CN112574576B - Polymer foam material and preparation method thereof - Google Patents

Polymer foam material and preparation method thereof Download PDF

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CN112574576B
CN112574576B CN201910944562.4A CN201910944562A CN112574576B CN 112574576 B CN112574576 B CN 112574576B CN 201910944562 A CN201910944562 A CN 201910944562A CN 112574576 B CN112574576 B CN 112574576B
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庞永艳
郑文革
覃康培
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/04—Oxidation
    • C08C19/06—Epoxidation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/24—Incorporating phosphorus atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/40—Introducing phosphorus atoms or phosphorus-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • 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
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • 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
    • C08J2387/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

Abstract

The invention relates to a polymer foaming material and a preparation method thereof, wherein the preparation method comprises the following steps: providing a polymer with a main chain containing double bonds, mixing the polymer with a hyperoxidant and a first solvent, and reacting at a first temperature to obtain a first intermediate product; then mixing with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a second solvent, reacting at a second temperature to obtain a solution containing a second intermediate product, wherein the molecular chain of the second intermediate product contains a chemical structure shown in a formula (1),
Figure DDA0002223798660000011
mixing the solution containing the second intermediate product with polyaniline, and reacting at a third temperature to obtain a third intermediate product, wherein the molecular chain of the third intermediate product contains a chemical structure shown as a formula (1) and a chemical structure shown as a formula (2),
Figure DDA0002223798660000012
and mixing and hot-pressing the third intermediate product with a cross-linking agent and a foaming agent to obtain a prefabricated product, and simultaneously cross-linking and foaming the prefabricated product at the temperature of 140-250 ℃ to obtain the polymer foaming material with excellent flame retardance, heat preservation, sound insulation and elasticity.

Description

Polymer foam material and preparation method thereof
Technical Field
The invention relates to the technical field of high molecular materials, in particular to a polymer foam material and a preparation method thereof.
Background
Polymers such as rubber are organic combustible materials, so that various rubber products such as rubber conveyer belts for mines and vehicles and ships are required to have flame retardant property. The traditional method for improving the flame retardance of the rubber is mainly to blend the difficult-to-burn rubber such as chloroprene rubber, silicon rubber and the like with the rubber to be modified, or to add the chlorinated paraffin and small molecular flame retardants such as antimony trioxide, aluminum hydroxide, sodium borate, molybdenum oxide, triphenyl phosphate and the like or difficult-to-burn fillers such as pottery clay, white carbon black and the like into the rubber to be modified.
However, different rubbers have different foaming characteristics, and the foam structure of the rubber foam material is seriously influenced by mixing a large amount of flame-retardant rubber. If a small molecular flame retardant or other flame-retardant fillers are added, the foaming is also seriously influenced if the addition amount is large; meanwhile, the small molecular flame retardant is easy to exude from a rubber matrix due to poor compatibility of the small molecular flame retardant and rubber, and the phenomenon is particularly obvious in a foaming material. Therefore, these conventional flame retardant modification methods are not suitable for rubber foams.
Disclosure of Invention
In view of the above, there is a need to provide a polymer foam material and a method for preparing the same; the preparation method comprises the steps of firstly obtaining the polymer with the intrinsic flame-retardant effect, and then foaming to obtain the polymer foam material with excellent flame retardance, heat preservation, sound insulation and elasticity.
A method of making a polymer foam comprising:
providing a polymer, mixing the polymer with a peroxide and a first solvent, and reacting at a first temperature to obtain a first intermediate product, wherein the main chain of the polymer contains double bonds;
mixing the first intermediate product with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a second solvent, reacting at a second temperature to obtain a solution containing a second intermediate product, wherein the molecular chain of the second intermediate product contains a chemical structure shown in a formula (1),
Figure BDA0002223798640000021
mixing the solution containing the second intermediate product with polyaniline, and reacting at a third temperature to obtain a third intermediate product, wherein the molecular chain of the third intermediate product contains a chemical structure shown as a formula (1) and a chemical structure shown as a formula (2),
Figure BDA0002223798640000022
and mixing and hot-pressing the third intermediate product, a cross-linking agent and a foaming agent to obtain a prefabricated product, and simultaneously cross-linking and foaming the prefabricated product at the temperature of 140-250 ℃ to obtain the polymer foam material.
