CN116102872A - Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof - Google Patents

Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof Download PDF

Info

Publication number
CN116102872A
CN116102872A CN202310147976.0A CN202310147976A CN116102872A CN 116102872 A CN116102872 A CN 116102872A CN 202310147976 A CN202310147976 A CN 202310147976A CN 116102872 A CN116102872 A CN 116102872A
Authority
CN
China
Prior art keywords
ppo
modified
foaming
modified ppo
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310147976.0A
Other languages
Chinese (zh)
Inventor
赵玲
余加保
陈弋翀
钟文宇
赵艳菲
胡冬冬
奚桢浩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
East China University of Science and Technology
Original Assignee
East China University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by East China University of Science and Technology filed Critical East China University of Science and Technology
Priority to CN202310147976.0A priority Critical patent/CN116102872A/en
Publication of CN116102872A publication Critical patent/CN116102872A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • 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
    • C08J9/0014—Use of organic additives
    • C08J9/0038—Use of organic additives containing phosphorus
    • 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
    • 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
    • C08J9/142—Compounds containing oxygen but no halogen atom
    • 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
    • C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
    • 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
    • C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12—Polyphenylene oxides
    • 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
    • C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2451/04—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Abstract

The invention provides a modified PPO material and a preparation method thereof, and a PPO foaming material and a preparation method thereof, belonging to the technical field of modification. The modified PPO material comprises modified PPO, high impact polystyrene and an antioxidant; the modified PPO comprises PPO and a branched chain grafted on the PPO through an ether bond; the branched chain is formed by etherifying the PPO after the ring of the multi-epoxy functional group modifier is opened. The branched chain of the modified PPO can occur under the stress in the foaming processEntanglement allows for improved strength. On the one hand, the strength is improved, so that bubbles are not easy to crack in the growth process, and therefore, the bubbles can continuously grow, and the foaming multiplying power is improved; on the other hand, the prepared foaming material has good strength. The results of the examples show that the density of the foaming material prepared by the modified PPO of the invention is 17-21 kg/m 3 The bending strength of the modified PPO material is 75.42-97.52 MPa.

