CN108822378A - Cross-linked foam polyolefin material and preparation method thereof with antibacterial functions - Google Patents

Cross-linked foam polyolefin material and preparation method thereof with antibacterial functions Download PDF

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Publication number
CN108822378A
CN108822378A CN201810517348.6A CN201810517348A CN108822378A CN 108822378 A CN108822378 A CN 108822378A CN 201810517348 A CN201810517348 A CN 201810517348A CN 108822378 A CN108822378 A CN 108822378A
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foaming agent
parts
agent
antibacterial
catalyst
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段建平
魏琼
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Hubei Xiangyuan New Material Technology Inc
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Hubei Xiangyuan New Material Technology Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—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
    • C08J9/103—Azodicarbonamide
    • 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
    • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
    • 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
    • C08J9/06—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
    • C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
    • C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
    • 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
    • C08J9/06—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
    • C08J9/107—Nitroso compounds
    • 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
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • 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
    • 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
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene

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

Abstract

The present invention discloses a kind of cross-linked foam polyolefin material and preparation method thereof with antibacterial functions；It includes 45~91.5 parts of polythylene resin, 5~30 parts of ethylene copolymer, 2~20 parts of modified foaming agent, 0.05~0.8 part of antibacterial agent and 0.4~3 part of processing aid that its raw material is counted by ratio of weight and the number of copies；This method is first by a part of polythylene resin, the ethylene copolymer, modified foaming agent and processing aid mixing granulation of a part；Obtain spherolite A；Again by the polythylene resin of remainder, the ethylene copolymer of remainder, antibacterial agent mixing granulation；Obtain spherolite B；Spherolite A and spherolite B mixing is extruded into sheet material；By high-energy electron irradiation crosslinking Treatment, foam process processing obtains cross-linked foam polyolefin material.Foamed material of the invention has extraordinary antibacterial effect, and antimicrobial efficiency is high.

Description

Cross-linked foam polyolefin material and preparation method thereof with antibacterial functions
Technical field
The present invention relates to foam polyolefin material fields, in particular to a kind of crosslinking polyolefin foaming with antibacterial functions Material and preparation method thereof.
Background technique
Foam polyolefin material more and more penetrates into the various fields of the development of the national economy, the effect in economic construction It is more and more important.When application field is related to people and animals, the concern in terms of foamed material is particularly important.There is sweat, or Foamed material in moist and dark environment use is particularly easy to breed bacterium and mould.Although polyolefine material itself provides The not nutritional ingredient of bacterium and fungus growth and procreation, but some other small molecule component and use environment in being formulated Etc. factors create the atmosphere for being suitable for bacterium and fungus growth, the threat in health is brought to user.Such as air-conditioning duct, Sports goods, building materials field etc. increasingly pay close attention to problems, require antibacterial more more and more urgent, it is desirable that also increasingly increase.
Polyolefin resin itself does not have antibacterial and mildew-proof function, needs to add antibacterial agent and assigns the effect of its antibacterial and mouldproof. There are many antibacterial and mouldproof auxiliary agent type, not all to be suitable for polyolefin crosslinked foaming field.Inorganic antiseptic high temperature resistant, But it is most of can only antibacterium, cannot be mould proof, limit its scope of application；Natural antibacterial agent raw material environmental protection, but antibiotic property is imitated Fruit is poor, poor with compatible polyolefin；Organic antibacterial agent good anti-bacterial effect, but need to consider the suitability with blowing temperature.It is existing Organic foaming agent decomposition temperature is between 200~230 DEG C in technology, and organic antibacterial agent decomposition temperature is 180~200 DEG C, just In normal foam process, blowing temperature needs to reach foaming agent decomposition temperature, is easy to cause antibacterial agent decomposition and loss in this way, causes Antibacterial agent additive amount is big, while antibacterial effect is poor.
102286164 B of patent CN discloses a kind of antibacterial polyethylene foamed plastic and preparation method thereof, therein anti- Microbial inoculum is polyguanidine/polysilicate complex antimicrobials, and in preparation method, blending temperature is controlled at 150~170 DEG C, is both guaranteed Base polyethylene melts completely and antibacterial agent will not be made to decompose, but in foam process, in order to guarantee foam performance, in moulding press Interior foaming, blowing temperature are 220~230 DEG C, lead to the decomposed of antibacterial agent.
102286164 A of patent CN discloses a kind of irradiated crosslinked polyalkene foam and preparation method thereof, is formulated as poly- second Alkene, nanoscale bamboo fibre powder, metallocene PE, catalyst, foaming concentrate, color masterbatch, wherein foaming concentrate is foaming agent, gathers Ethylene, antioxidant, catalyst is zinc borate, magnesia, zinc stearate, polyethylene, although using catalyst in formula, Do not achieve the effect that reduce blowing temperature, in preparation method, blowing temperature is 230 DEG C~260 DEG C, and antibacterial effect is weaker.