In one embodiment, the polymer comprises at least one of polybutadiene, polyisoprene, styrene butadiene rubber, nitrile rubber, styrene-butadiene-styrene block copolymer, acrylonitrile-butadiene-styrene copolymer.
In one embodiment, the peroxide is capable of partially oxidizing double bonds in the main chain of the polymer to epoxy groups, and the molar ratio of the epoxy groups to remaining double bonds in the main chain of the first intermediate product is 1:9 to 9: 1.
In one embodiment, the molecular chain of the third intermediate product contains the chemical structure represented by formula (1) in a molar amount equal to or greater than the mole of the chemical structure represented by formula (2).
In one embodiment, the molar ratio of the chemical structure represented by formula (1) to the double bonds in the main chain of the third intermediate product in the molecular chain of the third intermediate product is 1: 8-4: 5.
In one embodiment, the molar ratio of the chemical structure shown in formula (2) to the double bonds in the main chain of the third intermediate product in the molecular chain of the third intermediate product is 0.5: 8-1: 5.
In one embodiment, the first temperature is 25 ℃ to 70 ℃, the second temperature is 100 ℃ to 140 ℃, and the third temperature is 100 ℃ to 140 ℃.
In one embodiment, the crosslinking agent comprises at least one of a sulfur cure system, a peroxide, a maleimide, and derivatives thereof.
In one embodiment, the blowing agent comprises at least one of an azo compound, a sulfonphthalein trap compound, a nitroso compound, a microsphere blowing agent.
The polymer foam material is prepared by the preparation method, the aperture size of the polymer foam material is 50-500 mu m, and the cell density is 105～1015Per cm3The expansion ratio is 1 to 15 times.
In the preparation method, firstly, 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and polyaniline are used as a reactive flame retardant and a char forming agent to graft and modify a polymer containing double bonds, so that the modified polymer (namely a third intermediate product) has excellent flame retardance and char forming property, the reduction of molten drops in the combustion process is facilitated, and the structure of a polymer foaming material does not collapse while the flame retardant effect is realized. And secondly, because the modified polymer has excellent flame retardance and char formation, a large amount of flame-retardant rubber, a small molecular flame retardant or other flame-retardant fillers do not need to be mixed into the modified polymer, the foaming characteristic of the modified polymer is not influenced, and the polymer foaming material with excellent performances such as flame retardance, heat preservation, sound insulation, buffering and the like can be obtained only by simultaneously crosslinking and foaming the modified polymer.
In addition, the preparation method has simple process, safety, high efficiency and good controllability, and can regulate the flame retardant property and expansion ratio, the cell size and distribution and the cell density of the polymer foam material by regulating the grafting amount of DOPO and polyaniline and the dosage of the cross-linking agent and the foaming agent, thereby regulating the performance of the polymer foam material.
Drawings
FIG. 1 is an electron micrograph of a polybutadiene rubber foam obtained in example 1 of the present invention;
FIG. 2 is an electron micrograph of an isoprene rubber foam obtained in example 6 of the present invention.
Detailed Description
The polymer foam material and the preparation method thereof provided by the present invention will be further explained below.
According to the preparation method of the polymer foaming material, the polymer has flame retardance and char formation property through graft modification, so that flame-retardant rubber, a small molecular flame retardant or other flame-retardant fillers do not need to be mixed in the polymer, the foaming characteristic of the polymer is not affected, and the polymer foaming material with excellent performances such as flame retardance, heat preservation, sound insulation and buffering can be obtained.
The preparation method of the polymer foaming material provided by the invention comprises the following steps:
s1, providing a polymer, mixing the polymer with a hyperoxidant and a first solvent, and reacting at a first temperature to obtain a first intermediate product, wherein the main chain of the polymer contains double bonds;
s2, mixing the first intermediate product with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a second solvent, reacting at a second temperature to obtain a solution containing a second intermediate product, wherein the molecular chain of the second intermediate product contains a chemical structure shown in a formula (1),
Figure BDA0002223798640000051
s3, mixing the solution containing the second intermediate product with polyaniline, and reacting at a third temperature to obtain a third intermediate product, wherein the molecular chain of the third intermediate product contains a chemical structure as shown in formula (1) and a chemical structure as shown in formula (2),
Figure BDA0002223798640000052
s4, mixing the third intermediate product with a cross-linking agent and a foaming agent, carrying out hot pressing to obtain a prefabricated product, and simultaneously carrying out cross-linking and foaming on the prefabricated product at the temperature of 140-250 ℃ to obtain the polymer foam material.
