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CN118994701B - Fluororesin microporous foam material and preparation method thereof - Google Patents

Fluororesin microporous foam material and preparation method thereof Download PDF

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CN118994701B
CN118994701B CN202411491339.6A CN202411491339A CN118994701B CN 118994701 B CN118994701 B CN 118994701B CN 202411491339 A CN202411491339 A CN 202411491339A CN 118994701 B CN118994701 B CN 118994701B
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foaming
pressure
preparation
temperature
parts
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CN118994701A (en
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王镇
张恺亮
翁成龙
陈俊桦
徐鑫
王佳林
张超
党彦飞
于君
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Zhejiang Xinhengtai 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C08J3/246—Intercrosslinking of at least two polymers
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • 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
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

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

Abstract

本发明公开了一种氟树脂微孔发泡材料及其制备方法，发泡材料的制备包括以下步骤：改性多孔SiO2的制备及其与均聚PVDF、P(VDF‑HFP)共聚物进行熔融共混制备发泡前驱体，然后将发泡前驱体进行辐照交联及高压低温浸润，最后利用超临界流体发泡。发泡材料包括3‑15重量份改性SiO2、5‑20重量份均聚PVDF、60‑90重量份P(VDF‑HFP)共聚物。通过加入改性SiO2实现对超临界流体的高溶解度，缩短扩散路径，均聚PVDF、P(VDF‑HFP)共聚物进行熔融共混拓宽发泡窗口，辐照交联提高熔体强度，制备了具有均一泡孔结构的高倍率氟树脂微孔发泡材料，发泡材料的性能优异，制备方法简单，生产效率高。

The invention discloses a fluororesin microporous foam material and a preparation method thereof. The preparation of the foam material comprises the following steps: preparation of modified porous SiO2 and melt blending thereof with homopolymerized PVDF and P (VDF-HFP) copolymer to prepare a foaming precursor, and then subjecting the foaming precursor to irradiation cross-linking and high-pressure low-temperature infiltration, and finally foaming with a supercritical fluid. The foaming material comprises 3-15 parts by weight of modified SiO2 , 5-20 parts by weight of homopolymerized PVDF, and 60-90 parts by weight of P (VDF-HFP) copolymer. By adding modified SiO2 , high solubility in supercritical fluid is achieved, the diffusion path is shortened, homopolymerized PVDF and P (VDF-HFP) copolymer are melt blended to broaden the foaming window, irradiation cross-linking improves melt strength, and a high-ratio fluororesin microporous foam material with a uniform pore structure is prepared, the foaming material has excellent performance, a simple preparation method, and high production efficiency.

Description

Fluororesin microporous foam material and preparation method thereof
Technical Field
The invention relates to the technical field of high molecular polymers, in particular to a fluororesin microporous foam material and a preparation method thereof.
Background
Polyvinylidene fluoride (PVDF) is a typical semicrystalline fluororesin polymer, which has outstanding heat stability, corrosion resistance, incombustibility and hydrophobicity, excellent weather resistance and mechanical strength, easy processing, and other characteristics, and has a wide range of industrial uses. Foaming is an important means of expanding the polymer properties and application range. The PVDF-based foaming material with high foaming ratio is prepared by the foaming technology, so that the buffering and heat-preserving properties of the PVDF-based foaming material are greatly improved under the condition of keeping the original excellent properties of the PVDF, and the application of the PVDF-based foaming material in the fields of aerospace, semiconductors, medical treatment and the like is expanded.
However, due to the high processing temperature, the conventional chemical foaming agent cannot be applied, and has the problems of environmental protection and the like. Therefore, the supercritical fluid foaming can be used as an effective foaming method to prepare PVDF-based foaming materials, however, the conventional PVDF has the problems of poor melt strength, limited multiplying power, poor cell structure and the like of the prepared foaming materials, and limits the application and development of PVDF-based fluororesin foaming materials.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art, and provides a fluororesin microporous foam material and a preparation method thereof, which are realized by adopting the following technical scheme.
