CN114591553A - Radiation crosslinking polyethylene composition, foamed sheet and application thereof - Google Patents
Radiation crosslinking polyethylene composition, foamed sheet and application thereof Download PDFInfo
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- 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
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- C08J3/00—Processes of treating or compounding macromolecular substances
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- C08J2205/00—Foams characterised by their properties
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- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
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Abstract
The invention relates to the technical field of high polymer materials, in particular to a radiation crosslinking polyethylene composition, a foaming sheet and application thereof, wherein the radiation crosslinking polyethylene composition comprises low-density polyethylene, a toughening modified polyimide prepolymer, a foaming agent, a sensitizer and an auxiliary agent; wherein the end of the toughening modified polyimide prepolymer contains unsaturated double bonds, and the main chain of the toughening modified polyimide prepolymer contains polyethylene glycol chain segments. The invention overcomes the defect that the IXPE electronic cross-linked polyethylene foam in the prior art has poor heat preservation performance due to low closed cell rate, and introduces rigid toughened modified polyimide prepolymer into the traditional low-density polyethylene by the technical means of soft and hard doping through the radiation cross-linked polyethylene composition in the invention, so that the prepared foamed sheet has the closed cell rate of more than 95 percent and the foaming ratio of more than 45 times, thereby having good heat preservation effect and being capable of being applied in the field of heat preservation.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a radiation crosslinking polyethylene composition, a foaming sheet and application thereof.
Background
In modern decoration industry, wood floors are more and more favored by users and become a main form of ground decoration. In the finishing process of wood flooring, floor mats are indispensable important components. IXPE electron crosslinked polyethylene bubble is that the electron accelerator irradiation in-process makes PE intermolecular formation network cross-linking through the effect of high energy electron, is a novel environmental protection packaging material with thermal-insulated heat preservation function, and its epidermis and cell are more exquisite, the aperture is less, extensively is applicable to the thermal-insulated heat preservation of thermal-insulated packing, house construction, air conditioning engineering. It solves the problem that the previous glass fiber and foaming materials bring discomfort to human body and harm to environment.
The foamed material forms an open-cell or closed-cell structure within it during the foaming process, wherein the cell structure has a significant influence on the properties of the foam. In general, closed-cell foams have high mechanical strength, good thermal insulation and cushioning properties, and low water absorption, while open-cell foams are softer, more resilient, and have good sound insulation properties. Closed cell foams have low thermal conductivity and water absorption in addition to the properties of typical foams.
The closed porosity of the obtained foam pores of the conventional IXPE in the foaming process is usually 75-90%, so that the heat insulation and heat preservation of the conventional IXPE foam are better, but certain promotion space is still provided. For example, the application number is CN202011626110.0 a crosslinked polyolefin foamed sheet and its preparation method, it is a macromolecule foam field, the foamed sheet thickness is 0.01 mm-0.5 mm, the density is 0.3g/cm 3-0.8 g/cm3, when the compression deformation becomes 50%, the compressive stress is less than or equal to 2MPa, the foamed sheet body is not cracked when at least 60g globules fall from the height of more than 35mm, the closed cell rate is more than 85%, its crosslinking density is 15% -70%. The foaming sheet material has lower closed-cell rate, so the actual heat preservation and mechanical properties of the foaming sheet material still have a further improvement space.
Disclosure of Invention
The invention provides a radiation crosslinking polyethylene composition, a foaming sheet and application thereof to overcome the defects of poor heat insulation performance caused by low closed cell rate of IXPE electronic crosslinking polyethylene foam in the prior art.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a radiation crosslinking polyethylene composition comprises low density polyethylene, toughening modified polyimide prepolymer, foaming agent, sensitizer and auxiliary agent;
wherein the end of the toughening modified polyimide prepolymer contains unsaturated double bonds, and the main chain of the toughening modified polyimide prepolymer contains polyethylene glycol chain segments.
In the prior art, IXPE electronic cross-linked polyethylene foam is generally prepared by low-density polyethylene after electronic radiation cross-linking and foaming. Because the low-density polyethylene molecular chains are mainly composed of flexible carbon-carbon bonds, cells generated in the foaming process are easy to break and open, and the closed cell rate of the finally obtained IXPE electronic crosslinked polyethylene foam is low.