In step S1, the polymer includes at least one of polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile rubber, styrene-butadiene-styrene block copolymer, and acrylonitrile-butadiene-styrene copolymer. The main chains of the polymers all contain double bonds, and the peroxidation agent can oxidize the double bonds in the main chains of the polymers into epoxy groups, so that the main chains of the polymers have chemically active sites capable of being used for graft modification.
In some embodiments, the molar ratio of the epoxy groups formed to the remaining double bonds in the backbone of the first intermediate product is from 1:9 to 9: 1. Considering that too many double bonds in the main chain of the polymer are oxidized to form epoxy groups, which affect the elasticity of the polymer foam material, further, the molar ratio of the epoxy groups to the remaining double bonds in the main chain of the first intermediate product is preferably 2:8 to 5: 5.
In some embodiments, the over-oxidizing agent is a mixed solution of hydrogen peroxide and formic acid, and when the over-oxidizing agent is a mixed solution of hydrogen peroxide and formic acid, the molar ratio of hydrogen peroxide to formic acid is preferably 1: 1. The first solvent comprises at least one of toluene, xylene, cyclohexane and dichloromethane.
In some embodiments, the polymer is dissolved in a first solvent, the peroxide is added, the polymer is oxidized at a first temperature of 25 ℃ to 70 ℃ to partially oxidize double bonds in the main chain of the polymer into epoxy groups, and the epoxy groups are purified and dried to obtain a first intermediate product.
In the invention, when the first intermediate product is subjected to graft modification, polyaniline belongs to a macromolecular chain, and if the polyaniline is grafted firstly, the grafting rate of small molecular side groups DOPO can be reduced due to the influence of steric hindrance. Therefore, the application grafts DOPO first through step S2 and then grafts polyaniline through step S3.
In step S2, the second temperature is 100 to 140 ℃, at which the DOPO reacts with the epoxy group in the first intermediate product to graft DOPO on the first intermediate product to obtain a second intermediate product.
In some embodiments, the second solvent comprises at least one of toluene, xylene, cyclohexane, dichloromethane.
The second intermediate product does not need to be purified and may be directly subjected to step S3. In step S3, the third temperature is 100 ℃ to 140 ℃, at which the epoxy groups remaining in the main chain of the second intermediate product are used as chemically active sites, and the polyaniline is grafted to the second intermediate product by a grafting reaction with the polyaniline, and the third intermediate product co-grafted with DOPO and polyaniline is obtained by purification.
The molecular chain of the third intermediate product contains a chemical structure as shown in the formula (1) and a chemical structure as shown in the formula (2), so that the third intermediate product has flame retardance and char formation, and the reduction of molten drops is facilitated. Therefore, it is no longer necessary to add a large amount of a flame-retardant rubber, a small-molecule flame retardant or other flame-retardant filler to the third intermediate product, and therefore, the third intermediate product has good foaming characteristics.
Considering that the lateral group DOPO mainly plays a role in flame retardance, the lateral chain polyaniline promotes the carbon formation of the material and assists in improving the flame retardant effect. Therefore, the molar content of the chemical structure represented by formula (1) in the molecular chain of the third intermediate product is equal to or greater than the molar content of the chemical structure represented by formula (2). Further, the molar content of the chemical structure represented by formula (1) is greater than the molar content of the chemical structure represented by formula (2).
In addition, polyaniline is considered as a macromolecular side chain and contains more aniline structural units. Therefore, in some embodiments, in the molecular chain of the third intermediate product, the molar ratio of the chemical structure represented by formula (1) to the double bonds in the main chain of the third intermediate product is 1:8 to 4:5, preferably 1.5:8 to 4:5, and the molar ratio of the chemical structure represented by formula (2) to the double bonds in the main chain of the third intermediate product is 0.5:8 to 1: 5.
Specifically, when the polymer is butadiene rubber, the molecular chain of the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 1:1:8, or has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 3:1: 16.
Specifically, when the polymer is styrene-butadiene rubber, the molecular chain of the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 2:1: 7.
Specifically, when the polymer is nitrile rubber, the molecular chain of the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2) and a molar ratio of double bonds in the main chain of 5:1: 14.
