CN107955343A - Crosslinking with radiation biodegradable foam material and preparation method thereof - Google Patents
Crosslinking with radiation biodegradable foam material and preparation method thereof Download PDFInfo
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- CN107955343A CN107955343A CN201711196120.3A CN201711196120A CN107955343A CN 107955343 A CN107955343 A CN 107955343A CN 201711196120 A CN201711196120 A CN 201711196120A CN 107955343 A CN107955343 A CN 107955343A
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- 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
- C08J9/06—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 chemical blowing agent
- C08J9/10—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 chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
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- C08J3/246—Intercrosslinking of at least two polymers
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08K5/00—Use of organic ingredients
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Abstract
Crosslinking with radiation biodegradable foam material and preparation method thereof, belongs to foam technology field.Solve the problems, such as how to provide the foamed material that a kind of excellent physical properties, water-tolerant, durability are good, expansion ratio is higher, can regulate and control mechanical property in a wide range.The foamed material of the present invention, it is made of 50 100 parts by weight polyadipate mutual-phenenyl two acid bromide two alcohol esters, 0 50 parts by weight biodegradable polymers, 1 10 parts by weight of inorganic fillers, 0.5 15 parts by weight of blowing agent, 0.01 5 parts by weight blowing promotors and 0.1 10 parts by weight of crosslinking agent, wherein, crosslinking agent is the one or more in vinyl trimethylsilane, vinyltriethoxysilane, vinyl three (β methoxy ethoxies) silane.The foamed material possesses the advantages of excellent physical properties, water-tolerant, durability are good, expansion ratio is higher, and can regulate and control mechanical property in a wide range.
Description
Technical field
The invention belongs to foam technology field, and in particular to a kind of crosslinking with radiation biodegradable foam material and its
Preparation method.
Background technology
Foamed material be using plastics as solvent and containing a large amount of bubbles polymeric material, therefore could also say that with
Gas is the composite plastic of filler.Compared with pure plastics, it has many excellent performances, such as light, specific strength is high, absorbable
Shock loading, heat-insulated and sound insulation value are good etc..Extensively should thus it be obtained in the field such as industry, agricultural, building, communications and transportation
With.
Foamed material is mainly based on polystyrene, polyethylene, polyvinyl chloride and polyurethane etc. at present, general foam material
Expect that volume is big, non-degradable, recycling is difficult, exacerbates white pollution.Therefore, Devoting Major Efforts To Developing and promote degradable foamed material by
To the concern of worldwide academia and industrial quarters.Compared with universal foam material, degradable foamed material currently on the market
Expect poor mechanical property, water resistance is poor, and the durability of product is poor.
Polyadipate-mutual-phenenyl two acid bromide two alcohol ester, is made by adipic acid, terephthalic acid (TPA) and butanediol through polycondensation, it
The materials such as carbon dioxide and water, environmental sound can be finally degraded under the action of bacterium or enzyme.And due to synthesis
Raw materials used to be easy to get relatively, synthesis technique is also easy relative to microbe fermentation method etc., so having in cost obvious excellent
Gesture.It is hopeful to substitute general polyethylene or polypropylene and enter general-purpose plastics field, it is dirty caused by environment alleviates conventional plastic
Dye.BASF Aktiengesellschaft has been realized in the industrialization production of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, trade name It is a kind of biodegradable plastic truly of BASF AG's production, because it is in soil
Only with can rot in several weeks in earth or in fertilizer, and it will not leave behind any residue.Therefore, it is prepared into foaming
After material, the pollution problem that traditional expanded material is brought can be effectively solved.BASF AG is to be pushed away in 1998 in the market
Go out this product, since it possesses very excellent quality so that it becomes the leading position that occupy in world markets
Artificial creature's degradable material.At home, at present, Ye You many enterprises realize polyadipate-mutual-phenenyl two acid bromide two alcohol ester's production
Industry metaplasia is produced.Although polyadipate-mutual-phenenyl two acid bromide two alcohol ester possesses excellent degradability, widely should obtain
With, but as people are for the raising of the pursuit of product quality, the performance requirement of foamed material has not been contented just to merely
Its feature of environmental protection, people, which are more desirable to it, can have both excellent comprehensive performance, such as physical property, water resistance, durability, and be
Meet different application demand, to the controllability of material property also there is certain vision.