Therefore, a certain amount of toughening modified polyimide prepolymer is added in the traditional low-density polyethylene, and as the polyimide structure in the polyimide prepolymer has higher rigidity compared with flexible carbon-carbon bonds, the rigid chain segment is introduced into the flexible chain segment of the polyethylene, so that cells generated in the foaming process are not easy to break, and the closed cell rate can be greatly improved.
Although the improvement of the rigidity of the polyethylene composition can have a certain effect on the closed cell ratio of the final foamed product, after research and development personnel tests, it is found that when the rigidity of the polyimide prepolymer is too high, the final foaming ratio is reduced, and meanwhile, cells are brittle and easy to break under the action of external force, so that the closed cell ratio of the finally obtained radiation crosslinked polyethylene foam cannot be further improved.
According to the invention, a certain amount of polyethylene glycol chain segment is added into the main chain of the polyimide prepolymer, and the polyethylene glycol chain segment has good flexibility, so that the defect of over-strong rigidity of the polyimide prepolymer can be effectively improved, and the polyimide prepolymer has the advantages of good rigidity and toughness. Therefore, the toughened and modified polyimide prepolymer added into the polyethylene composition can simultaneously have higher foaming ratio and closed cell ratio.
Preferably, the paint comprises the following components in parts by weight: 100 parts of low-density polyethylene, 20-40 parts of toughened and modified polyimide prepolymer, 20-35 parts of foaming agent, 1-3 parts of sensitizer and 0-10 parts of auxiliary agent.
The addition amount of the toughening modified polyimide prepolymer in the radiation crosslinking polyethylene composition accounts for 20-40% of that of the low-density polyethylene, and research and development personnel experiments show that when the addition amount of the toughening modified polyimide prepolymer is less than 20%, the improvement of the closed cell ratio of the radiation crosslinking polyethylene foam is less helpful, and the effect of higher closed cell ratio cannot be achieved; however, when the amount of the toughening modified polyimide prepolymer added is higher than 40%, the closed cell ratio is high, but the foaming ratio of the whole foam is low, and a low thermal conductivity cannot be achieved.
Preferably, the preparation method of the toughening modified polyimide prepolymer comprises the following steps:
(S.1) reacting polyethylene glycol with dimethylchlorosilane to obtain dimethyl silicon-based end-capped polyethylene glycol, and then reacting the dimethyl silicon-based end-capped polyethylene glycol with p-nitrophenol under the catalysis of tris (pentafluorobenzene) borane to obtain nitro end-capped polyethylene glycol;
(S.2) reducing the nitro group of the nitro-terminated polyethylene glycol to obtain diamino-terminated polyethylene glycol;
and (S.3) reacting the diamine-terminated polyethylene glycol, the diamine monomer, the dianhydride monomer and the capping agent containing unsaturated double bonds to obtain the polyimide prepolymer.
Preferably, the foaming agent is any one of azodicarbonamide, benzenesulfonyl hydrazide, dinitrosopentamethylenetetramine, toluenesulfonyl hydrazide or 4, 4' -oxybis-benzenesulfonyl hydrazide.
Preferably, the sensitizer is a compound containing two or more propylene groups.
More preferably, the sensitizer is at least one of N, N-methylenebisacrylamide, trimethylolpropane trimethacrylate, and triallyl isocyanurate.
Preferably, the auxiliary agent comprises one or more of inorganic filler, lubricant, antioxidant and conductive agent.
Further preferably, the inorganic filler includes any one of white carbon black, graphene, hollow glass beads, calcium oxide, and zinc oxide.
More preferably, the lubricant comprises any one of stearic acid, sodium stearate, zinc stearate and dimethyl silicone oil.
More preferably, the antioxidant comprises any one of antioxidant BHT, antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant DNP and antioxidant DLTP.
A foamed sheet is obtained by radiation crosslinking and foaming of the radiation crosslinked polyethylene composition.
The preparation method of the foaming sheet comprises the following steps:
(a) banburying low-density polyethylene, toughened and modified polyimide prepolymer and foaming agent to obtain foaming master batches; banburying the rest low-density polyethylene, sensitizer and auxiliary agent to obtain basic master batch;
(b) blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
(c) carrying out radiation crosslinking on the substrate through a high-speed electronic field to obtain a radiation crosslinked polyethylene sheet;
(d) and (3) carrying out foaming treatment on the radiation crosslinking polyethylene sheet to obtain a foamed sheet.