Specifically, when the polymer is an acrylonitrile-butadiene-styrene copolymer, the molecular chain of the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 3:1: 6.
Specifically, when the polymer is cis-isoprene rubber, the molecular chain of the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 4:1: 15.
When the third intermediate product is subjected to conventional foaming, a high-quality polymer foam cannot be obtained, or even a polymer foam cannot be obtained. The applicant has found, after long-term and intensive research, that the reason for this is that: the glass transition temperature of the first intermediate product and the third intermediate product is low, and crosslinking is needed, so that if the third intermediate product is foamed without crosslinking, or is foamed first and then crosslinked, gas escapes in the foaming process, and a foaming material with a good cell structure cannot be obtained; secondly, if the third intermediate product is crosslinked first, the crosslinked third intermediate product is difficult to thermally deform again, and the third intermediate product cannot foam.
To this end, in step S4, the third intermediate product is mixed with a cross-linking agent and a foaming agent, hot-pressed into a preform, and the preform is simultaneously cross-linked and foamed at a temperature of 140 to 250 ℃ so that the cross-linking process and the foaming process are simultaneously performed, and the termination of the cross-linking process is the termination of the foaming process, thereby obtaining a closed-cell polymer foam.
In some embodiments, the crosslinking agent comprises at least one of a sulfur cure system, a peroxide, a maleimide, and derivatives thereof. Further, the crosslinking agent is preferably a sulfur vulcanization system.
In some embodiments, the blowing agent includes at least one of azodicarbonamide, azo compounds such as azobisisobutyronitrile, sulfonphthalein trap compounds such as p-sulfoethertrap, nitroso compounds such as dinitrosopentamethylenetetramine, and microsphere blowing agents such as EXPANCEL. Further, the foaming agent is preferably a microsphere foaming agent.
Considering the problems that the foaming effect is poor when the amount of the foaming agent is too small and the foaming agent is easy to agglomerate when the amount of the foaming agent is too large, the amount of the foaming agent is 1 to 2 parts based on 100 parts of the third intermediate product.
The invention also provides a polymer foam material prepared by the preparation method, the aperture size of the polymer foam material is 50-500 mu m, and the cell density is 105～1015Per cm3The expansion multiplying power is 1-15 times, and the flame-retardant, heat-preservation, sound-insulation and buffering performances are excellent.
It can be understood that the flame retardant property and expansion ratio of the polymer foam material, the cell size and distribution, and the cell density can be regulated and controlled by the grafting amount of DOPO and polyaniline, and the dosage of the cross-linking agent and the foaming agent.
Hereinafter, the polymer foam and the method for preparing the same will be further described by the following specific examples.
Example 1:
firstly, dissolving butadiene rubber in a toluene solvent, adding peroxyformic acid obtained by mixing 2.32g of 88% chemically pure formic acid and 4.19g of 30% chemically pure hydrogen peroxide, and oxidizing the butadiene rubber at room temperature of 25 ℃ for about 3-12 hours to obtain a reaction solution. And washing the reaction liquid in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized butadiene rubber in the reaction liquid by using an ethanol precipitation method, and drying to obtain a first intermediate product epoxidized butadiene rubber, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized butadiene rubber is 2: 8.
Dissolving the epoxidized butadiene rubber in an organic solvent xylene, adding 7.2g of DOPO powder, heating to 140 ℃, and reacting at constant temperature for 12 hours. Then 6.7g of polyaniline is added, and the temperature is maintained at 140 ℃ for about 6h, and the next grafting reaction is carried out to obtain a reaction solution containing a third intermediate product. And separating the organic solvent from the third intermediate product by a rotary evaporator and a vacuum oven to obtain a third intermediate product. Wherein the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 1:1: 8.
And (3) blending 100 parts of the obtained third intermediate product with 2 parts of microsphere foaming agent EXPANCEL and a sulfur vulcanization system (15 parts of ring-pill oil, 3 parts of zinc oxide, 2 parts of stearic acid, 1 part of promoter PPD, 0.9 part of promoter CZ and 1.5 parts of sulfur) in an internal mixer at 90 ℃ for about 8min, putting the blended material into a mold with a specific shape, and carrying out hot pressing at 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out cross-linking and foaming for about 6min, and opening the mould to release pressure to obtain the polymer foaming material shown in the figure 1.