The content of the invention
The purpose of the present invention is how to provide a kind of excellent physical properties, water-tolerant, durability be good, expansion ratio compared with
The crosslinking with radiation biodegradable foam material and its system of mechanical property high, that expanded material can be regulated and controled in a wide range
Preparation Method.
Crosslinking with radiation biodegradable foam material, composition and parts by weight are：
The biodegradable polymers are polylactic acid, carbon dioxide-epoxy propane copolymer, poly butylene succinate
In one or more mixing in any proportion；
The crosslinking agent is vinyl trimethylsilane, vinyltriethoxysilane, (the 'beta '-methoxy ethoxy of vinyl three
Base) one or more mixing in any proportion in silane.
Preferably, composition and parts by weight are：
Preferably, the inorganic filler is that the one or more in silica, talcum powder, calcium carbonate, montmorillonite are pressed
The mixing of arbitrary proportion.
Preferably, the foaming agent for azodicarbonamide, Barium azodicarboxylate, diisopropyl azodiformate, N,
One or more mixing in any proportion in N- dinitrosopentamethlyene tetramines, 4,4 '-oxobenzenesulfonyl hydrazide.
Preferably, the blowing promotor is that the one or more in zinc oxide, zinc stearate, calcium stearate press any ratio
The mixing of example.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material, step are as follows：
Step 1: weighing each raw material by composition and parts by weight, add in extruder and carry out mixing granulator, mixing granulator temperature
For 80-170 DEG C, the obtained mixing granulator material extrusion sheet on sheet extruder, sheet thickness 0.5-3.0mm, extrusion temperature
Spend for 100-170 DEG C；
Step 2: at room temperature in air, crosslinking with radiation is carried out to blend sheet, irradiation dose 0.5-9KGy, obtains
Precrosslink material；
Step 3: by precrosslink material, 2-48h is further crosslinked in 50-80 DEG C of hot bath, obtains crosslinking material；
Step 4: crosslinking material is foamed, temperature is 190-250 DEG C, and time 1-20min, obtains crosslinking with radiation
Biodegradable foam material.
Preferably, mixing granulator is completed in double screw extruder, and the equipment of extrusion sheet is extruded for single screw rod sheet material
Machine.
Preferably, ionized radiation source is60Co sources or electron accelerator.
Preferably, crosslinking material foams in vertical or horizontal foaming furnace.
Compared with prior art, beneficial effects of the present invention：
The present invention crosslinking with radiation biodegradable foam material possess excellent physical properties, water-tolerant, durability it is good,
The advantages of expansion ratio is higher, and by with other biological degradable macromolecule, as polylactic acid, carbon dioxide-epoxy propane are common
Polymers, poly butylene succinate etc. carry out blending foaming, can regulate and control the mechanical property of expanded material in a wide range,
Such as compressive strength, compression modulus, allows it to meet more application fields, after testing, foamed material of the invention
Apparent density is 50-500Kg/m3, tensile strength 1.10-2.64MPa, elongation at break 370-560%, compressive strength is
0.45-5.56MPa。
The preparation method of the crosslinking with radiation biodegradable foam material of the present invention uses the silane conduct for containing vinyl
Crosslinking agent, realizes and carries out cross-linking radiation to polyadipate-mutual-phenenyl two acid bromide two alcohol ester and its blend under low radiation dose,
RADIATION PROCESSING cost is reduced, meanwhile, it can accelerate these biodegradable foamed materials after molecule interchain introduces silica chemical bond
Biodegradation rate；
The preparation method of the crosslinking with radiation biodegradable foam material of the present invention is using cross-linking radiation and hydro-thermal crosslinking knot
Close, it is ensured that material meets the needs of foaming, excellent physical properties, water-tolerant is made, durability is good, expansion ratio is higher
Foamed plastics, and further reduce dose of radiation；
The preparation method of the crosslinking with radiation biodegradable foam material of the present invention is using cross-linking radiation at room temperature, operation letter
It is single.
Embodiment
In order to further appreciate that the present invention, the preferred embodiments of the invention are retouched with reference to embodiment
State, but it is to be understood that these descriptions are intended merely to further illustrate the spy of the present invention and are weighed just with advantage rather than to the present invention
The limitation that profit requires.