Description

Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof
Technical Field
The invention belongs to the technical field of modification, and particularly relates to a modified PPO material and a preparation method thereof, and a PPO foaming material and a preparation method thereof.
Background
2, 6-dimethyl-1, 4-diphenyl ether (PPO) is one of the cheapest and lightest engineering plastics with high temperature resistance, and has excellent mechanical strength, stress relaxation resistance, creep resistance, heat resistance, water resistance, steam resistance and dimensional stability. Meanwhile, PPO has good flame retardance and extremely low dielectric property, is hardly influenced by temperature and humidity, and can be applied to the field of high-frequency communication.
Supercritical fluid foaming is an effective way for realizing the light weight of polymer materials, and has the characteristics of green and environment protection. After foaming, the polyphenyl ether can be light, and the material has unique functions such as heat insulation, sound insulation, buffering performance and low dielectric property. The polyphenyl ether foaming material has excellent heat resistance and dimensional stability, and has wide application prospect in the fields of automobiles, new energy batteries, precise instruments and the like.
CN202210428833.2 discloses a foaming method of PPO/polypropylene (PP) composite beads, and the material density is 25kg/m by kettle-pressure foaming 3 The PPO/PP expanded beads of (C).
CN202111674095.1 discloses a process for preparing a shaped body of modified polyphenyl ether foam beads, which comprises blending PPO, PS and flame retardant, modifying, extruding, granulating, then putting into a shaping mould, charging CO 2 Quick pressure relief foaming to obtain polyphenyl ether foaming bead molding bodyDensity of 100-200 kg/m 3 。
As can be seen from the published reports, the PPO foaming materials prepared by the prior art have higher density which is more than 25kg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the And most of the materials are physical blending systems, and the strength needs to be further improved.
Disclosure of Invention
The invention aims to provide a modified PPO material and a preparation method thereof, and a PPO foaming material and a preparation method thereof.
The invention provides a modified PPO material which is characterized by comprising modified PPO, high impact polystyrene and an antioxidant; the modified PPO comprises PPO and a branched chain grafted on the PPO through an ether bond;
the branched chain is formed by etherifying the PPO after the ring of the multi-epoxy functional group modifier is opened.
Preferably, the polyepoxide functional modifier comprises TGIC or basf chain extender ADR.
Preferably, when the polyepoxy functional group modifier is a basf chain extender ADR, the basf chain extender ADR is 2.0 to 6.0wt% of PPO; when the polyepoxy functional group modifier is TGIC, the TGIC is 0.6-2.0wt% of PPO.
The invention also provides a preparation method of the modified PPO material, which comprises the following steps:
performing first co-extrusion on PPO, high impact polystyrene and an antioxidant to obtain a physical modified substance;
and (3) performing second coextrusion on the physical modifier and the polyepoxy functional group modifier to perform ring opening and etherification to obtain the modified PPO material.
Preferably, the temperature of the first and second coextrudates is independently 240 to 285 ℃.
Preferably, the mass ratio of the PPO to the high impact polystyrene is 1:0.05-13.
Preferably, the mass ratio of the PPO to the antioxidant is 0.3-30:1.
The invention also providesThe PPO foaming material is obtained by foaming the modified PPO material according to the scheme or the modified PPO material obtained by the preparation method according to the scheme; the density of the PPO foaming material is 17-21 kg/m 3 The bending strength of the modified PPO material is 75.42-97.52 MPa.
The invention also provides a preparation method of the PPO foaming material, which comprises the following steps:
processing the modified PPO material to obtain a sheet-shaped to-be-foamed body;
the sheet-shaped to-be-foamed body is subjected to pressure relief after being saturated in a gas foaming agent, so that the PPO foaming material is obtained;
the saturation temperature is 100-250 ℃, the pressure is 10-20 Mpa, and the time is more than or equal to a× (d/2) 1.75 Wherein a= 0.2762h/mm 1.75 D is the thickness of the body to be foamed, and the unit is mm.
Preferably, the pressure relief rate is 100-1000 MPa/s.
The invention provides a modified PPO material, which comprises modified PPO, high impact polystyrene and an antioxidant; the modified PPO comprises PPO and a branched chain grafted on the PPO through an ether bond; the branched chain is formed by etherifying the PPO after the ring of the multi-epoxy functional group modifier is opened. The branched chain of the modified PPO is entangled under the action of stress in the foaming process, so that the strength of the modified PPO is improved, and on one hand, bubbles are not easy to crack in the growth process due to the improvement of the strength, so that the modified PPO can continuously grow, and the foaming multiplying power is improved; on the other hand, the prepared foaming material has good strength. The results of the examples show that the density of the foaming material prepared from the modified PPO material of the invention is 17-21 kg/m 3 The aperture is 8.91-12.53 mu m, and the bending strength of the modified PPO material is 75.42-97.52 MPa.
Drawings
FIG. 1 is a scanning image of a cross section of a PPO foaming material in application example 1 by an electron microscope;
FIG. 2 is a scanning image of a cross section of the PPO foaming material of application example 2 by an electron microscope;
fig. 3 is a scanning image of a cross section of the PPO foaming material of comparative application example 1 by electron microscopy.
Detailed Description
The invention provides a modified PPO material, which comprises modified PPO, high impact polystyrene and an antioxidant; the modified PPO comprises PPO and a branched chain grafted on the PPO through an ether bond;
the branched chain is formed by etherifying the PPO after the ring of the multi-epoxy functional group modifier is opened.
In the present invention, the polyepoxy functional modifier preferably comprises TGIC or basf chain extender ADR.
In the present invention, when the polyepoxy functional modifier is a basf chain extender ADR, the basf chain extender ADR is preferably 2 to 6wt% of PPO, more preferably 4 to 5wt%; when the polyepoxy functional modifier is TGIC, the TGIC is preferably 0.6 to 2wt% of PPO, more preferably 1 to 1.5wt%. Controlling the amount of the polyepoxy-functional modifier within the above-described range allows the PPO to react substantially with the polyepoxy-functional modifier to form branches. If the content of the polyepoxy functional group modifier is low, the amount of PPO participating in the reaction is less, and the modification effect is not obvious; the content of the polyepoxy functional group modifier is higher, so that self-polymerization is easy to occur, and the material performance is influenced.