Example 2:
firstly, dissolving butadiene rubber in a toluene solvent, adding peroxyformic acid obtained by mixing 2.32g of 88% chemically pure formic acid and 4.19g of 30% chemically pure hydrogen peroxide, and oxidizing the butadiene rubber at room temperature of 25 ℃ for about 3-12 hours to obtain a reaction solution. And washing the reaction liquid in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized butadiene rubber in the reaction liquid by using an ethanol precipitation method, and drying to obtain a first intermediate product epoxidized butadiene rubber, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized butadiene rubber is 2: 8.
Dissolving the epoxidized butadiene rubber in an organic solvent xylene, adding 4.8g of DOPO powder, heating to 140 ℃, and reacting at constant temperature for 12 hours. And adding 13.4g of polyaniline, maintaining the temperature at 140 ℃ for about 9 hours, and carrying out the next grafting reaction to obtain a reaction solution containing a third intermediate product. And separating the organic solvent from the third intermediate product by a rotary evaporator and a vacuum oven to obtain a third intermediate product. Wherein the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 3:1: 16.
And (3) blending 100 parts of the obtained third intermediate product with 2 parts of microsphere foaming agent EXPANCEL and a sulfur vulcanization system (15 parts of ring-pill oil, 3 parts of zinc oxide, 2 parts of stearic acid, 1 part of promoter PPD, 0.9 part of promoter CZ and 1.5 parts of sulfur) in an internal mixer at 90 ℃ for about 8min, putting the blended material into a mold with a specific shape, and carrying out hot pressing at 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out crosslinking and foaming for about 6min, and opening the mould to release pressure to obtain the polymer foaming material.
Example 3:
firstly, styrene butadiene rubber is dissolved in a cyclohexane solvent, then performic acid obtained by mixing 3.48g of 88% chemically pure formic acid and 6.30g of 30% chemically pure hydrogen peroxide is added, and styrene butadiene rubber is oxidized for about 3-12 hours at room temperature of 25 ℃ to obtain reaction liquid. And washing the reaction liquid in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized styrene butadiene rubber in the reaction liquid by using an ethanol precipitation method, and drying to obtain a first intermediate epoxidized styrene butadiene rubber, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized styrene butadiene rubber is 3: 7.
Dissolving the epoxidized styrene-butadiene rubber in an organic solvent xylene, adding 9.6g of DOPO powder, heating to 140 ℃, and reacting at constant temperature for 12 hours. And adding 13.4g of polyaniline, maintaining the temperature at 140 ℃ for about 9 hours, and carrying out the next grafting reaction to obtain a reaction solution containing a third intermediate product. And separating the organic solvent from the third intermediate product by a rotary evaporator and a vacuum oven to obtain a third intermediate product. Wherein the chemical structure shown in the formula (1) and the chemical structure shown in the formula (2) in the third intermediate product, and the molar ratio of double bonds in the main chain is 2:1: 7.
And (3) blending 100 parts of the third intermediate product obtained in the step (1) with 1.5 parts of microsphere foaming agent EXPANCEL and a sulfur vulcanization system (10 parts of zinc oxide, 1.5 parts of stearic acid, 1 part of accelerator PPD, 1.2 parts of accelerator CZ, 1 part of accelerator DPTT and 1 part of vulcanizing agent TMTD) in an internal mixer at the temperature of 90 ℃ for about 10min, putting the blended material into a mold with a specific shape, and hot-pressing at the temperature of 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out crosslinking and foaming for about 10min, and opening the mould to release pressure to obtain the polymer foaming material.
Example 4:
firstly, dissolving nitrile rubber in a cyclohexane solvent, adding peroxyformic acid obtained by mixing 3.48g of 88% chemically pure formic acid and 6.30g of 30% chemically pure hydrogen peroxide, and oxidizing the nitrile rubber for about 3-12 hours at room temperature and 25 ℃ to obtain a reaction solution. And washing the reaction liquid in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized nitrile rubber in the reaction liquid by using an ethanol precipitation method, and drying to obtain a first intermediate product, namely epoxidized nitrile rubber, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized nitrile rubber is 3: 7.