The preparation method of the fluororesin microporous foam material comprises the following steps:
(1) Adding porous SiO 2 and a silane coupling agent into dimethylbenzene, uniformly mixing, namely, carrying out ultrasonic mixing, refluxing in an N 2 atmosphere, removing the silane coupling agent which is not completely reacted after the reaction is finished to obtain SiO 2 with the surface modified epoxy group, and then carrying out melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 with the surface grafted polyethylene. Preferably, the weight part ratio of the porous SiO 2, the silane coupling agent and the polyethylene grafted maleic anhydride is 1:1-3:3-6. The silane coupling agent is selected from gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane, 3- (2, 3-epoxypropoxy) propyl triethoxy silane and 2- (3, 4-epoxycyclohexane) ethyl triethoxy silane. Further, after the reaction of the porous SiO 2 and the silane coupling agent is finished, the crude product is obtained by suction filtration, and the incomplete reaction of the silane coupling agent is removed by washing with methylene dichloride.
(2) The modified SiO 2, homo-PVDF and P (VDF-HFP) copolymer are melt blended to prepare the foaming precursor. The P (VDF-HFP) is vinylidene fluoride-hexafluoropropylene copolymer.
(3) And (3) carrying out irradiation crosslinking on the foaming precursor to enable crosslinking reaction to occur between the modified SiO 2 and PVDF molecular chains, wherein the irradiation dose is preferably 5-80 KGy.
(4) And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 15-25 MPa, the temperature is 120-140 ℃, the temperature is reduced to below 100 ℃ after a certain time, and then the pressure is slowly released to the room temperature. Preferably, the time for high pressure low temperature infiltration of the foaming precursor is 4-10 h.
(5) And (3) performing supercritical fluid foaming on the foaming precursor obtained in the step (4), wherein the specific foaming condition is that the foaming precursor is placed into a mould pressing foaming cavity, the temperature is controlled to be 140-160 ℃, the pressure of the injected supercritical fluid is 8-15 MPa, the constant temperature and the constant pressure are 1-4 h, then the pressure is released to normal pressure, and the mould is opened to obtain the fluororesin microporous foaming material. The supercritical fluid is at least one of supercritical carbon dioxide and supercritical nitrogen.
The foaming material comprises, by weight, 3-15 parts of modified SiO 2, 5-20 parts of homo-PVDF and 60-90 parts of P (VDF-HFP) copolymer. In the P (VDF-HFP) copolymer, the weight percentage of HFP is 4% -20%.
The fluororesin microporous foam material provided by the invention is prepared by adopting the preparation method.
The invention has the advantages that:
1. The modified porous SiO 2 is prepared, so that the gas solubility of the foaming precursor is improved, sufficient power is provided for subsequent cell nucleation and cell growth, a gas diffusion path is shortened, the infiltration time is reduced, and the high-pressure infiltration efficiency is improved. Meanwhile, the modified porous SiO 2 can be used as a heterogeneous nucleation point, so that the nucleation efficiency of the bubble nuclei is improved, and the cell density is improved.
2. Melt blending of the homo-PVDF and the P (VDF-HFP) copolymer can widen the melting range of the blend, widen the foaming window, reduce the sensitivity of the foaming multiplying power to temperature and prepare a more uniform foaming material.
3. The irradiation crosslinking can lead the polyethylene molecular chain on the surface of the porous SiO 2 to be crosslinked with the PVDF molecular chain to form an integrated structure, simultaneously improve the melt strength of the foaming precursor, prepare a uniform cell structure and can effectively inhibit the shrinkage of the PVDF-based foaming material after foaming.
Drawings
FIG. 1 is a scanning electron microscope image of the foaming material prepared in example 4.
Detailed Description
The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and processes are given, but the protection scope of the invention is not limited to the following embodiment. Unless otherwise indicated, the materials used are all commercially available conventional articles. The parts of the raw materials used in the following examples and comparative examples are parts by weight.
The homo-PVDF is PVDF with the brand of DE 6-4 of Zhejiang macro, or PVDF with the model Flurine ℃ of FL2006 of Zhejiang Funulin new chemical materials Co.