The crosslinking with radiation biodegradable foam material of the present invention, by 50-100 parts by weight polyadipate-terephthalic acid (TPA)
Butanediol ester, 0-50 parts by weight biodegradable polymers, 1-10 parts by weight of inorganic filler, 0.5-15 parts by weight of blowing agent,
0.01-5 parts by weight blowing promotor and 0.1-10 parts by weight of crosslinking agent composition.
Wherein, polyadipate-mutual-phenenyl two acid bromide two alcohol ester's parts by weight are preferably 60-80, more preferably 65-75, especially
Preferably 70.Biodegradable polymers are polylactic acid, in carbon dioxide-epoxy propane copolymer, poly butylene succinate
One or more mixing in any proportion, parts by weight are preferably 10-40, more preferably 15-30, especially preferably 20-25.
Inorganic filler is silica, talcum powder, calcium carbonate, one or more mixing in any proportion in montmorillonite, parts by weight
Preferably 5-8, more preferably 6-7.5, especially preferably 6.5-7.Foaming agent is azodicarbonamide, Barium azodicarboxylate, idol
Nitrogen dioctyl phthalate diisopropyl ester, N, N- dinitrosopentamethlyene tetramines, 4, the one or more in 4 '-oxobenzenesulfonyl hydrazide are pressed
The mixing of arbitrary proportion, parts by weight are preferably 8-13, more preferably 10-12, and especially preferably 11.Blowing promotor for zinc oxide,
One or more mixing in any proportion in zinc stearate, calcium stearate, parts by weight are preferably 2-4, more preferably 2.5-
3.5, especially preferably 3.Crosslinking agent is vinyl trimethylsilane, vinyltriethoxysilane, three ('beta '-methoxy of vinyl
Ethyoxyl) one or more mixing in any proportion in silane, parts by weight are preferably 5-8, more preferably 5.5-7, especially
Preferably 6-6.5.
The preparation method of the crosslinking with radiation biodegradable foam material of the present invention, step are as follows：
Step 1: weighing each raw material by composition and parts by weight, add in double screw extruder and carry out mixing granulator, mixing is made
Grain temperature is 80-170 DEG C, obtained mixing granulator material extrusion sheet on single screw rod sheet extruder, sheet thickness 0.5-
3.0mm, preferably 1mm, extrusion temperature are 100-170 DEG C；
Step 2: at room temperature in air, crosslinking with radiation is carried out to blend sheet, irradiation dose 0.5-9KGy, obtains
Precrosslink material；
Step 3: by precrosslink material, 2-48h is further crosslinked in 50-80 DEG C of hot bath, obtains crosslinking material；
Step 4: crosslinking material is foamed in vertical or horizontal foaming furnace, temperature is 190-250 DEG C, time 1-
20min, is preferably 220-240 DEG C, time 4-10min, obtains crosslinking with radiation biodegradable foam material.
The further details of explanation present invention of embodiment will be passed through below.But the invention is not limited in these examples.
Embodiment 1
Crosslinking with radiation biodegradable foam material, by by 100 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester,
5 parts by weight of azodicarbonamide, 0.5 parts by weight group of 5 parts by weight of calcium carbonate, 1 parts by weight of zinc oxide and vinyl trimethylsilane
Into.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm, then using electron accelerator, at room temperature air
In to sheet material carry out pre-irradiation, irradiation dose 9KGy, the sheet material after pre-irradiated is crosslinked, in 80 DEG C of hot bath further
After being crosslinked 2h, obtained crosslinking material foams in vertical-foaming stove, and blowing temperature is 220 DEG C, foamed time 4min.
Embodiment 2
Crosslinking with radiation biodegradable foam material, by 70 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly- breast
Sour 30 parts by weight, 5 parts by weight of azodicarbonamide, 5 parts by weight of calcium carbonate, 1 parts by weight of zinc oxide and vinyl triethoxyl silicon
0.5 parts by weight of alkane form.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm.Using60Co sources, at room temperature to sheet material in air
Pre-irradiation is carried out, irradiation dose 9KGy, the sheet material after pre-irradiated is crosslinked, is further crosslinked 48h in 50 DEG C of hot bath,
Foam in vertical-foaming stove, blowing temperature is 220 DEG C, foamed time 4min.
The crosslinking with radiation biodegradable foam material obtained to embodiment 2 carries out performance detection, the testing result such as institute of table 1
Show.
Embodiment 3
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of lactic acid, 5 parts by weight of azodicarbonamide, three (beta-methoxy of 5 parts by weight of calcium carbonate, 1 parts by weight of zinc oxide and vinyl
Base oxethyl) silane 0.5 parts by weight composition.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm.Using electron accelerator, at room temperature in air
Pre-irradiation is carried out to sheet material, irradiation dose 9KGy, the sheet material after pre-irradiated is crosslinked, is further handed in 70 DEG C of hot bath
Join 24h, foam in vertical-foaming stove, blowing temperature is 220 DEG C, foamed time 4min.
The crosslinking with radiation biodegradable foam material obtained to embodiment 3 carries out performance detection, the testing result such as institute of table 1
Show.
Embodiment 4
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, two
50 parts by weight of carbonoxide-epoxy propane copolymer, 5 parts by weight of azodicarbonamide, 5 parts by weight of calcium carbonate, 1 parts by weight of zinc oxide
Formed with 0.5 parts by weight of vinyl three ('beta '-methoxy ethyoxyl) silane.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm.Using electron accelerator, at room temperature in air
Pre-irradiation is carried out to sheet material, irradiation dose 9KGy, the sheet material after pre-irradiated is crosslinked, is further handed in 70 DEG C of hot bath
Join 24h, foam in vertical-foaming stove, blowing temperature is 220 DEG C, foamed time 4min.
Embodiment 5
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of succinic acid-butanediol ester, 5 parts by weight of azodicarbonamide, 5 parts by weight of calcium carbonate, 1 parts by weight of zinc oxide and ethene
0.5 parts by weight of base three ('beta '-methoxy ethyoxyl) silane form.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm.Using electron accelerator, at room temperature in air
Pre-irradiation is carried out to sheet material, irradiation dose 6KGy, the sheet material after pre-irradiated is crosslinked, is further handed in 70 DEG C of hot bath
Join 24h, foam in vertical-foaming stove, blowing temperature is 220 DEG C, foamed time 4min.
The crosslinking with radiation biodegradable foam material obtained to embodiment 5 carries out performance detection, the testing result such as institute of table 1
Show.
Embodiment 6
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of succinic acid-butanediol ester, 0.5 parts by weight of Barium azodicarboxylate, silica 1 parts by weight, 0.01 weight of zinc stearate
Part and 0.1 parts by weight of vinyl three ('beta '-methoxy ethyoxyl) silane composition.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 3.0mm.Using electron accelerator, at room temperature in air
Pre-irradiation is carried out to sheet material, irradiation dose 2KGy, the sheet material after pre-irradiated is crosslinked, is further handed in 70 DEG C of hot bath
Join 24h, foam in horizontal foaming furnace, blowing temperature is 250 DEG C, foamed time 1min.
The crosslinking with radiation biodegradable foam material obtained to embodiment 6 carries out performance detection, the testing result such as institute of table 1
Show.
Embodiment 7
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of succinic acid-butanediol ester, 15 parts by weight of diisopropyl azodiformate, 10 parts by weight of montmorillonite, 5 weight of calcium stearate
Measure part and 10 parts by weight of vinyl three ('beta '-methoxy ethyoxyl) silane composition.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 0.5mm.Using electron accelerator, at room temperature in air
It is further in 70 DEG C of hot bath to sheet material progress pre-irradiation, irradiation dose 0.5KGy, the sheet material after pre-irradiated is crosslinked
24h is crosslinked, is foamed in horizontal foaming furnace, blowing temperature is 220 DEG C, foamed time 1min.
The crosslinking with radiation biodegradable foam material obtained to embodiment 7 carries out performance detection, the testing result such as institute of table 1
Show.
Embodiment 8
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of succinic acid-butanediol ester, N, 15 parts by weight of N- dinitrosopentamethlyene tetramines, 10 parts by weight of montmorillonite, stearic acid
5 parts by weight of calcium and 10 parts by weight of vinyl three ('beta '-methoxy ethyoxyl) silane composition.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.5mm.Using electron accelerator, at room temperature in air
Pre-irradiation is carried out to sheet material, irradiation dose 5KGy, the sheet material after pre-irradiated is crosslinked, is further handed in 70 DEG C of hot bath
Join 24h, foam in horizontal foaming furnace, blowing temperature is 220 DEG C, foamed time 1min.
The crosslinking with radiation biodegradable foam material obtained to embodiment 8 carries out performance detection, the testing result such as institute of table 1
Show.
Embodiment 9
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of succinic acid-butanediol ester, 4,4 '-oxobenzenesulfonyl hydrazide, 15 parts by weight, 10 parts by weight of talcum powder, 5 weight of stearic acid
Part and 10 parts by weight of vinyl three ('beta '-methoxy ethyoxyl) silane composition.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm.Using electron accelerator, at room temperature in air
Pre-irradiation is carried out to sheet material, irradiation dose 1KGy, the sheet material after pre-irradiated is crosslinked, is further handed in 70 DEG C of hot bath
Join 36h, foam in horizontal foaming furnace, blowing temperature is 190 DEG C, foamed time 20min.
The crosslinking with radiation biodegradable foam material obtained to embodiment 9 carries out performance detection, the testing result such as institute of table 1
Show.
Comparative example 1
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of succinic acid-butanediol ester, 4,4 '-oxobenzenesulfonyl hydrazide, 15 parts by weight, 10 parts by weight of talcum powder, 5 weight of stearic acid
Part and 10 parts by weight of Triallyl isocyanurate composition.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm.Using electron accelerator, at room temperature in air
Pre-irradiation is carried out to sheet material, irradiation dose 1KGy, the sheet material after pre-irradiated is crosslinked, is further handed in 70 DEG C of hot bath
Join 36h, foam in horizontal foaming furnace, blowing temperature is 190 DEG C, foamed time 20min.
Comparative example 2
Crosslinking with radiation biodegradable foam material, by by 50 parts by weight of polyadipate-mutual-phenenyl two acid bromide two alcohol ester, poly-
50 parts by weight of succinic acid-butanediol ester, 4,4 '-oxobenzenesulfonyl hydrazide, 15 parts by weight, 10 parts by weight of talcum powder, 5 weight of stearic acid
Part and 10 parts by weight of Triallyl isocyanurate composition.
The preparation method of above-mentioned crosslinking with radiation biodegradable foam material：First above-mentioned original is weighed by composition and parts by weight
Material, then carries out mixing granulator, mixing granulator temperature is 80-170 DEG C, then using Single screw extrusion using double screw extruder
Machine is extruded into sheet material, and extrusion temperature is 100-170 DEG C, sheet thickness 1.0mm.Using electron accelerator, at room temperature in air
Sheet material is irradiated, irradiation dose 100KGy.Sheet material after radiation is foamed in horizontal foaming furnace, blowing temperature is
190 DEG C, foamed time 20min.
To the apparent density of the biodegradable radiation cross-linked foam material of embodiment 1-9 and comparative example 1-2, expansion ratio,
Tensile strength, elongation at break, compressive strength and durability are detected.Wherein, apparent density passes through GB-T-6343-2009
It is detected；Tensile strength and elongation at break use the method in GBGB/T6344-1996 to be detected；Compressive strength uses
Method in GBGB/T8813-2008 is detected；The method that durability uses is detected.Testing result is as shown in table 1.
The performance of the biodegradable radiation cross-linked foam material of table 1 embodiment 1-9 and comparative example 1-2
As it can be seen from table 1 crosslinking agent only using the present invention, could the excellent foam material of two steps crosslinking processability
Material, crosslinking agent of the prior art can not be crosslinked (comparative example 1) using low irradiation dose, and crosslinking with radiation of the invention can give birth to
Thing degraded foamed material possesses the advantages of excellent physical properties, durability are good, expansion ratio is higher, not less than adopting in the prior art
With big irradiation dose crosslinking prepare foamed material technology (comparative example 2), and by with other biological degradable macromolecule, such as
Polylactic acid, carbon dioxide-epoxy propane copolymer, poly butylene succinate etc. carry out blending foaming, can be in very wide model
Enclose the mechanical property of interior regulation and control expanded material.
The water resistance of the foamed material of embodiment 1-9 is detected, detection method is：Crosslinking with radiation is biodegradable
Foamed material soaks 15 days in 80 DEG C waters.After testing, after soaking 15 days, the good-looking of foamed material of the invention,
There is no significant change, tensile strength is reduced without obvious.Illustrate the foamed material water-tolerant of the present invention.
Claims (9)
1. crosslinking with radiation biodegradable foam material, it is characterised in that composition and parts by weight are：
The biodegradable polymers are polylactic acid, in carbon dioxide-epoxy propane copolymer, poly butylene succinate
One or more mixing in any proportion；
The crosslinking agent is vinyl trimethylsilane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl)
One or more mixing in any proportion in silane.
2. crosslinking with radiation biodegradable foam material according to claim 1, it is characterised in that the composition and weight
Part it is：
3. crosslinking with radiation biodegradable foam material according to claim 1, it is characterised in that the inorganic filler is
One or more mixing in any proportion in silica, talcum powder, calcium carbonate, montmorillonite.
4. crosslinking with radiation biodegradable foam material according to claim 1, it is characterised in that the foaming agent is even
Nitrogen diformamide, Barium azodicarboxylate, diisopropyl azodiformate, N, N- dinitrosopentamethlyene tetramines, 4,4 '-oxo
One or more mixing in any proportion in double benzene sulfonyl hydrazides.
5. crosslinking with radiation biodegradable foam material according to claim 1, it is characterised in that the blowing promotor is
One or more mixing in any proportion in zinc oxide, zinc stearate, calcium stearate.
6. the preparation method of the crosslinking with radiation biodegradable foam material described in claim 1-5 any one, its feature exist
In step is as follows：
Step 1: weighing each raw material by composition and parts by weight, add in extruder and carry out mixing granulator, mixing granulator temperature is
80-170 DEG C, obtained mixing granulator material extrusion sheet on sheet extruder, sheet thickness 0.5-3.0mm, extrusion temperature
For 100-170 DEG C；
Step 2: at room temperature in air, crosslinking with radiation is carried out to blend sheet, irradiation dose 0.5-9KGy, is pre-payed
Join material；
Step 3: by precrosslink material, 2-48h is further crosslinked in 50-80 DEG C of hot bath, obtains crosslinking material；
Step 4: crosslinking material is foamed, temperature is 190-250 DEG C, time 1-20min, and obtaining crosslinking with radiation can give birth to
Thing degraded foamed material.
7. the preparation method of crosslinking with radiation biodegradable foam material according to claim 6, it is characterised in that be kneaded
Granulation is completed in double screw extruder, and the equipment of extrusion sheet is single screw rod sheet extruder.
8. the preparation method of crosslinking with radiation biodegradable foam material according to claim 6, it is characterised in that ionization
Radiation source is60Co sources or electron accelerator.
9. the preparation method of crosslinking with radiation biodegradable foam material according to claim 6, it is characterised in that crosslinking
Material foams in vertical or horizontal foaming furnace.
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| CN111040088A (en) * | 2019-11-27 | 2020-04-21 | 瑞欢环保科技(上海)有限公司 | Method for preparing compatible organic or inorganic mixture by reactive extrusion |
| CN112552650A (en) * | 2019-09-25 | 2021-03-26 | 天津科技大学 | Full-biodegradable foam material of modified PBS (Poly Butylene succinate) and preparation method thereof |
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| CN110606971A (en) * | 2019-09-24 | 2019-12-24 | 北京百奥新材科技有限公司 | Biodegradable polyester composition and preparation method thereof |
| CN112552650A (en) * | 2019-09-25 | 2021-03-26 | 天津科技大学 | Full-biodegradable foam material of modified PBS (Poly Butylene succinate) and preparation method thereof |
| CN111040088A (en) * | 2019-11-27 | 2020-04-21 | 瑞欢环保科技(上海)有限公司 | Method for preparing compatible organic or inorganic mixture by reactive extrusion |
| CN112812515A (en) * | 2020-12-31 | 2021-05-18 | 浙江工业大学 | Degradable foaming material and preparation method thereof |
| CN112795154A (en) * | 2021-01-30 | 2021-05-14 | 汕头市三马塑胶制品有限公司 | Foaming-grade biodegradable polyester material and preparation method thereof |
| CN112920565A (en) * | 2021-01-30 | 2021-06-08 | 汕头市三马塑胶制品有限公司 | High-melt-strength biodegradable polyester material and preparation method thereof |
| CN113025002A (en) * | 2021-02-01 | 2021-06-25 | 浙江工业大学 | Degradable foaming material and preparation method thereof |
| CN113025002B (en) * | 2021-02-01 | 2022-08-23 | 浙江工业大学 | Degradable foaming material and preparation method thereof |
| CN115232351A (en) * | 2022-07-14 | 2022-10-25 | 湖北工业大学 | Preparation method of silicone rubber foam material |
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