Dissolving the epoxidized nitrile rubber in an organic solvent xylene, adding 12g of DOPO powder, heating to 140 ℃, and reacting at constant temperature for 16 h. Then 6.7g of polyaniline is added, and the temperature is maintained at 140 ℃ for about 9 hours, and the next grafting reaction is carried out, so as to obtain reaction liquid containing a third intermediate product. And separating the organic solvent from the third intermediate product by a rotary evaporator and a vacuum oven to obtain a third intermediate product. Wherein the molar ratio of the chemical structure shown in the formula (1) to the chemical structure shown in the formula (2) in the third intermediate product to the double bonds in the main chain is 5:1: 14.
And (3) blending 100 parts of the obtained third intermediate product with 2 parts of microsphere foaming agent EXPANCEL and a sulfur vulcanization system (1 part of plasticizer, 3 parts of zinc oxide, 2 parts of stearic acid, 1 part of accelerator PPD, 0.9 part of accelerator CZ and 1.75 parts of sulfur) in an internal mixer at 60 ℃ for about 10min, putting the blended material into a mold with a specific shape, and carrying out hot pressing at 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out crosslinking and foaming for about 10min, and opening the mould to release pressure to obtain the polymer foaming material.
Example 5:
firstly, dissolving an acrylonitrile-butadiene-styrene copolymer in a cyclohexane solvent, adding peroxyformic acid obtained by mixing 4.65g of 88% chemically pure formic acid and 8.40g of 30% chemically pure hydrogen peroxide, and oxidizing the acrylonitrile-butadiene-styrene copolymer at room temperature of 25 ℃ for about 3-12 hours to obtain a reaction solution. And washing the reaction liquid in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized acrylonitrile-butadiene-styrene copolymer in the reaction liquid by using an ethanol precipitation method, and drying to obtain a first intermediate product, namely the epoxidized acrylonitrile-butadiene-styrene copolymer, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized acrylonitrile-butadiene-styrene copolymer is 4: 6.
The epoxidized acrylonitrile-butadiene-styrene copolymer is dissolved in organic solvent xylene, 14.4g of DOPO powder is added, the temperature is raised to 140 ℃, and the constant temperature reaction is carried out for 12 hours. And adding 13.4g of polyaniline, maintaining the temperature at 140 ℃ for about 9 hours, and carrying out the next grafting reaction to obtain a reaction solution containing a third intermediate product. And separating the organic solvent from the third intermediate product by a rotary evaporator and a vacuum oven to obtain a third intermediate product. Wherein the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 3:1: 6.
And (3) blending 100 parts of the obtained third intermediate product with 2 parts of a microsphere foaming agent EXPANCEL and a sulfur vulcanization system (zinc oxide 5, stearic acid 3, an accelerator MBT 2, an accelerator TMDT 1 and 0.75 part of sulfur) in an internal mixer at the temperature of 90 ℃ for about 10min, putting the blended material into a mold with a specific shape, and carrying out hot pressing at the temperature of 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 200 ℃, simultaneously carrying out crosslinking and foaming for about 15min, and opening the mould to release pressure to obtain the polymer foaming material.
Example 6:
dissolving isoprene rubber in a toluene solvent, adding peroxyformic acid obtained by mixing 2.90g of 88% chemically pure formic acid and 5.24g of 30% chemically pure hydrogen peroxide, and oxidizing the isoprene rubber at room temperature of 25 ℃ for about 3-12 hours to obtain a reaction solution. And washing the reaction liquid in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized isoprene rubber in the reaction liquid by using an ethanol precipitation method, and drying to obtain a first intermediate product epoxidized isoprene rubber, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized isoprene rubber is 1: 3.
Dissolving the epoxidized isoprene rubber in an organic solvent xylene, adding 9.6g of DOPO powder, heating to 140 ℃, and reacting at constant temperature for 12 hours. Then 6.7g of polyaniline is added, and the temperature is maintained at 140 ℃ for about 9 hours, and the next grafting reaction is carried out, so as to obtain reaction liquid containing a third intermediate product. And separating the organic solvent from the third intermediate product by a rotary evaporator and a vacuum oven to obtain a third intermediate product. Wherein the third intermediate product has a chemical structure represented by formula (1), a chemical structure represented by formula (2), and a molar ratio of double bonds in the main chain of 4:1: 15.