Summary of the invention
It is an object of the invention to provide a kind of cross-linked foam polyolefin material and preparation method thereof with antibacterial functions. Solve in the prior art organic foaming agent decomposition temperature be 200~230 DEG C between, organic antibacterial agent decomposition temperature be 180~ 200 DEG C, in normal foam process, blowing temperature needs to reach foaming agent decomposition temperature, is easy to cause antibacterial agent to decompose in this way And loss, cause antibacterial agent additive amount big, while the defect of antibacterial effect difference.
To achieve the above object, a kind of cross-linked foam polyolefin material with antibacterial functions provided by the invention, it is special Sign is：The raw material of the cross-linked foam polyolefin material counts the polyethylene kind tree including 45~91.5 parts by ratio of weight and the number of copies Rouge, 5~30 parts of ethylene copolymer, 2~20 parts of modified foaming agent, 0.05~0.8 part of antibacterial agent and 0.4~3 part plus Work auxiliary agent；Wherein, the modified foaming agent is made of foaming agent and catalyst, and the 0.5 of catalyst accounting modified foaming agent weight ~15%.
Further, the raw material weight number of the cross-linked foam polyolefin material is than counting the polyethylene including 60~80 parts Resinoid, 10~20 parts of ethylene copolymer, 2~20 parts of modified foaming agent, 0.05~0.8 part of antibacterial agent and 0.5~3 part Processing aid；Wherein, the 4~10% of the catalyst accounting modified foaming agent weight.
Still further, the foaming agent is selected from five methylene of azodicarbonamide, OBSH foaming agent and N, N- dinitroso Urotropine；It is zinc oxide, zinc stearate, citric acid, zinc carbonate, zinc acetate and malic acid that the catalyst, which is selected from,；Wherein, it foams The partial size D of agent50：1μm≤D50≤ 100 μm, and catalyst particle size：0.1 μm≤catalyst particle size≤1/10 foaming agent partial size.
Still further, the foaming agent is azodicarbonamide；The partial size D of foaming agent50：1μm≤D50≤40μm；
The catalyst is zinc oxide；
Foaming agent includes azodicarbonamide, OBSH foaming agent, N, N- dinitrosopentamethylene tetramine, wherein it is preferred that even Nitrogen diformamide.Although OBSH foaming agent decomposition temperature is at 150 DEG C, it is in the foamed material added with HDPE, due to cutting Heat is cut, the decomposition of OBSH foaming agent can be caused, abscess is uneven when rear end being caused to be foamed；In addition, since OBSH foaming agent is special Different smell limits its use in sport, building and automobile.And N, N- dinitrosopentamethylene tetramine decomposition temperature reach 230 DEG C, so easily causing the decomposition of antibacterial agent when being applied to antibacterial field；Although can reduce the phase by auxiliary agent decomposes temperature Degree, but bubbling efficiency greatly reduces less than 160ml in its gas forming amount, leads to increased costs.
For azodicarbonamide decomposition temperature between 200~220 DEG C, decomposing and generating gas is mainly nitrogen, titanium dioxide Carbon, so its smell is very low.1 μm≤D of foaming agent partial size50≤ 100 μm, preferably 1 μm≤D50≤40μm.When partial size is less than 1 μm, Adsorption capacity between foaming agent is larger, it is difficult to disperse；When foaming agent partial size is greater than 40 μm, decomposition temperature is very high, specific surface area It is too small, it is unfavorable for modification of the catalyst to foaming agent.
Foaming agent with antibacterial agent in use, decomposition temperature or excessively high, easily causes the decomposition of antibacterial agent.So necessary Catalyst is introduced, to reduce foaming agent decomposition temperature.In existing catalyst system, including zinc carbonate, zinc acetate, zinc octoate, Malic acid, citric acid, stearic acid, zinc stearate and zinc oxide etc..Wherein preferred zinc carbonate, zinc stearate and zinc oxide, wherein More preferable zinc oxide.
Zinc acetate, zinc octoate, malic acid, stearic acid and zinc stearate and polyethylene compatible are poor, and analysis is easy when squeezing out Out；Zinc oxide and zinc carbonate are inorganic particle, seldom there is a phenomenon where being precipitated and migrating, and can be used as suitable blowing agent decomposition and urge Agent.But consider from catalytic activity, zinc carbonate is lower in catalytic activity, needs to increase usage amount, will cause abscess pattern The possibility of distortion.
The dosage of catalyst is catalyst accounting foaming agent 0.5~15%, preferably accounting foaming agent 4~10%.Control hair 140 DEG C≤Td≤185 DEG C in infusion decomposition temperature section, preferably 145 DEG C≤Td≤175 DEG C.Less catalyst amount is to foaming The temperature of agent reduces limitation, i.e., can reduce bubbling efficiency, and foaming agent residual is excessive, does not meet Reach laws and regulations requirement, limits The application of product, while will increase antibacterial agent decomposition risk again.Excessive catalyst can make foaming agent decomposition temperature be reduced to 140 DEG C hereinafter, squeeze piece stage foaming agent just have decomposition risk.The decomposition risk of foaming agent can reduce the extrusion production capacity in extrusion stage, Also subsequent product section abscess pattern can be had an impact, causes foam sheet apparently coarse.