In the present invention, the raw materials used are commercially available products well known in the art, unless specifically described otherwise.
The invention also provides a preparation method of the modified PPO material, which comprises the following steps:
performing first co-extrusion on PPO, high impact polystyrene and an antioxidant to obtain a physical modified substance;
and (3) performing second coextrusion on the physical modifier and the polyepoxy functional group modifier to perform ring opening and etherification to obtain the modified PPO material.
The invention carries out first co-extrusion on PPO, high impact polystyrene and an antioxidant to obtain a physical modified substance. In the present invention, the mass ratio of the PPO to the high impact polystyrene is preferably 1:0.05 to 13, more preferably 1:2 to 10, still more preferably 1:5 to 8. The addition of high impact polystyrene can improve the processability of PPO. In the present invention, the mass ratio of the PPO to the antioxidant is preferably 0.3 to 30:1, more preferably 5 to 20:1, and still more preferably 10 to 15:1. In the invention, the antioxidant preferably comprises an antioxidant 1010 and an antioxidant 168, and the mass ratio of the antioxidant 1010 to the antioxidant 168 is preferably 1:2. In the present invention, the temperature of the first coextrusion is preferably 240 to 285 ℃. In the present invention, the first coextrusion is preferably carried out in a twin-screw extruder. In the present invention, the screw speed of the twin-screw extruder is preferably 40 to 200rpm, more preferably 80 to 150rpm, and still more preferably 100 to 120rpm. In the present invention, the temperature zone of the twin-screw extruder is preferably divided into six zones, and the temperatures of the temperature zones from the feeding zone to the die head are preferably: 240 ℃,260 ℃,280 ℃,285 ℃ and 285 ℃.
After the first coextrusion, the present invention preferably granulates the obtained first coextrudate to obtain the physical modification. In the present invention, the particle diameter of the physical modifier is preferably 0.1 to 2mm, more preferably 0.5 to 1.5mm.
After the physical modifier is obtained, the physical modifier and the polyepoxy functional group modifier are subjected to second coextrusion to carry out ring opening and etherification, so that the modified PPO material is obtained.
In the present invention, the temperature of the second coextrusion is preferably 240 to 285 ℃. In the present invention, the second coextrusion is preferably carried out in a twin-screw extruder. In the present invention, the screw speed of the twin-screw extruder is preferably 40 to 200rpm, more preferably 80 to 150rpm, and still more preferably 100 to 120rpm. In the present invention, the temperature zone of the twin-screw extruder is preferably divided into six zones, and the temperature ethylene from the feed zone to the die head is preferably: 240 ℃,260 ℃,280 ℃,285 ℃ and 285 ℃.
After the second coextrusion, the present invention preferably granulates the obtained second coextrusion to obtain the modified PPO material. In the present invention, the particle size of the modified PPO material is preferably 0.1 to 2mm, more preferably 0.5 to 1.5mm. In the second coextrusion process, the epoxy group of the polyepoxy functional group modifier is subjected to ring opening reaction, and etherified with the hydroxyl end group of the PPO to form an ether bond, so that the epoxy group is grafted to the PPO.
When the polyepoxy functional modifier is TGIC, the equation of ring opening and etherification reaction is:
Figure BDA0004092009560000041
the invention also provides a PPO foaming material, which is obtained by foaming the modified PPO material according to the scheme or the modified PPO material obtained by the preparation method according to the scheme; the density of the PPO foaming material is 17-21 kg/m 3 The bending strength of the modified PPO material is 75.42-97.52 MPa.
The invention also provides a preparation method of the PPO foaming material, which comprises the following steps: :
processing the modified PPO material to obtain a sheet-shaped to-be-foamed body;
and (3) saturating the sheet-shaped to-be-foamed body in a gas foaming agent, and then decompressing to obtain the PPO foaming material.
The invention processes the modified PPO material to obtain a sheet-shaped to-be-foamed body. In the present invention, the thickness of the sheet-like foam to be foamed is preferably 1 to 20mm, more preferably 5 to 15mm, still more preferably 8 to 12mm; the length is preferably 10 to 1000mm, more preferably 200 to 800mm, still more preferably 400 to 600mm; the width is preferably 10 to 1000mm, more preferably 200 to 800mm, and still more preferably 400 to 600mm. The method of the present invention is not particularly limited, and may be any method known to those skilled in the art, such as hot pressing, injection molding, extrusion.
After the sheet-shaped to-be-foamed body is obtained, the PPO foaming material is obtained by saturating the sheet-shaped to-be-foamed body in a gas foaming agent and then decompressing. In the present invention, the gaseous foaming agent preferably comprises CO 2 、N 2 One or more of methanol and butane. In the present invention, the saturation temperature is 100 to 250 ℃, preferably 120 to 200 ℃, and more preferably 150 to 180 ℃. In the present invention, the saturation pressure is 10 to 20Mpa, preferably 12 to 18Mpa,more preferably 15 to 16MPa. In the present invention, the saturated pressure is preferably provided by a gaseous blowing agent. The saturation time is equal to or longer than a× (d/2) 1.75 Wherein a= 0.2762h/mm 1.75 D is the thickness of the body to be foamed, and the unit is mm. For example, when d is 3mm, the saturation time is 0.57 hours. After saturation, the gaseous blowing agent reaches a dissolution equilibrium in the foam to be foamed.
In the present invention, the pressure release rate of the pressure release foaming is 100 to 1000MPa/s, preferably 200 to 700MPa/s, and more preferably 400 to 600MPa/s. The pressure relief rate within the above range may provide a sufficient driving force for cell nucleation and growth.
For further explanation of the present invention, the modified PPO material and the preparation method thereof, the PPO foam material and the preparation method thereof provided by the present invention are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
PPO (Nantong star synthetic materials Co., ltd., LXN 040), high impact polystyrene particles (Qimei chemical industry, PH-60), antioxidant 1010 and antioxidant 168 are mixed according to the mass ratio of 90:7:2:1, then extrusion granulation is carried out in a double screw extruder, the temperature of the extruder is controlled by six areas, and the temperatures from a feeding area to a die head are respectively: 240 ℃,260 ℃,280 ℃,285 ℃, and the screw speed of 150rpm, to form a physical modification of 1.5mm.