P (VDF-HFP) copolymer was purchased from Solef 11010.
Example 1
Adding porous SiO 2 and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing under the atmosphere of N 2, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with methylene dichloride to remove incompletely reacted gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to obtain SiO 2 with an epoxy group modified on the surface. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and polyethylene grafted maleic anhydride in the embodiment is 1:2:3.
3 Parts of modified SiO 2, 10 parts of homo-PVDF and 90 parts of P (VDF-HFP) copolymer are melt blended to prepare a foaming precursor.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 30 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 20 MPa, the temperature is 120 ℃, the temperature is reduced to 80 ℃ after the infiltration is 8 h, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical carbon dioxide to be 12 MPa, keeping the constant temperature and the constant pressure to be 2h, then releasing the pressure to normal pressure, and opening the mould to obtain the foaming material.
Example 2
Adding porous SiO 2 and 3- (2, 3-epoxypropoxy) propyl triethoxysilane into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing under the atmosphere of N 2, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with dichloromethane to remove incompletely reacted 3- (2, 3-epoxypropoxy) propyl triethoxysilane to obtain SiO 2 with an epoxy group modified on the surface. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, 3- (2, 3-epoxypropoxy) propyl triethoxysilane and polyethylene grafted maleic anhydride in the embodiment is 1:1:3.
A foaming precursor was prepared by melt blending 5 parts of modified SiO 2, 10 parts of homo-PVDF and 90 parts of P (VDF-HFP) copolymer.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 30 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 20 MPa, the temperature is 120 ℃, the temperature is reduced to 80 ℃ after the infiltration is 8 h, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical nitrogen at a pressure of 12 MPa, keeping the temperature and the pressure constant of 2h, releasing pressure to normal pressure, and opening the mould to obtain the foaming material.
Example 3
Adding porous SiO 2 and 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing under the atmosphere of N 2, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with dichloromethane to remove incompletely reacted 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane to obtain SiO 2 with the surface modified epoxy groups. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane and polyethylene grafted maleic anhydride in this example is 1:3:3.
10 Parts of modified SiO 2, 10 parts of homo-PVDF and 90 parts of P (VDF-HFP) copolymer are melt blended to prepare a foaming precursor.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 30 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 20 MPa, the temperature is 120 ℃, the temperature is reduced to 80 ℃ after the infiltration is 8 h, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical nitrogen at a pressure of 12 MPa, keeping the temperature and the pressure constant of 2h, releasing pressure to normal pressure, and opening the mould to obtain the foaming material.
Example 4
Adding porous SiO 2 and 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing under the atmosphere of N 2, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with dichloromethane to remove incompletely reacted 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane to obtain SiO 2 with the surface modified epoxy groups. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, 2- (3, 4-epoxycyclohexane) ethyl triethoxysilane and polyethylene grafted maleic anhydride in this example is 1:3:6.
A foaming precursor was prepared by melt blending 15 parts of modified SiO 2, 10 parts of homo-PVDF and 90 parts of P (VDF-HFP) copolymer.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 30 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 20 MPa, the temperature is 120 ℃, the temperature is reduced to 80 ℃ after the infiltration is 8 h, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical nitrogen at a pressure of 12 MPa, keeping the temperature and the pressure constant of 2h, releasing pressure to normal pressure, and opening the mould to obtain the foaming material.
Example 5
Adding porous SiO 2 and 3- (2, 3-epoxypropoxy) propyl triethoxysilane into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing under the atmosphere of N 2, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with dichloromethane to remove incompletely reacted 3- (2, 3-epoxypropoxy) propyl triethoxysilane to obtain SiO 2 with an epoxy group modified on the surface. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, 3- (2, 3-epoxypropoxy) propyl triethoxysilane and polyethylene grafted maleic anhydride in the embodiment is 1:3:4.