Still further, the processing aid is selected from coupling agent, antioxidant, colorant and lubricant.
Still further, the processing aid is by including 0.2~0.8 part of coupling agent, 0.1~1.2 part of antioxidant, 0 ~0.4 part of colorant and 0.1~1.5 part of lubricant composition.
Still further, the polythylene resin is selected from low density polyethylene, metallocene PE mLDPE, line Type low density polyethylene (LDPE) LLDPE, high density polyethylene, ultra-low density polyethylene VLDPE；
The antibacterial agent is selected from triclosan, N- octylisothiazolinone, 2- (4- pyridine) benzimidazole, 2,3,5, The different peptide nitrile of 6- tetrachloro, 2- pyridol -1- sodium oxide molybdena；Wherein, the antibacterial agent partial size D50≤10μm。
The ethylene copolymer increases the gluing and hot plyability of material in later period application, is selected from ethane-acetic acid ethyenyl ester Copolymer EVA, ethylene-methyl acrylate copolymer EMA, ethylene acrylic acid co polymer
EAA, 80~105 DEG C of fusing point.
Although inorganic antiseptic decomposition temperature is high, it will not decompose and volatilize in foaming stages, inorganic antiseptic antibacterial Type has been lacked much compared to organic antibacterial agent.Consider to have in the application field (sport, building and automobile) of foamed material very much Dark moist place, so selecting the organic antibacterial agent of preferred spectrum sterilization.
Include in antibacterial agent triclosan, N- butyl-benzene and isothiazolinone, N- trichloro-methylthio phthalimide, 2- butyl -1,2- benzisothiazole-3-ketone, poly- methylene hydrochloric acid, N- octylisothiazolinone, N- (fluorine dichloromethyl sulphur) Titanium acid imide, 2- (4- pyridine) benzimidazole, the different peptide nitrile of 2,3,5,6- tetrachloro, zinc pyrithione, 2- pyridol -1- sodium oxide molybdena, N, N ', N "-trihydroxy Hexahydrotriazine, benzyldimethyldodecylammonium ammonium chloride, copper 8-quinolinolate, 1,1- hexamethylene bis [5- (4- chlorphenyl) biguanides] digluconate.Wherein preferred triclosan, N- octylisothiazolinone, 2- (4- pyrrole Pyridine) benzimidazole, the different peptide nitrile of 2,3,5,6- tetrachloro, 2- pyridol -1- sodium oxide molybdena.Partial size D50≤10μm。
Still further, the polythylene resin is by low density polyethylene, metallocene PE mLDPE, line style Low density polyethylene (LDPE) LLDPE composition, wherein low density polyethylene, metallocene PE mLDPE, the poly- second of linear, low density The weight ratio of alkene LLDPE is 1:0.5~2:0.2~1
The antibacterial agent is made of triclosan and N- octylisothiazolinone, wherein triclosan and N- Octylisothiazolinone weight ratio is 1:0.5~2.
Still further, the raw material of the cross-linked foam polyolefin material counts the low-density including 25 parts by ratio of weight and the number of copies Polyethylene LDPE, 20 parts of metallocene PE mLDPE, 25 parts of linear low density polyethylene (LLDPE) LLDPE, 15 parts of ethylene copolymer Object, 5 parts of modified foaming agent, 0.1 part of triclosan, 0.1 part of N- octylisothiazolinone, 0.5 part of coupling agent, 0.8 part of antioxidant, 0.1 part of colorant and 1.2 parts of lubricant；Wherein, the modified foaming agent is by partial size D50It is 20 μm Azodicarbonamide and partial size be 1 μm zinc oxide form, the 6% of zinc oxide accounting modified foaming agent weight；Dichlorophenoxy The partial size of chlorophenol and N- octylisothiazolinone is 5 μm.
The present invention also provides a kind of methods for preparing the above-mentioned cross-linked foam polyolefin material with antibacterial functions, including Following steps：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 0.5~15% of amount；
2) polythylene resin, ethylene copolymer, modified foaming agent, antibacterial agent and processing are weighed by above-mentioned weight fraction ratio Auxiliary agent, it is spare；
3) polythylene resin and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, by a part of polythylene resin, a part ethylene copolymer, Modified foaming agent and processing aid mixing granulation, obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the polythylene resin of remainder, the ethylene copolymer of remainder Object, antibacterial agent mixing granulation, obtain spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material be X be 10~ 70%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material.
Preferably, in the step 7), the degree of cross linking of sheet material is X, is 45~65%.
Above method advantage is as follows：
1) temperature is controlled at 90~120 DEG C when calendering process；
2) temperature is controlled at 90~125 DEG C when extrusion process；
3) temperature is controlled at 140~185 DEG C when foam process.
Both it ensure that the extrusion production capacity in extrusion stage, subsequent product section abscess pattern will not have been had an impact, foamed sheet Material is apparently flat and smooth.It can sufficiently be decomposed in foaming stages foaming agent simultaneously, improve bubbling efficiency, there is no foaming agents to remain The problem of, the characteristic of foamed material itself is remained, while antibacterial agent will not decompose, in the seldom situation of antibacterial agent additive amount Under, there is extraordinary antibacterial effect, antimicrobial efficiency is high.