Subsequently, the physical modifier and the polyepoxy functional group modifier TGIC are subjected to reaction chemical modification in a twin-screw extruder in a mass ratio of 100:1.093, the extruder is divided into six zones for temperature control, and the temperatures from a feeding zone to a die head are respectively as follows: 240 ℃,260 ℃,280 ℃,280 ℃,285 ℃,285 ℃, screw speed of 120rpm, followed by pelletization by a pelletizer, forms a 1.5mm modified PPO material.
Application example 1
The modified PPO material of example 1 is manufactured into a to-be-foamed body with the thickness of 5mm, the length of 50mm and the width of 50mm by an injection molding mode, the to-be-foamed body is placed in a high-pressure die cavity with the temperature of 225 ℃, and the high pressure is realized through a hydraulic system at the bottom of the die cavityThe die cavity is closed and subsequently CO is injected into the die cavity 2 To 15MPa, saturated for 1.5h and CO 2 A dissolution equilibrium is reached in the material matrix. And finally, rapidly releasing pressure through a high-pressure ball valve connected with the high-pressure die cavity, wherein the pressure release rate is 400MPa/s, rapidly opening the high-pressure die cavity, and taking out the foaming sample.
Example 2
The only differences from example 1 are: the polyepoxy functional group modifier is a basf chain extender ADR, and the mass ratio of the physical modifier to the polyepoxy functional group modifier is 100:1.837.
Application example 2
The only differences from application example 1 are: the modified PPO material of example 2 was used.
Example 3
The only differences from example 1 are: the mass ratio of PPO raw powder (Nantong star synthetic materials Co., ltd., LXN 040), high impact polystyrene particles (Qimei chemical industry, PH-60), antioxidant 1010 and antioxidant 168 is 10:87:2:1, and the mass ratio of physical modifier to poly epoxy functional group modifier is 100:0.121.
Application example 3
The only differences from application example 1 are: the modified PPO material of example 3 was used with a saturation temperature of 110 ℃.
Comparative example 1
The only differences from example 1 are: the multi-epoxy functional modifier is not added during chemical modification.
Comparative application example 1
The only differences from application example 1 are: the modified PPO material of comparative example 1 was used.
Comparative example 2
The only differences from example 3 are: the polyepoxy functional group modifier is not added during the secondary modification.
Comparative application example 2
The only differences from application example 1 are: the modified PPO material of comparative example 2 was used.
Comparative example 3
The only differences from example 1 are: the mass ratio of PPO raw powder (Nantong star synthetic materials Co., ltd., LXN 040), high impact polystyrene particles (Qimei chemical industry, PH-60), antioxidant 1010 and antioxidant 168 is 90:10:0:0.
Comparative application example 3
The only differences from application example 1 are: the modified PPO material of comparative example 3 was used.
Comparative example 4
The only differences from example 1 are: the mass ratio of PPO raw powder (Nantong star synthetic materials Co., ltd., LXN 040), high impact polystyrene particles (Qimei chemical industry, PH-60), antioxidant 1010 and antioxidant 168 is 97:0:2:1.
Comparative application example 4
The only differences from application example 1 are: the modified PPO material of comparative example 4 was used.
Comparative application example 5
The only differences from application example 1 are: the saturation temperature was 255 ℃.
Comparative application example 6
The only differences from application example 3 are: the saturation temperature was 90 ℃.
The molecular weight of the modified PPO and the flexural strength of the modified PPO materials of examples 1 to 3 and comparative examples 1 to 6 were measured, and the results are shown in table 1.
TABLE 1 molecular weight of modified PPOs of examples 1 to 3 and comparative examples 1 to 6 and flexural Strength of modified PPO materials
Figure BDA0004092009560000071
As can be seen from Table 1, the molecular weight of the modified PPO was increased. This demonstrates that the polyepoxy modifier reacts with the PPO, otherwise the molecular weight should not change much.
The densities and average pore diameters of the foam materials finally produced in application examples 1 to 3 and comparative examples 1 to 3 and 5 to 6 were measured, and the results are shown in table 2.
TABLE 2 foam density and average cell size
Figure BDA0004092009560000072
Figure BDA0004092009560000081
As can be seen from Table 2, the modified PPO material of the invention has a density of less than 25kg/m 3 The PPO foaming material with the average pore diameter smaller than 15 mu m has better foamability.
Meanwhile, it was found that the long-chain branching modification by the epoxy functional group modifier can increase the molecular weight and can increase the flexural strength of the material by comparing the application examples 1 to 2 with the comparative application example 1 and the application example 3 with the comparative application example 2. The modified PPO materials in the comparative application examples 1 and 2 do not adopt epoxy functional group modifier, so that the polymer chain segment is a linear chain segment, heterogeneous nucleation sites cannot be provided, and meanwhile, the lower melt strength of the linear chain segment cannot support the cell structure, so that more coalescence occurs in cells, the cell size is larger, and the material density is higher.
The modified PPO material in comparative example application example 3 has no antioxidant added, so that the material is severely degraded in the processing process, the molecular weight and the bending strength are low, and the melt strength cannot support cells, so that the cells are huge, and the material density is high.
The modified PPO material in the comparative application example 4 is not added with high impact polystyrene, PPO is difficult to process, and when the twin-screw is processed, the die head pressure is too high, the machine is stopped in an alarm mode, and the subsequent operation cannot be carried out.
The foaming temperature of comparative application example 5 was high and the cells collapsed in large amounts, so the material density was high and the cells were not observed.
The foaming temperature of comparative application example 6 was low, at which time the melt strength of the matrix was too high and the cells were difficult to grow, so the material density was high and the cell size was small.
The cross-sectional electron microscope scan analysis of the PPO foam material of application example 1 shows the results of fig. 1. As can be seen from FIG. 1, the average pore size of the foam material is small, only 8.91. Mu.m.
The cross-sectional electron microscope scan analysis of the PPO foam material of application example 2 shows the results of fig. 2. As can be seen from FIG. 2, the average pore size of the foamed material is small, only 9.72. Mu.m.
The PPO foam material of comparative application example 1 was subjected to cross-sectional electron microscopy scanning analysis, and the results are shown in fig. 3. As is clear from FIG. 3, the average pore size of the foam material is large, exceeding 20. Mu.m.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.