In the invention, a part of low-density polyethylene, toughening modified polyimide prepolymer and foaming agent are banburied to prepare foaming master batch, and the aim is to fully mix the foaming agent and the toughening modified polyimide prepolymer, so that the foaming agent can be completely wrapped by the toughening modified polyimide prepolymer, and the foaming process can be completed under the wrapping of the toughening modified polyimide prepolymer in the foaming process. Therefore, the formed foam holes are not easy to damage, and the closed porosity is greatly improved.
Preferably, the closed cell rate of the foamed sheet is not less than 95%, the thermal conductivity is not more than 0.035W/m.k, and the foaming ratio is not less than 45.
Use of the above radiation crosslinked polyethylene composition or foamed sheet in the field of insulation.
Therefore, the invention has the following beneficial effects:
the radiation crosslinking polyethylene composition is prepared by introducing rigid toughening modified polyimide prepolymer into the traditional low-density polyethylene through a soft-hard doping technical means, so that the prepared foamed sheet has a closed cell rate of more than 95% and a foaming ratio of more than 45 times, has a good heat insulation effect and can be applied to the field of heat insulation. Meanwhile, due to the introduction of the polyimide, the performance of the finally obtained foamed sheet can be greatly improved.
Detailed Description
The invention is further described with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
The preparation method of the toughened and modified polyimide prepolymer used in the embodiment of the invention is as follows:
the preparation method of the toughened and modified polyimide prepolymer comprises the following steps:
(S.1) under the protection of nitrogen, dissolving 2g (10mmol) of polyethylene glycol 200 and 2g (20mmol) of triethylamine in 50mol of dichloromethane, dropwise adding a mixed solution containing 1.88g (20mmol) of dimethylchlorosilane and 20ml of dichloromethane, reacting at 0 ℃ for 3h, filtering to remove triethylamine hydrochloride generated by the reaction, washing the filtrate with water, and evaporating to remove the solvent to obtain the dimethyl silicon-based end-capped polyethylene glycol, wherein the reaction formula is shown as the following formula (I).
(S.2) under the protection of nitrogen, dissolving 2g (10mmol) of dimethyl silicon-based end-capped polyethylene glycol and 10mg of tris (pentafluorobenzene) borane in 100mol of toluene, dropwise adding a mixed solution of 2.78g (20mmol) of p-nitrophenol and 30mol of toluene, reacting at 40 ℃ for 3h, adding 1g of activated carbon after the reaction is finished, adsorbing for 30min, filtering, and evaporating the solvent in the filtrate to obtain the nitro end-capped polyethylene glycol, wherein the reaction formula is shown in the following formula (II).
(S.3) under the protection of nitrogen, adding 1L of butanol into a reduction kettle, adding 10g of ammonium chloride and 50g of scrap iron under stirring, heating to 95 ℃, adding 35g of nitro-terminated polyethylene glycol represented by formula (II), stirring for reaction for 0.5h, then adding 40g of second batch of scrap iron and 25g of nitro-terminated polyethylene glycol represented by formula (II), stirring for reaction for 0.5h, then adding 40g of third batch of scrap iron and 25g of nitro-terminated polyethylene glycol represented by formula (II), continuing to react for 1.5h, and sampling to analyze the reaction end point. After the reaction is finished, 10g of sodium bisulfite is added, after stirring and dissolving, the reaction material is transferred to a crystallization kettle while the reaction material is hot, cooled and crystallized, then filtered, the filter cake is washed by water until no butanol exists, dried, and finally purified and decontaminated to obtain the amino-terminated polyethylene glycol, wherein the reaction formula is shown as the following formula (III).