The beneficial effects of the present invention are：
1, the present invention selects content, the relationship of partial size of suitable catalyst and foaming agent, controls foaming agent decomposition temperature It (Td) is 140 DEG C≤Td≤185 DEG C, preferably 145 DEG C≤Td≤175 DEG C.The dosage of catalyst is catalyst accounting modified foaming Agent 0.5~15%, preferably accounting modified foaming agent 4~10%.It is 140 DEG C≤Td that foaming agent decomposition temperature section, which can be effectively controlled, ≤ 185 DEG C, preferably 145 DEG C≤Td≤175 DEG C.Less catalyst amount reduces limitation to the temperature of foaming agent, i.e., can Bubbling efficiency is reduced, foaming agent residual is excessive, does not meet Reach laws and regulations requirement, limits the application of product, while will increase again anti- Microbial inoculum decomposition risk, antibacterial effect are poor.Excessive catalyst can make foaming agent decomposition temperature be reduced to 140 DEG C hereinafter, squeezing piece rank Section foaming agent just has decomposition risk.The decomposition risk of foaming agent can reduce the extrusion production capacity in extrusion stage, also can be to subsequent production Product section abscess pattern has an impact, and causes foam sheet apparently coarse.When catalyst accounting modified foaming agent 0.5~15%, First is that guarantee that, in the crowded piece stage, foaming agent is not present decomposition risk, ensure that the extrusion production capacity in extrusion stage, it will not be to subsequent production Product section abscess pattern has an impact, and foam sheet is apparently flat and smooth.Simultaneously in foaming stages, blowing temperature control is existed The problem of within the scope of 140~185 DEG C, foaming agent can be decomposed sufficiently, improve bubbling efficiency, and there is no foaming agent residuals, retains The characteristic of foamed material itself, while antibacterial agent will not decompose, in the case where antibacterial agent additive amount is seldom, there have to be very good Antibacterial effect, antimicrobial efficiency is high.
2, in raw material of the present invention, catalyst particle size is less than 0.1 μm, and 0.1 μm≤catalyst particle size≤1/10 foaming agent grain Diameter, catalyst are easy to reunite, and catalytic action has loss；Catalyst particle size is less than foaming agent partial size, and when identical additive amount originates Decomposition temperature is lower, when decomposition temperature is lower than 140 DEG C, squeezes out decomposition risk and increases, unfavorable to squeezing out；Catalyst particle size is greater than Foaming agent partial size, decomposition temperature section is excessive, and upper limit decomposition temperature is well over 185 DEG C, can accelerate the decomposition and ease of antibacterial agent Speed is dissipated, antibacterial effect is influenced.
Detailed description of the invention
Fig. 1 is different catalysts usage amount accounting, the apparent figure of foam sheet；
In figure, the apparent figure of foam sheet when Figure 1A is catalyst usage amount accounting 10%；
The apparent figure of foam sheet when Figure 1B is catalyst usage amount accounting 18%.
Specific embodiment
In order to better explain the present invention, below in conjunction with the specific embodiment main contents that the present invention is furture elucidated, but The contents of the present invention are not limited solely to following embodiment.
Cross-linked foam polyolefin material with antibacterial functions, the raw material of the cross-linked foam polyolefin material is by weight Number than meter include 45~91.5 parts of polythylene resin, 5~30 parts of ethylene copolymer, 2~20 parts of modified foaming agent, 0.05~0.8 part of antibacterial agent and 0.4~3 part of processing aid；Wherein, the modified foaming agent is by foaming agent and catalyst group At the 0.5~15% of catalyst accounting modified foaming agent weight.
The method of the above-mentioned cross-linked foam polyolefin material with antibacterial functions, includes the following steps：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 0.5~15% of amount；
2) polythylene resin, ethylene copolymer, modified foaming agent, antibacterial agent and processing are weighed by above-mentioned weight percent Auxiliary agent, it is spare；
3) polythylene resin and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, the ethylene copolymer of a part of polythylene resin, a part is changed Property foaming agent and processing aid mixing granulation, obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the polythylene resin of remainder, the ethylene copolymer of remainder Object antibacterial agent mixing granulation, obtains spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 10% ~70%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material.
Compare different material in conjunction with above-mentioned formula and preparation method and theoretical basis that effect that component uses is of the invention：
1, the influence of catalyst and modified foaming agent difference accounting to foamed material
Catalyst amount is catalyst accounting foaming agent 0.5~15%, preferably accounting foaming agent 4~10%.When accounting is low When 0.5%, catalyst reduces limitation to the temperature of foaming agent, i.e., can reduce bubbling efficiency, foaming agent residual is excessive, no Meet Reach laws and regulations requirement, limit the application of product, while will increase antibacterial agent decomposition risk again.When accounting is higher than 15%, Excessive catalyst can make foaming agent decomposition temperature be reduced to 140 DEG C hereinafter, crowded piece stage foaming agent just has decomposition risk.Hair The decomposition risk of infusion can reduce the extrusion production capacity in extrusion stage, can also have an impact to subsequent product section abscess pattern, cause Foam sheet is apparently coarse.