A foaming precursor was prepared by melt blending 5 parts of modified SiO 2, 10 parts of homo-PVDF and 90 parts of P (VDF-HFP) copolymer.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 50 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 20 MPa, the temperature is 120 ℃, the temperature is reduced to 80 ℃ after the infiltration is 8 h, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical nitrogen at a pressure of 12 MPa, keeping the temperature and the pressure constant of 2h, releasing pressure to normal pressure, and opening the mould to obtain the foaming material.
Example 6
Adding porous SiO 2 and a silane coupling agent into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing in an N 2 atmosphere, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with methylene dichloride to remove the incompletely reacted silane coupling agent to obtain SiO 2 with the surface modified epoxy groups. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, silane coupling agent and polyethylene grafted maleic anhydride in this example is 1:2:6. The silane coupling agent consists of 3- (2, 3-epoxypropoxy) propyl triethoxysilane and gamma- (2, 3-epoxypropoxy) propyl trimethoxysilane in a mass ratio of 1:1.
The foaming precursor was prepared by melt blending 8 parts of modified SiO 2, 20 parts of homo-PVDF and 60 parts of P (VDF-HFP) copolymer.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 5 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 15 MPa, the temperature is 140 ℃, the temperature is reduced to 80 ℃ after infiltration is 6 h, and then the pressure is slowly released to the room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature at 140 ℃, injecting a supercritical fluid at 15 MPa, wherein the supercritical fluid is a mixture of supercritical carbon dioxide and supercritical nitrogen, keeping the constant temperature and the constant pressure at 1: 1h, releasing pressure to normal pressure, and opening the mould to obtain the foaming material.
Example 7
Adding porous SiO 2 and a silane coupling agent into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing in an N 2 atmosphere, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with methylene dichloride to remove the incompletely reacted silane coupling agent to obtain SiO 2 with the surface modified epoxy groups. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, silane coupling agent and polyethylene grafted maleic anhydride in this example is 1:1:6. The silane coupling agent consists of gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and 2- (3, 4-epoxycyclohexane) ethyl triethoxy silane in the mass ratio of 2:1.
A foaming precursor was prepared by melt blending 12 parts of modified SiO 2 parts of homo-PVDF and 70 parts of P (VDF-HFP) copolymer.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 80 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 25 MPa, the temperature is 130 ℃, the temperature is reduced to 90 ℃ after 4: 4h infiltration, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature at 160 ℃, injecting supercritical fluid at 8 MPa, wherein the supercritical fluid is a mixture of supercritical carbon dioxide and supercritical nitrogen, keeping the constant temperature and the constant pressure at 4: 4h, releasing pressure to normal pressure, and opening the mould to obtain the foaming material.
Example 8
Adding porous SiO 2 and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane into dimethylbenzene, carrying out ultrasonic treatment until the materials are mixed uniformly, refluxing under the atmosphere of N 2, carrying out suction filtration after the reaction is finished to obtain a crude product, and washing with methylene dichloride to remove incompletely reacted gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane to obtain SiO 2 with an epoxy group modified on the surface. And then melt blending with polyethylene grafted maleic anhydride to prepare the modified SiO 2 of the surface grafted polyethylene. The weight part ratio of porous SiO 2, gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane and polyethylene grafted maleic anhydride in the embodiment is 1:2:5.
9 Parts of modified SiO 2, 15 parts of homo-PVDF and 80 parts of P (VDF-HFP) copolymer are melt blended to prepare a foaming precursor.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 65 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and PVDF molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 18 MPa, the temperature is 135 ℃, the temperature is reduced to 70 ℃ after the infiltration is 10h, and then slowly releasing the pressure to room temperature.
And (3) placing the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature at 155 ℃, injecting supercritical carbon dioxide at 10 MPa, maintaining the temperature and the pressure at 3: 3 h, releasing the pressure to normal pressure, and opening the mould to obtain the foaming material.
Comparative example 1
10 Parts of homo-PVDF and 90 parts of P (VDF-HFP) copolymer were melt blended to prepare a foaming precursor.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical carbon dioxide to be 12 MPa, keeping the constant temperature and the constant pressure to be 2h, then releasing the pressure to normal pressure, and opening the mould to obtain the foaming material.
The difference from example 1 is that the starting material does not use modified SiO 2 and the preparation process does not have an irradiation step.
Comparative example 2
10 Parts of homo-PVDF and 90 parts of P (VDF-HFP) copolymer were melt blended to prepare a foaming precursor.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 30 Kgy.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 20 MPa, the temperature is 120 ℃, the temperature is reduced to 80 ℃ after the infiltration is 8 h, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical carbon dioxide to be 12 MPa, keeping the constant temperature and the constant pressure to be 2h, then releasing the pressure to normal pressure, and opening the mould to obtain the foaming material.
The difference from example 1 is that no modified SiO 2 was added to the starting material.
Comparative example 3
The preparation of modified SiO 2 was carried out as in example 1.
A foaming precursor was prepared by melt blending 3 parts of modified SiO 2 and 100 parts of P (VDF-HFP) copolymer.
And (3) carrying out irradiation crosslinking on the foaming precursor, wherein the irradiation dose is 30 Kgy, so that crosslinking reaction is carried out between polyethylene molecular chains and P (VDF-HFP) molecular chains on the surface of the modified SiO 2.
And (3) placing the irradiated foaming precursor into a high-pressure cavity for high-pressure low-temperature infiltration, wherein the pressure is 20 MPa, the temperature is 120 ℃, the temperature is reduced to 80 ℃ after the infiltration is 8 h, and then slowly releasing the pressure to room temperature.
And (3) putting the obtained foaming precursor into a mould pressing foaming cavity, controlling the temperature to be 150 ℃, injecting supercritical carbon dioxide to be 12 MPa, keeping the constant temperature and the constant pressure to be 2h, then releasing the pressure to normal pressure, and opening the mould to obtain the foaming material.
The difference from example 1 is that no homo-PVDF was added to the starting materials and only P (VDF-HFP) copolymer was used.
Performance testing
Table 1 example 1-example 5 and comparative example 1-comparative example 3 using parts by weight of raw materials and irradiation dose
The foaming materials prepared in examples 1 to 5 and comparative examples 1 to 3 were each tested for their respective properties according to the following criteria, the test was repeated three times, and the test results are shown in table 2 below. The foamed material was tested using the following method and conditions:
the density is obtained according to GB/T6343 test;
the dimensional shrinkage is obtained by testing according to the standard GB/T8811 at-55 ℃ to 70 ℃;
cell size, namely shooting the section of the foaming material by a scanning electron microscope, and counting the diameters of 200 cells to obtain the average diameter.
Table 2 parameters of the foaming materials prepared in example 1-example 5 and comparative example 1-comparative example 3
From examples 1-4, it is understood that the content of modified SiO 2 affects cell size and dimensional shrinkage, and that the higher the content of modified SiO 2, the smaller the cell diameter and dimensional shrinkage. This is because the modified SiO 2 increases the gas solubility, provides sufficient power for cell nucleation, and can serve as heterogeneous nucleation sites to promote the formation of cell nuclei, increase the cell density and reduce the cell diameter. FIG. 1 is a scanning electron microscope image of the foaming material prepared in example 4.
From examples 2 and 5, it is understood that the larger the irradiation dose, the smaller the cell diameter and dimensional shrinkage, but the higher the foaming density.
Comparative example 1 differs from example 1 in that modified SiO 2 was not used as a raw material, and there was no irradiation step in the production method, and the result showed that the cell size was 2 times that of example 1, the dimensional shrinkage was 3 times or more that of example, the cell wall of large cells was thinner, the supporting force was weak, and the dimensional shrinkage of the material was deteriorated.
Comparative example 2 and example 1 differ in that no modified SiO 2 was added, and the results showed that the cell diameter was much larger than that of example 1 and the dimensional shrinkage was higher.
Comparative example 3 differs from example 1 in that no homopolymerized PVDF was added to the starting material, the cell diameter was larger than in example 1, and the dimensional shrinkage was higher.