Claims (10)

1. The modified PPO material is characterized by comprising modified PPO, high-impact polystyrene and an antioxidant; the modified PPO comprises PPO and a branched chain grafted on the PPO through an ether bond;
the branched chain is formed by etherifying the PPO after the ring of the multi-epoxy functional group modifier is opened.
2. A modified PPO material as claimed in claim 1, wherein the polyepoxy functional modifier comprises TGIC or basf chain extender ADR.
3. A modified PPO material as claimed in claim 2, wherein when the polyepoxy functional modifier is a basf chain extender ADR, the basf chain extender ADR is 2.0 to 6.0wt% of PPO; when the polyepoxy functional group modifier is TGIC, the TGIC is 0.6-2.0wt% of PPO.
4. A process for the preparation of a modified PPO material as claimed in any of claims 1-3, characterized by the steps of:
performing first co-extrusion on PPO, high impact polystyrene and an antioxidant to obtain a physical modified substance;
and (3) performing second coextrusion on the physical modifier and the polyepoxy functional group modifier to perform ring opening and etherification to obtain the modified PPO material.
5. The method of claim 4, wherein the first and second coextrusion temperatures are independently 240 to 285 ℃.
6. The preparation method according to claim 4, wherein the mass ratio of the PPO to the high impact polystyrene is 1:0.05-13.
7. The preparation method according to claim 4 or 6, wherein the mass ratio of the PPO to the antioxidant is 0.3-30:1.
8. A PPO foam material characterized by being obtained by foaming a modified PPO material as defined in any one of claims 1 to 3 or a modified PPO material obtained by the production method as defined in any one of claims 4 to 7; the density of the PPO foaming material is 17-21 kg/m 3 。
9. The method for preparing the PPO foam material as defined in claim 8, comprising the steps of:
processing the modified PPO material to obtain a sheet-shaped to-be-foamed body;
the sheet-shaped to-be-foamed body is subjected to pressure relief after being saturated in a gas foaming agent, so that the PPO foaming material is obtained;
the saturation temperature is 100-250 ℃, the pressure is 10-20 Mpa, and the time is more than or equal to a× (d/2) 1 . 75 Wherein a= 0.2762h/mm 1.75 D is the thickness of the body to be foamed, and the unit is mm.
10. The method according to claim 9, wherein the pressure release rate is 100 to 1000MPa/s.
CN202310147976.0A 2023-02-21 2023-02-21 Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof Pending CN116102872A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310147976.0A CN116102872A (en) 2023-02-21 2023-02-21 Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310147976.0A CN116102872A (en) 2023-02-21 2023-02-21 Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof

Publications (1)

Publication Number Publication Date
CN116102872A true CN116102872A (en) 2023-05-12

Family

ID=86254155

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310147976.0A Pending CN116102872A (en) 2023-02-21 2023-02-21 Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN116102872A (en)

Similar Documents

Publication Publication Date Title
CN111087701B (en) Antibacterial polypropylene composition, microporous antibacterial polypropylene foamed sheet, preparation method of microporous antibacterial polypropylene foamed sheet and foamed sheet
CN111138755A (en) Low-density low-dielectric polypropylene composite material and preparation method thereof
CN106589440B (en) A kind of production method of polyethylene foamed/polystyrene bead
CN103819885B (en) A kind of polylactic acid foam material and preparation method thereof
CN114316458B (en) Foamed polyolefin beads and molded articles thereof
CN110746749A (en) Method for preparing micro-nano cellulose polyester microcellular foam sheet by step method
CN108409985B (en) Method for improving foaming ratio of polylactic acid through pre-isothermal cold crystallization treatment
CN111961309A (en) Modified ABS reclaimed material and preparation method thereof
CN115135704A (en) Expanded polypropylene beads, process for producing expanded polypropylene beads, molded article formed from expanded polypropylene beads, and process for forming such molded article
CN112759825B (en) Fiber reinforced polypropylene composition, foamed polypropylene composite material and preparation method thereof
CN111978585A (en) Preparation method and application of polymer foam material with trimodal cellular structure
CN104072880B (en) The preparation method of a kind of TPO foam microspheres and application
CN116144147B (en) Environment-friendly composite material and preparation method thereof
CN109265825B (en) Polypropylene or polypropylene compound foamed product and preparation method thereof
EP2267066A1 (en) Aliphatic polyester resin foam, flower arrangement holder made of the foam, and processes for production of both
CN112795091A (en) Foaming material and foaming product prepared from same
CN116102872A (en) Modified PPO material and preparation method thereof, PPO foam material and preparation method thereof
CN110283372B (en) Microcellular foam material of bimodal high-density polyethylene and preparation method thereof
CN102408629A (en) Preparation method for polypropylene foaming material based on novel auxiliary system
CN114605694B (en) Reinforced polybutene foam material and preparation method thereof
CN114874594B (en) High-resilience wave-absorbing foam material and preparation method thereof
CN114605623B (en) Flexible PET-based copolyester and bead foam prepared from same
CN110128741B (en) Polyolefin foam material and preparation method thereof
CN114106506B (en) PP/PA6 porous composite material and preparation method thereof
CN115368680A (en) Polypropylene micro-foaming material and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination