大学 Preparation method and application of foam particles wrapping carbon dioxide gas

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Application publication date: 20190222