According to the invention, the modified porous SiO 2 is added to realize the high solubility of the supercritical fluid, the diffusion path is shortened, the melt blending of the homo-PVDF and P (VDF-HFP) copolymer is carried out to widen the foaming window, the irradiation crosslinking is carried out to improve the melt strength and other measures, so that the high-magnification fluororesin microporous foaming material with a uniform cell structure is prepared, the foaming material has excellent performance, the preparation method is simple, and the production efficiency is high.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.

Claims (9)

1.一种氟树脂微孔发泡材料的制备方法，其特征在于，包括以下步骤：1. A method for preparing a fluororesin microporous foam material, characterized in that it comprises the following steps: （1）将多孔SiO2和硅烷偶联剂加入二甲苯中混匀，N2氛围下回流，反应结束后除去未完全反应的硅烷偶联剂，获得表面修饰环氧基团的SiO2，随后与聚乙烯接枝马来酸酐熔融共混，制备表面接枝聚乙烯的改性SiO2；(1) adding porous SiO 2 and a silane coupling agent into xylene and mixing them evenly, refluxing under a N 2 atmosphere, removing the unreacted silane coupling agent after the reaction is completed, obtaining SiO 2 with surface modified epoxy groups, and then melt-blending with polyethylene grafted maleic anhydride to prepare modified SiO 2 with surface grafted polyethylene; 所述的硅烷偶联剂选自γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷、3-(2,3-环氧丙氧基)丙基三乙氧基硅烷、2-(3,4-环氧环己烷基)乙基三乙氧基硅烷；The silane coupling agent is selected from γ-(2,3-epoxypropoxy)propyltrimethoxysilane, 3-(2,3-epoxypropoxy)propyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane; （2）将改性SiO2、均聚PVDF和P(VDF-HFP)共聚物进行熔融共混制备发泡前驱体；(2) melt blending the modified SiO 2 , homopolymer PVDF and P(VDF-HFP) copolymer to prepare a foaming precursor; （3）将发泡前驱体进行辐照交联，使改性SiO2、PVDF分子链之间发生交联反应；(3) irradiating and cross-linking the foaming precursor to cause a cross-linking reaction between the modified SiO 2 and PVDF molecular chains; （4）将辐照后的发泡前驱体放入高压腔体中进行高压低温浸润，压力15-25 MPa，温度120-140℃，一定时间后降低到100℃以下，随后缓慢泄压至室温；(4) placing the irradiated foaming precursor into a high-pressure chamber for high-pressure and low-temperature infiltration at a pressure of 15-25 MPa and a temperature of 120-140°C. After a certain period of time, the temperature is reduced to below 100°C, and then the pressure is slowly released to room temperature; （5）将步骤（4）获得的发泡前驱体进行超临界流体发泡，得到氟树脂微孔发泡材料；(5) subjecting the foaming precursor obtained in step (4) to supercritical fluid foaming to obtain a fluororesin microporous foam material; 所述发泡材料包括如下重量份数的组分：3-15份改性SiO2、5-20份均聚PVDF、60-90份P(VDF-HFP)共聚物。The foaming material comprises the following components in parts by weight: 3-15 parts of modified SiO 2 , 5-20 parts of homopolymer PVDF, and 60-90 parts of P (VDF-HFP) copolymer. 2.根据权利要求1所述的制备方法，其特征在于，所述的P(VDF-HFP)共聚物中，HFP的重量百分比为4%-20%。2. The preparation method according to claim 1, characterized in that the weight percentage of HFP in the P (VDF-HFP) copolymer is 4%-20%. 3.根据权利要求1所述的制备方法，其特征在于，步骤（1）中所述的多孔SiO2、硅烷偶联剂和聚乙烯接枝马来酸酐的重量份数比为1∶(1-3)∶(3-6)。3. The preparation method according to claim 1, characterized in that the weight ratio of the porous SiO2 , silane coupling agent and polyethylene grafted maleic anhydride in step (1) is 1:(1-3):(3-6). 4.根据权利要求1所述的制备方法，其特征在于，步骤（1）中多孔SiO2和硅烷偶联剂反应结束后抽滤得到粗产物，采用二氯甲烷洗涤除去未完全反应的硅烷偶联剂。4. The preparation method according to claim 1, characterized in that, after the reaction between the porous SiO2 and the silane coupling agent in step (1) is completed, the crude product is filtered out by suction, and the incompletely reacted silane coupling agent is removed by washing with dichloromethane. 5.根据权利要求1所述的制备方法，其特征在于，步骤（3）中所述辐照剂量为5-80 KGy。5. The preparation method according to claim 1, characterized in that the irradiation dose in step (3) is 5-80 KGy. 6.根据权利要求1所述的制备方法，其特征在于，步骤（4）中发泡前驱体进行高压低温浸润的时间为4-10 h。6. The preparation method according to claim 1, characterized in that the time for high pressure and low temperature infiltration of the foaming precursor in step (4) is 4-10 hours. 7.根据权利要求1所述的制备方法，其特征在于，步骤（5）中所述的超临界流体为超临界二氧化碳、超临界氮气中的至少一种。7. The preparation method according to claim 1, characterized in that the supercritical fluid in step (5) is at least one of supercritical carbon dioxide and supercritical nitrogen. 8.根据权利要求1所述的制备方法，其特征在于，步骤（5）中所述的超临界流体发泡条件为：将步骤（4）获得的发泡前驱体放入模压发泡腔体中，控制温度在140-160℃，注入超临界流体的压力为8-15 MPa，恒温恒压1-4 h，然后泄压至常压，开模得到发泡材料。8. The preparation method according to claim 1, characterized in that the supercritical fluid foaming conditions described in step (5) are: placing the foaming precursor obtained in step (4) into a mold foaming cavity, controlling the temperature at 140-160°C, injecting the supercritical fluid at a pressure of 8-15 MPa, maintaining constant temperature and pressure for 1-4 h, then releasing the pressure to normal pressure, and opening the mold to obtain the foaming material. 9.一种氟树脂微孔发泡材料，其特征在于，采用权利要求1-8任一项所述的制备方法得到。9. A fluororesin microporous foam material, characterized in that it is obtained by the preparation method according to any one of claims 1 to 8.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102348745A (en) * 2009-03-10 2012-02-08 株式会社Jsp Polyvinylidene fluoride resin expanded beads, and molded articles of polyvinylidene fluoride resin expanded beads
CN106987050A (en) * 2017-03-17 2017-07-28 浙江森川家具有限公司 It is a kind of for PP composite material of supercritical carbon dioxide foaming and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6960633B2 (en) * 2001-10-25 2005-11-01 Virginia Commonwealth University Fluoropolymer-carbon dioxide compositions and methods of processing fluoropolymers
CN103545548B (en) * 2013-11-07 2015-11-25 湘潭大学 A kind of preparation method of three-dimensional porous polymer dielectric film
EP4048722A4 (en) * 2019-10-21 2023-11-15 Arkema, Inc. FLUOROPOLYMER COMPOSITION AND PREPARATION METHOD
CN111574744B (en) * 2020-05-22 2023-03-31 常州长园特发科技有限公司 Preparation method of clean environment-friendly polyvinylidene fluoride foamed sheet
CN115232353A (en) * 2021-04-23 2022-10-25 中国石油化工股份有限公司 A kind of low-odor and scratch-resistant polypropylene composition, foamed beads and preparation method thereof, and polypropylene foamed bead molded body
CN114085479B (en) * 2021-12-09 2022-10-28 郑州大学 Polyvinylidene fluoride-hexafluoropropylene magnetic porous piezoelectric composite film and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102348745A (en) * 2009-03-10 2012-02-08 株式会社Jsp Polyvinylidene fluoride resin expanded beads, and molded articles of polyvinylidene fluoride resin expanded beads
CN106987050A (en) * 2017-03-17 2017-07-28 浙江森川家具有限公司 It is a kind of for PP composite material of supercritical carbon dioxide foaming and preparation method thereof

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