And (3) blending 100 parts of the obtained third intermediate product with 1.5 parts of microsphere foaming agent EXPANCEL and a sulfur vulcanization system (3 parts of zinc oxide, 2 parts of stearic acid, 1 part of accelerator TMTD, 1 part of accelerator CZ and 2 parts of sulfur) in an internal mixer at 90 ℃ for about 10min, putting the blended material into a mold with a specific shape, and carrying out hot pressing at 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out cross-linking and foaming for about 12min, and opening the mould to release pressure to obtain the polymer foaming material shown in figure 2.
Comparative example 1:
firstly, dissolving butadiene rubber in a toluene solvent, adding peroxyformic acid obtained by mixing 2.32g of 88% chemically pure formic acid and 4.19g of 30% chemically pure hydrogen peroxide, and oxidizing the butadiene rubber at room temperature of 25 ℃ for about 3-12 hours to obtain a reaction solution. And washing the reaction liquid in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized butadiene rubber in the reaction liquid by using an ethanol precipitation method, and drying to obtain a first intermediate product epoxidized butadiene rubber, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized butadiene rubber is 2: 8.
Dissolving the epoxidized butadiene rubber in an organic solvent xylene, adding 7.2g of DOPO powder, heating to 140 ℃, and reacting at constant temperature for 12 hours. And separating the organic solvent from the second intermediate product by a rotary evaporator and a vacuum oven to obtain a second intermediate product. Wherein the molar ratio of the chemical structure shown in formula (1) in the second intermediate product to the double bonds in the main chain is 2: 8.
And (3) blending 100 parts of the obtained second intermediate product with 2 parts of microsphere foaming agent EXPANCEL and a sulfur vulcanization system (15 parts of ring-pill oil, 3 parts of zinc oxide, 2 parts of stearic acid, 1 part of promoter PPD, 0.9 part of promoter CZ and 1.5 parts of sulfur) in an internal mixer at 90 ℃ for about 8min, putting the blended material into a mold with a specific shape, and carrying out hot pressing at 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out crosslinking and foaming for about 6min, and opening the mould to release pressure to obtain the polymer material.
Comparative example 2:
dissolving butadiene rubber in a toluene solvent at 90 ℃, precipitating the butadiene rubber from the toluene solvent by an ethanol precipitation method, separating and drying. 100 parts of precipitated butadiene rubber, 2 parts of microsphere foaming agent EXPANCEL and a vulcanization formula (15 parts of pill oil, 3 parts of zinc oxide, 2 parts of stearic acid, 1 parts of promoter PPD, 0.9 part of promoter CZ and 1.5 parts of sulfur) are blended in an internal mixer at 90 ℃ for about 10min, and then the blended materials are put into a mold with a specific shape and are hot-pressed for about 8min at 100 ℃ to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out crosslinking and foaming for about 6min, and opening the mould to release pressure to obtain the polymer material.
Comparative example 3:
dissolving isoprene rubber in 100 deg.C toluene solvent, precipitating with ethanol, separating, and oven drying. 100 parts of precipitated isoprene rubber, 1.5 parts of microsphere foaming agent EXPANCEL and a vulcanization formula (3 parts of zinc oxide, 2 parts of stearic acid, an accelerator TMTD, an accelerator CZ1 and 2 parts of sulfur) are blended in an internal mixer at 90 ℃ for about 10min, and then the blended materials are put into a mold with a specific shape and are hot-pressed for about 8min at 100 ℃ to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out crosslinking and foaming for about 12min, and opening the mould to release pressure to obtain the polymer material.
Comparative example 4:
firstly, dissolving butadiene rubber in a toluene solvent, adding peroxyformic acid obtained by mixing 2.32g of 88% chemically pure formic acid and 4.19g of 30% chemically pure hydrogen peroxide, and oxidizing the butadiene rubber at room temperature of 25 ℃ for about 3-12 hours to obtain a reaction solution. Washing the reaction solution in a separating funnel by using distilled water, separating unreacted formic acid and hydrogen peroxide, precipitating the epoxidized butadiene rubber in the reaction solution by using an ethanol precipitation method, and drying to obtain a first intermediate product epoxidized butadiene rubber, wherein the molar ratio of epoxy groups to double bonds in the main chain of the epoxidized butadiene rubber is 2: 8.
Dissolving the epoxidized butadiene rubber in an organic solvent xylene, adding 26.8g of polyaniline, heating to 140 ℃, and reacting at constant temperature for 12 hours. And separating the organic solvent from the second intermediate product by a rotary evaporator and a vacuum oven to obtain a second intermediate product. Wherein the molar ratio of the chemical structure shown in formula (2) in the second intermediate product to the double bonds in the main chain is 2: 8.