(S.4) at a low temperature of 10 ℃ and under a nitrogen atmosphere, firstly dissolving 10.6g (20mmol) of amino-terminated polyethylene glycol shown as a formula (III) in 100g of N-methyl-2-pyrrolidone (NMP), adding 5.616g (18mmol) of bis (3, 4-dicarboxyphenyl) ether dianhydride (ODPA) and 0.4g (4.1mmol) of maleic anhydride after all the amino-terminated polyethylene glycol is dissolved, reacting for 4h to obtain a clear and transparent glue solution, then adding toluene (the amount of the toluene is equal to that of the solvent), stirring and reacting for 4h at a temperature of 180 ℃, cooling to room temperature after the reaction is finished, adding 1: 1, precipitating the mixed solution with the amount 4 times of the glue solution amount, washing for many times, and drying in a vacuum oven at 80 ℃ for 12 hours to obtain the toughened and modified polyimide prepolymer, wherein the structure schematic formula of the prepolymer is shown in the following formula (IV).
The comparative polyimide prepolymer was prepared as follows:
4g (20mmol) of 4, 4' -diaminodiphenyl ether was dissolved in 10g of N-methyl-2-pyrrolidone (NMP) at a low temperature of 10 ℃ under a nitrogen atmosphere, and after complete dissolution, 5.616g (18mmol) of bis (3, 4-dicarboxyphenyl) ether dianhydride (ODPA) was added thereto, followed by 0.4g (4.1mmol) of maleic anhydride as a capping agent, and reacted for 5 hours to obtain a clear and transparent gum solution. Then adding toluene (the amount of the toluene is equal to that of the solvent), stirring and reacting for 6h at 180 ℃, cooling to room temperature after the reaction is finished, and adding 1: 1, precipitating the mixed solution, washing the precipitate for multiple times, and drying the precipitate in a vacuum oven at 80 ℃ for 12 hours to obtain a comparative polyimide prepolymer.
Example 1
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 20 parts of toughened and modified polyimide prepolymer and 30 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of auxiliary agent (silicon dioxide) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 2
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 25 parts of toughened and modified polyimide prepolymer and 30 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of auxiliary agent (silicon dioxide) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 3
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 30 parts of toughened and modified polyimide prepolymer and 30 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of auxiliary agent (silicon dioxide) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 4
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 35 parts of toughened and modified polyimide prepolymer and 30 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of auxiliary agent (silicon dioxide) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder in each zone were 115 deg.C, 116 deg.C, 118 deg.C, 120 deg.C, 118 deg.C, and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 5
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 40 parts of toughened and modified polyimide prepolymer and 30 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of auxiliary agent (silicon dioxide) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 6
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 30 parts of toughened and modified polyimide prepolymer and 20 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of assistant (zinc stearate) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 7
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 30 parts of toughened and modified polyimide prepolymer and 25 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of assistant (zinc stearate) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 8
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 30 parts of toughened and modified polyimide prepolymer and 35 parts of foaming agent (azodicarbonamide) are banburied for 10min at 130 ℃ and 25rmp rotating speed, and granulation is carried out to obtain the foaming master batch.
50 parts of low-density polyethylene, 2 parts of sensitizer (N, N-methylene bisacrylamide) and 5 parts of assistant (zinc stearate) are subjected to banburying at 110 ℃ and 25rmp of rotation speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 9
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 30 parts of toughened and modified polyimide prepolymer and 30 parts of foaming agent (dinitrosopentamethylenetetramine) are banburied for 10min at the temperature of 130 ℃ and the rotating speed of 25rmp, and the foaming master batch is obtained through granulation.
50 parts of low-density polyethylene, 1 part of sensitizer (trimethylolpropane trimethacrylate) and 10 parts of assistant (antioxidant BHT) are subjected to banburying at 110 ℃ and 25rmp of rotating speed for 10min, and granulation is carried out to obtain the basic master batch.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
Example 10
A foamed sheet is prepared by the following steps:
(a) 50 parts of low-density polyethylene, 30 parts of toughened and modified polyimide prepolymer and 30 parts of foaming agent (dinitrosopentamethylenetetramine) are banburied for 10min at the temperature of 130 ℃ and the rotating speed of 25rmp, and the foaming master batch is obtained through granulation.
50 parts of low-density polyethylene and 3 parts of sensitizer (trimethylolpropane trimethacrylate) are banburied for 10min at the temperature of 110 ℃ and the rotating speed of 25rmp, and the basic master batch is obtained through granulation.
(b) Uniformly blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
the temperatures of the extruder zones were 115 ℃, 116 ℃, 118 ℃, 120 ℃, 118 ℃ and the screw rotation speed was 15 rmp.