And (3) blending 100 parts of the obtained second intermediate product with 2 parts of microsphere foaming agent EXPANCEL and a sulfur vulcanization system (15 parts of ring-pill oil, 3 parts of zinc oxide, 2 parts of stearic acid, 1 part of promoter PPD, 0.9 part of promoter CZ and 1.5 parts of sulfur) in an internal mixer at 90 ℃ for about 8min, putting the blended material into a mold with a specific shape, and carrying out hot pressing at 100 ℃ for about 8min to obtain a prefabricated product. And putting the prefabricated product into a mould pressing foaming device, heating to 160 ℃, simultaneously carrying out crosslinking and foaming for about 6min, and opening the mould to release pressure to obtain the polymer material.
The materials in examples 1-6 and comparative examples 1-4 were subjected to horizontal combustion test according to standard GB/T8332 and limited oxygen index characterization according to standard GB/T2406.2, and the mass fraction of combustion residue was analyzed by thermogravimetric analyzer, with the specific results shown in Table 1.
TABLE 1
Figure BDA0002223798640000161
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that various changes and modifications can be made by those skilled in the art without departing from the spirit of the invention, and these changes and modifications are all within the scope of the invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A method of making a polymer foam, comprising:
providing a polymer, mixing the polymer with a hyperoxidant and a first solvent, and reacting at a first temperature to obtain a first intermediate product, wherein the main chain of the polymer contains double bonds, the hyperoxidant enables the double bonds in the main chain of the polymer to be partially oxidized into epoxy groups, and the molar ratio of the generated epoxy groups to the remaining double bonds in the main chain of the first intermediate product is 2: 8-5: 5;
mixing the first intermediate product with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and a second solvent, reacting at a second temperature to obtain a solution containing a second intermediate product, wherein the molecular chain of the second intermediate product contains a chemical structure shown in a formula (1),
Figure FDA0003539695420000011
mixing the solution containing the second intermediate product with polyaniline, and reacting at a third temperature to obtain a third intermediate product, wherein the molecular chain of the third intermediate product contains a chemical structure shown as a formula (1) and a chemical structure shown as a formula (2), the molar content of the chemical structure shown as the formula (1) is greater than or equal to that of the chemical structure shown as the formula (2), the molar ratio of the chemical structure shown as the formula (1) to the double bonds in the main chain of the third intermediate product is 1: 8-4: 5, the molar ratio of the chemical structure shown as the formula (2) to the double bonds in the main chain of the third intermediate product is 0.5: 8-1: 5,
Figure FDA0003539695420000021
and mixing and hot-pressing the third intermediate product, a cross-linking agent and a foaming agent to obtain a prefabricated product, and simultaneously cross-linking and foaming the prefabricated product at the temperature of 140-250 ℃ to obtain the polymer foam material.
2. The method of claim 1, wherein the polymer comprises at least one of polybutadiene, polyisoprene, styrene-butadiene rubber, nitrile rubber, styrene-butadiene-styrene block copolymer, and acrylonitrile-butadiene-styrene copolymer.
3. The method of claim 1, wherein the molar content of the chemical structure represented by formula (1) in the molecular chain of the third intermediate product is greater than the molar content of the chemical structure represented by formula (2).
4. The method for preparing the polymer foam material according to claim 1, wherein the molar ratio of the chemical structure represented by the formula (1) to the double bonds in the main chain of the third intermediate product in the molecular chain of the third intermediate product is 1.5:8 to 4: 5.
5. The method of claim 1, wherein the first temperature is 25 ℃ to 70 ℃, the second temperature is 100 ℃ to 140 ℃, and the third temperature is 100 ℃ to 140 ℃.
6. The method of claim 1, wherein the cross-linking agent comprises at least one of a sulfur curing system, a peroxide, a maleimide, and derivatives thereof.
7. The method of claim 1, wherein the blowing agent comprises at least one of azo compounds, sulfonphthalein trap compounds, nitroso compounds, and microsphere blowing agents.
8. A polymer foam material, which is prepared by the preparation method of any one of claims 1 to 7, and has a pore size of 50 to 500 μm and a cell density of 105～1015Per cm3The expansion ratio is 1 to 15 times.
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