(c) Carrying out radiation crosslinking on the substrate through a high-speed electron field with the irradiation dose of 55KGy to obtain a radiation crosslinked polyethylene sheet;
(d) placing the radiation crosslinked polyethylene sheet in a horizontal foaming furnace for foaming treatment to obtain a foamed sheet;
the temperature of the preheating section of the foaming furnace is 155 ℃, the preheating is 5min, the temperature of the foaming section is 210 ℃, the foaming time is 60s, and the mesh belt speed is 3 m/min.
The raw material proportioning table of the examples 1 to 10 is shown in the following table 1:
TABLE 1 raw material compounding tables for examples 1 to 10
Note: the unit of the addition of each substance in the above table is parts.
Comparative example 1
Comparative example 1 is different from example 1 in that the toughening modified polyimide prepolymer is added in an amount of 0 part.
Comparative example 2
Comparative example 2 is different from example 1 in that the toughening-modified polyimide prepolymer is added in an amount of 15 parts.
Comparative example 3
Comparative example 3 is different from example 1 in that the toughening modified polyimide prepolymer is added in an amount of 45 parts.
Comparative example 4
Comparative example 4 is different from example 3 in that the amount of the blowing agent added is 15 parts.
Comparative example 5
Comparative example 5 is different from example 3 in that the amount of the blowing agent added is 40 parts.
Comparative example 6
Comparative example 6 differs from example 3 in that the toughened modified polyimide prepolymer is replaced with a comparative polyimide prepolymer.
The raw material proportioning tables of comparative examples 1 to 5 are shown in the following table 2:
TABLE 2 raw material proportioning tables for comparative examples 1 to 5
Note: the unit of the addition of each substance in the above table is parts.
The raw material ratio of comparative example 6 is shown in table 3 below:
TABLE 3 raw material proportioning Table for comparative example 6
Note: the unit of the addition of each substance in the above table is parts.
The foamed sheets prepared in examples 1 to 10 and comparative examples 1 to 5 were subjected to tests for properties such as closed cell ratio, expansion ratio, thermal conductivity, and the like, and the test results are shown in table 4 below.
The foaming ratio test method comprises the following steps: the foaming ratio is determined by measuring the volume ratio of the radiation crosslinked polyethylene sheet after foaming and before foaming.
The closed cell fraction test method is as follows: obtained by testing through an HX-TP type full-automatic opening and closing porosity tester.
Thermal conductivity: the purpose of the test is to test the heat conducting property of the material, specifically, a slice with a specified thickness is placed on a heat source, the other end of the heat source and the other end of the material are connected with temperature sensors to record real-time temperature, and the time required by the temperature of one side far away from the heat source to rise from 25 ℃ to 60 ℃ is recorded.
TABLE 4 test results of examples 1 to 10 and comparative examples 1 to 4
Analyzing the data in the table, the following results can be obtained:
as can be seen from examples 1 to 5 and comparative examples 1 to 3, the closed cell ratio of the final foamed sheet can be effectively increased by adding the toughened and modified polyimide prepolymer to the radiation crosslinked polyethylene composition. From the detailed analysis, it is found that the closed cell ratio of the toughened and modified polyimide prepolymer in the composition tends to increase to a certain extent as the amount of the toughened and modified polyimide prepolymer added to the composition increases. Meanwhile, on the premise of similar foaming multiplying power, the heat conductivity also has a certain promotion trend along with the promotion of the closed porosity. Meanwhile, when the addition amount of the toughened and modified polyimide prepolymer is within 40 parts, the influence on the foaming ratio is small, but when the addition amount of the toughened and modified polyimide prepolymer is increased to 45 parts, the foaming ratio is obviously reduced, and the thermal conductivity is increased along with the reduction of the foaming ratio.
As is clear from examples 3, 6 to 8 and comparative examples 4 to 5, the main factor affecting the expansion ratio is the amount of the blowing agent added, and generally, the expansion ratio increases with the addition of the blowing agent. However, when the amount of the blowing agent added is 40 parts, the closed cell ratio decreases, and the thermal conductivity increases. The reason is presumed to be that as the amount of the blowing agent added increases, the foaming process becomes too vigorous, and the gas generated by the foaming breaks the cells, resulting in a decrease in the closed cell ratio.
Comparing example 3 with comparative example 6, it can be seen that the structure of the toughened and modified polyimide prepolymer has a significant effect on the expansion ratio of the foamed sheet. On the premise of the same addition amount, the comparative polyimide prepolymer used in comparative example 6 had a higher rigidity, resulting in a poor foaming effect and a lower expansion ratio. The consequent result is an increase in thermal conductivity. In the invention, the polyethylene glycol chain segment is introduced into the polyimide, so that the rigidity of the polyimide is reduced, the flexibility of the chain segment is greatly improved, and the influence on the foaming multiplying power is greatly reduced.
In summary, the radiation crosslinked polyethylene composition of the present invention introduces the rigid toughened and modified polyimide prepolymer into the conventional low density polyethylene by a soft and hard doping technical means, so that the foamed sheet prepared has a closed cell ratio of 95% or more and a foaming ratio of 45 times or more, and thus has a good thermal insulation effect, and can be applied in the thermal insulation field.
Claims (10)
1. A radiation crosslinking polyethylene composition is characterized by comprising low-density polyethylene, a toughening modified polyimide prepolymer, a foaming agent, a sensitizer and an auxiliary agent;
wherein the end of the toughening modified polyimide prepolymer contains unsaturated double bonds, and the main chain of the toughening modified polyimide prepolymer contains polyethylene glycol chain segments.
2. The radiation crosslinked polyethylene composition according to claim 1, characterized by comprising, in parts by weight: 100 parts of low-density polyethylene, 20-40 parts of toughened and modified polyimide prepolymer, 20-35 parts of foaming agent, 1-3 parts of sensitizer and 0-10 parts of auxiliary agent.
3. A radiation crosslinked polyethylene composition according to claim 1 or 2,
the preparation method of the toughening modified polyimide prepolymer comprises the following steps:
(S.1) reacting polyethylene glycol with dimethylchlorosilane to obtain dimethyl silicon-based end-capped polyethylene glycol, and then reacting the dimethyl silicon-based end-capped polyethylene glycol with p-nitrophenol under the catalysis of tris (pentafluorobenzene) borane to obtain nitro end-capped polyethylene glycol;
(S.2) reducing the nitro group of the nitro-terminated polyethylene glycol to obtain diamino-terminated polyethylene glycol;
and (S.3) reacting the diamine-terminated polyethylene glycol, the diamine monomer, the dianhydride monomer and the capping agent containing unsaturated double bonds to obtain the polyimide prepolymer.
4. A radiation crosslinked polyethylene composition according to claim 1 or 2, wherein said blowing agent is any one of azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, toluenesulfonylhydrazide or 4, 4' -oxybis-benzenesulfonylhydrazide.
5. A radiation crosslinked polyethylene composition according to claim 1 or 2, characterized in that said sensitizer is a compound containing two or more acrylic groups.
6. A radiation crosslinked polyethylene composition according to claim 1 or 2, wherein said auxiliary agent comprises one or more of inorganic filler, lubricant, antioxidant, conductive agent.
7. A foamed sheet obtained by radiation crosslinking and foaming the radiation crosslinked polyethylene composition according to any one of claims 1 to 6.
8. The foamed sheet according to claim 6, wherein the foamed sheet is prepared by the following method:
(a) banburying low-density polyethylene, toughened and modified polyimide prepolymer and foaming agent to obtain foaming master batches;
banburying the rest low-density polyethylene, sensitizer and auxiliary agent to obtain basic master batch;
(b) blending the foaming master batch and the basic master batch, and extruding the mixture by an extruder to obtain a substrate;
(c) carrying out radiation crosslinking on the substrate through a high-speed electronic field to obtain a radiation crosslinked polyethylene sheet;
(d) and (3) carrying out foaming treatment on the radiation crosslinking polyethylene sheet to obtain a foamed sheet.
9. The foamed sheet according to claim 7 or 8, wherein the foamed sheet has a closed cell content of 95% or more, a thermal conductivity of 0.035W/m-k or less, and a foaming ratio of 45 or more.
10. Use of the radiation crosslinked polyethylene composition according to any one of claims 1 to 6 or the foamed sheet according to any one of claims 7 to 9 in the field of thermal insulation.
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