1 catalyst of table and influence of the modified foaming agent difference accounting to foamed material
When the accounting 10% of catalyst usage amount shown in Figure 1A, foam sheet it is apparent, it is flat and smooth；Catalyst shown in Figure 1B When usage amount accounting 18%, foaming agent initial decomposition temperature is 140 DEG C, causes to squeeze piece decomposition, last foam sheet is apparently coarse.
2, catalyst particle size and influence when foaming agent partial size difference accounting to foaming agent decomposition temperature
The partial size of catalyst is less than foaming agent partial size.Further 0.1 μm≤catalyst particle size≤1/10 foaming agent partial size. Less than 0.1 μm, catalyst is easy to reunite catalyst particle size, and catalytic action has loss；When partial size is excessive, since particle is excessive, A possibility that catalyst is contacted with foaming agent can be reduced.
It foams initial decomposition temperature compared with large-sized catalyst with small particle and decomposition rate obtains catalytic activity grain The relationship of diameter.
Following table proves that catalyst particle size accounting foaming agent partial size is smaller, and initial decomposition temperature is lower when identical additive amount, when When decomposition temperature is lower than 140 DEG C, squeezes out decomposition risk and increase, it is unfavorable to squeezing out；Catalyst particle size accounting foaming agent partial size is bigger, Decomposition temperature section is excessive, and upper limit decomposition temperature is well over 185 DEG C, can accelerate the decomposition and loss speed of antibacterial agent.
Influence when 2 catalyst particle size of table and foaming agent partial size difference accounting to foaming agent decomposition temperature
The test method of bacterium property is as follows：
1, testing standard A.A.T.C.C.TEST METHOD 30-2013 tests strain Aspergillusniger (ATCC#6275)
2, testing standard ISO 22196:2011, it tests strain Escherichia coli (ATCC#8739)
Embodiment 1
The raw material of cross-linked foam polyolefin material 1 with antibacterial functions counts the low-density including 40 parts by ratio of weight and the number of copies Polyethylene LDPE, mLDPE parts of metallocene PE of 20 parts, 20 parts of ethylene copolymer, 5 parts of modified foaming agent, 0.5 part Partial size D50 be 5 μm of 2- (4- pyridine) benzimidazole, 1 part of coupling agent and 1 part of antioxidant；Wherein, the modified hair Infusion is made of the zinc oxide that the partial size D50 azodicarbonamide for being 30 μm and partial size are 2 μm, zinc oxide accounting modified foaming agent The 0.5% of weight.
1 preparation method of cross-linked foam polyolefin material：
1) it is mixed with azodicarbonamide and zinc oxide to obtain modified foaming agent；
2) low density polyethylene, metallocene PE mLDPE, ethylene copolymer are weighed by above-mentioned weight percent, Modified foaming agent, 2- (4- pyridine) benzimidazole, coupling agent and antioxidant, it is spare；
3) low density polyethylene, metallocene PE mLDPE, ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, by 20 parts of low density polyethylene, 8 parts of metallocene PE MLDPE, 12 parts of ethylene copolymer, modified foaming agent, coupling agent and antioxidant mixing granulation, obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by 20 parts of low density polyethylene, 12 parts of metallocene PE MLDPE, 8 parts of ethylene copolymer and 2- (4- pyridine) benzimidazole mixing granulation, obtain spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 50%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material 1.
Embodiment 2
The raw material of cross-linked foam polyolefin material 2 with antibacterial functions counts the low-density including 25 parts by ratio of weight and the number of copies Polyethylene LDPE, 20 parts of metallocene PE mLDPE, 25 parts of linear low density polyethylene (LLDPE) LLDPE, 15 parts of ethylene copolymer Object, 5 parts of modified foaming agent, 0.1 part of triclosan, 0.1 part of N- octylisothiazolinone, 0.5 part of coupling agent, 0.8 part of antioxidant, 0.1 part of colorant and 1.2 parts of lubricant；Wherein, the modified foaming agent is by partial size D50It is 20 μm Azodicarbonamide and partial size be 1 μm zinc oxide form, the 6% of zinc oxide accounting modified foaming agent weight；Dichlorophenoxy The partial size of chlorophenol and N- octylisothiazolinone is 5 μm.
The method of the above-mentioned cross-linked foam polyolefin material 2 with antibacterial functions, includes the following steps：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 6% of amount；
2) low density polyethylene, metallocene PE mLDPE, linear, low density is weighed by above-mentioned weight fraction ratio to gather Ethylene LLDPE, ethylene copolymer, modified foaming agent, triclosan, N- octylisothiazolinone, coupling agent, antioxidant, Colorant and lubricant, it is spare；
3) low density polyethylene, metallocene PE mLDPE, linear low density polyethylene (LLDPE) LLDPE and ethylene are total to Polymers is divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, by 10 parts low density polyethylene part, 5 parts of metallocene gathers Ethylene mLDPE, 15 parts of linear low density polyethylene (LLDPE) LLDPE, 10 parts of ethylene copolymer, modified foaming agent, coupling agent, antioxygen Agent, colorant and mix lubricant are granulated, and obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the low density polyethylene of remainder, metallocene PE MLDPE and linear low density polyethylene (LLDPE) LLDPE, the ethylene copolymer of remainder, triclosan and N- octyl isothiazole Quinoline ketone mixing granulation, obtains spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 40%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material 2.
Embodiment 3
The raw material of cross-linked foam polyolefin material 3 with antibacterial functions counts the low-density including 45 parts by ratio of weight and the number of copies Polyethylene LDPE, 30 parts of ethylene copolymer, 20 parts of modified foaming agent, 0.8 part of partial size D50For 10 μm of 2- pyridol -1- Sodium oxide molybdena and 0.4 part of coupling agent；Wherein, the modified foaming agent is by partial size D50For 40 μm of OBSH foaming agents and partial size D50For 4 μm of citric acid compositions, the 10% of catalyst accounting modified foaming agent weight；
The method of the above-mentioned cross-linked foam polyolefin material 3 with antibacterial functions, includes the following steps：
1) by partial size D50For 40 μm of OBSH foaming agents and partial size D50It is mixed with to obtain modified foaming for 4 μm of citric acids Agent, wherein the 10% of catalyst accounting modified foaming agent weight；
2) low density polyethylene, ethylene copolymer, modified foaming agent, 2- pyridine are weighed by above-mentioned weight fraction ratio Phenol -1- sodium oxide molybdena and coupling agent, it is spare；
3) low density polyethylene and ethylene copolymer are divided into two parts；
4) temperature be 90~120 DEG C under the conditions of, by 20 parts of low density polyethylene, 15 parts of ethylene copolymer, Modified foaming agent and coupling agent mixing granulation, obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the low density polyethylene of remainder, the ethylene of remainder Copolymer, 2- pyridol -1- sodium oxide molybdena mixing granulation, obtain spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 30%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material 3.
Embodiment 4
The raw material of cross-linked foam polyolefin material 4 with antibacterial functions is counted low close including 41.5 parts by ratio of weight and the number of copies Spend polyethylene LDPE, 50 parts of metallocene PE mLDPE, 20 parts of ethylene copolymer, 10 parts of modified foaming agent, 0.05 part Antibacterial agent, 0.8 part of coupling agent, 0.1 part of antioxidant and 1.5 parts of lubricant；
Wherein, the modified foaming agent is made of foaming agent and catalyst, catalyst accounting modified foaming agent weight 4%.
Foaming agent is made of azodicarbonamide and OBSH foaming agent；Wherein, the partial size D of foaming agent50：80μm；Catalyst Selected from for partial size：For 0.2 μm of zinc stearate
Antibacterial agent is made of 0.02 part of triclosan and the different peptide nitrile of 0.03 part of 2,3,5,6- tetrachloro；Wherein, institute State antibacterial agent partial size D50It is 10 μm.The method for preparing the above-mentioned cross-linked foam polyolefin material 4 with antibacterial functions, including it is following Step：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 4% of amount；
2) low density polyethylene, metallocene PE mLDPE, ethylene copolymer are weighed by above-mentioned weight fraction ratio, Modified foaming agent, triclosan, 2, the different peptide nitrile of 3,5,6- tetrachloros, coupling agent, antioxidant and lubricant, it is spare；
3) low density polyethylene, metallocene PE mLDPE and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, by 10 parts of low density polyethylene, 30 parts of metallocene PE MLDPE, 10 parts of ethylene copolymer, modified foaming agent, coupling agent, antioxidant and mix lubricant are granulated, and obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the low density polyethylene of remainder, metallocene PE MLDPE, the ethylene copolymer of remainder, triclosan and 2, the different peptide nitrile mixing granulation of 3,5,6- tetrachloros, obtain spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 20%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material.
Embodiment 5
The raw material of cross-linked foam polyolefin material 5 with antibacterial functions counts the high density including 10 parts by ratio of weight and the number of copies Polyethylene HDPE, 45 parts of ultra-low density polyethylene VLDPE, 10 parts of ethylene copolymer, 2 parts of modified foaming agent, 0.1 part Antibacterial agent and 1 part of antioxidant；
Wherein, for modified foaming agent by N, N- dinitrosopentamethylene tetramine and catalyst composition, catalyst accounting are modified The 1% of blowing agent composition weight；
Catalyst is made of zinc oxide, zinc carbonate and zinc acetate, weight ratio 1:1:1；Wherein, the partial size of foaming agent D50：1 μm, and catalyst particle size：0.1μm.
The antibacterial agent is by 0.08 part of N- octylisothiazolinone and 0.02 part of 2- (4- pyridine) benzimidazole；Its In, the antibacterial agent partial size D50It is 0.1 μm.
The method for preparing the above-mentioned cross-linked foam polyolefin material 5 with antibacterial functions, includes the following steps：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 1% of amount；
2) high density polyethylene, ultra-low density polyethylene VLDPE, ethylene copolymer are weighed by above-mentioned weight fraction ratio Object, modified foaming agent, N- octylisothiazolinone, 2- (4- pyridine) benzimidazole and antioxidant are spare；
3) high density polyethylene, ultra-low density polyethylene VLDPE and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, by 4 parts of high density polyethylene, the poly- second of 25 parts of extremely-low density Alkene VLDPE, 4 parts of ethylene copolymer, modified foaming agent and antioxidant mixing granulation, obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the high density polyethylene of remainder, ultra-low density polyethylene VLDPE, the ethylene copolymer of remainder, N- octylisothiazolinone and 2- (4- pyridine) benzimidazole mixing granulation, obtain Spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 35%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material 5.
Embodiment 6
The raw material of cross-linked foam polyolefin material 6 with antibacterial functions counts the low-density including 20 parts by ratio of weight and the number of copies Polyethylene LDPE, 40 parts of linear low density polyethylene (LLDPE) LLDPE, 14 parts of ethylene copolymer, 15 parts of modified foaming agent, 0.3 Antibacterial agent, 0.8 part of the antioxidant, 1.2 parts of lubricant of part；
Wherein, the modified foaming agent is made of foaming agent and catalyst, catalyst accounting modified foaming agent weight 3%.
Foaming agent is by OBSH foaming agent and N, N- dinitrosopentamethylene tetramine composition, weight ratio 1:1；Catalyst It is made of zinc oxide and zinc stearate, weight ratio 1:2；Wherein, the partial size D of foaming agent50：50 μm, and catalyst particle size： 0.5μm。
The antibacterial agent is made of the N- octylisothiazolinone of 0.1 part of triclosan and 0.2 part；Wherein, institute State antibacterial agent partial size D50It is 0.5 μm.The method for preparing the above-mentioned cross-linked foam polyolefin material 6 with antibacterial functions, including with Lower step：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 3% of amount；
2) low density polyethylene, linear low density polyethylene (LLDPE) LLDPE, ethylene copolymer are weighed by above-mentioned weight fraction ratio Object, modified foaming agent, triclosan, N- octylisothiazolinone, antioxidant and lubricant are spare；
3) low density polyethylene, linear low density polyethylene (LLDPE) LLDPE and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, 15 parts of low density polyethylene, 10 parts of linear, low density are gathered Ethylene LLDPE, 6 parts of ethylene copolymer, modified foaming agent, antioxidant and mix lubricant are granulated, and obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the low density polyethylene of remainder, the poly- second of linear, low density Alkene LLDPE, the ethylene copolymer of remainder, triclosan and N- octylisothiazolinone mixing granulation, obtain spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 35%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material 6.
Embodiment 7
The raw material of cross-linked foam polyolefin material 7 with antibacterial functions is counted low including 75 parts of line style by ratio of weight and the number of copies Density polyethylene LLDPE, 5 parts of ethylene copolymer, 15 parts of modified foaming agent, 0.6 part of partial size D50For 2 μm of Dichlorophenoxy Chlorophenol, 0.2 part of coupling agent, 0.1 part of antioxidant, 0.1 part of lubricant；
Wherein, the modified foaming agent is made of foaming agent and catalyst, catalyst accounting modified foaming agent weight 5%.
Foaming agent is made of azodicarbonamide and OBSH foaming agent, weight ratio 1:3；Catalyst is by citric acid and carbon Sour zinc composition, weight ratio 1:1；Wherein, the partial size D of foaming agent50：10 μm, and catalyst particle size：0.8μm.
The method for preparing the above-mentioned cross-linked foam polyolefin material 7 with antibacterial functions, includes the following steps：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 5% of amount；
2) polythylene resin, ethylene copolymer, modified foaming agent, Dichlorophenoxy chlorine are weighed by above-mentioned weight fraction ratio Phenol, coupling agent, antioxidant and lubricant, it is spare；
3) linear low density polyethylene (LLDPE) LLDPE and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, by 50 parts of linear low density polyethylene (LLDPE) LLDPE, 4 parts of ethylene copolymer Object, modified foaming agent, coupling agent, antioxidant and mix lubricant are granulated, and obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by linear low density polyethylene (LLDPE) LLDPE, the remainder of remainder Ethylene copolymer and triclosan mixing granulation, obtain spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 70%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material 7.
Embodiment 8
The raw material of cross-linked foam polyolefin material 8 with antibacterial functions counts the metallocene including 30 parts by ratio of weight and the number of copies Polyethylene mLDPE, 25 parts of linear low density polyethylene (LLDPE) LLDPE, 25 parts of high density polyethylene, 25 parts of ethylene copolymer Object, 8 parts of modified foaming agent, 0.7 part of antibacterial agent and 0.5 part of lubricant；
Wherein, the modified foaming agent is made of foaming agent and catalyst, catalyst accounting modified foaming agent weight 15%.
Foaming agent is made of azodicarbonamide, OBSH foaming agent and N, N- dinitrosopentamethylene tetramine, weight Than being 1:2:1；Catalyst is zinc stearate；Wherein, the partial size D of foaming agent50：60 μm, and zinc stearate partial size：5μm.
Antibacterial agent is made of 0.5 part of the different peptide nitrile of 2,3,5,6- tetrachloro and 0.2 part of 2- pyridol -1- sodium oxide molybdena；Wherein, The antibacterial agent partial size D50It is 8 μm.The method for preparing the above-mentioned cross-linked foam polyolefin material 8 with antibacterial functions, including with Lower step：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 15% of amount；
2) metallocene PE mLDPE, linear low density polyethylene (LLDPE) LLDPE, high density are weighed by above-mentioned weight fraction ratio Polyethylene HDPE, ethylene copolymer, modified foaming agent, 2, the different peptide nitrile of 3,5,6- tetrachloros, 2- pyridol -1- sodium oxide molybdena and lubrication Agent, it is spare；
3) metallocene PE mLDPE, linear low density polyethylene (LLDPE) LLDPE, high density polyethylene and ethylene are total to Polymers is divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, 10 parts of metallocene PE mLDPE, 5 parts of linear, low density are gathered Ethylene LLDPE, 10 parts of high density polyethylene, 12 parts of ethylene copolymer, modified foaming agent and mix lubricant are granulated, Obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, metallocene PE mLDPE, the linear, low density of remainder are gathered The different peptide nitrile of ethylene LLDPE, high density polyethylene, the ethylene copolymer of remainder, 2,3,5,6- tetrachloro and 2- pyridol- 1- sodium oxide molybdena mixing granulation, obtains spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 55%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material 8.
Embodiment 9
The raw material of cross-linked foam polyolefin material 9 with antibacterial functions counts the low-density including 36 parts by ratio of weight and the number of copies Polyethylene LDPE, 36 parts of linear low density polyethylene (LLDPE) LLDPE, 18 parts of ultra-low density polyethylene VLDPE, 28 parts of ethylene are total Polymers, 20 parts of modified foaming agent, 0.2 part of antibacterial agent, 0.8 part of coupling agent, 1.2 parts of antioxidant, 1 part of lubricant；
Wherein, the modified foaming agent is by partial size D50It is formed for 100 μm of OBSH foaming agents and catalyst, catalyst accounting The 12% of modified foaming agent weight.
Catalyst is made of zinc acetate and malic acid, weight ratio 1:1；Wherein, catalyst particle size：7μm.
Antibacterial agent is by 0.14 part of N- octylisothiazolinone, the different peptide nitrile of 0.01 part of 2,3,5,6- tetrachloro and 0.05 part 2- pyridol -1- sodium oxide molybdena；Wherein, the antibacterial agent partial size D50It is 4 μm.
The method for preparing the above-mentioned cross-linked foam polyolefin material 9 with antibacterial functions, includes the following steps：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 12% of amount；
2) low density polyethylene, linear low density polyethylene (LLDPE) LLDPE, extremely-low density are weighed by above-mentioned weight fraction ratio Polyethylene VLDPE, ethylene copolymer, modified foaming agent, N- octylisothiazolinone, 2, the different peptide nitrile of 3,5,6- tetrachloros and 2- pyridine Phenol -1- sodium oxide molybdena, coupling agent, antioxidant and lubricant, it is spare；
3) by low density polyethylene, linear low density polyethylene (LLDPE) LLDPE, ultra-low density polyethylene VLDPE and ethylene Copolymer is divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, 20 parts of low density polyethylene, 12 parts of linear, low density are gathered Ethylene LLDPE, 5 parts of ultra-low density polyethylene VLDPE, 8 parts of ethylene copolymer, modified foaming agent, coupling agent, antioxidant and Mix lubricant is granulated, and obtains spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the low density polyethylene of remainder, the poly- second of linear, low density Alkene LLDPE, ultra-low density polyethylene VLDPE, the ethylene copolymer of remainder, N- octylisothiazolinone, 2,3,5,6- tetra- The different peptide nitrile of chlorine and 2- pyridol -1- sodium oxide molybdena mixing granulation, obtain spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 18%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material.
Embodiment 10
The raw material of cross-linked foam polyolefin material 10 with antibacterial functions is counted ultralow including 35 parts by ratio of weight and the number of copies Density polyethylene VLDPE, 40 parts of metallocene PE mLDPE, 15 parts of ethylene copolymer, 18 parts of modified foaming agent, 0.5 Antibacterial agent, 0.3 part of the coupling agent, 1.5 parts of lubricant of part；
Wherein, the modified foaming agent is by partial size D50For 25 μm of azodicarbonamides and partial size D50For 2 μm of citric acid groups At the 8% of catalyst accounting modified foaming agent weight.
The antibacterial agent is by 0.3 part of triclosan, the different peptide nitrile of 0.1 part of 2,3,5,6- tetrachloro and 0.1 part of 2- Pyridol -1- sodium oxide molybdena；Wherein, the antibacterial agent partial size D50It is 0.05 μm.
The method for preparing the above-mentioned cross-linked foam polyolefin material 10 with antibacterial functions, includes the following steps：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight The 8% of amount；
2) ultra-low density polyethylene VLDPE, metallocene PE mLDPE, ethylene copolymer are weighed by above-mentioned weight fraction ratio Object, modified foaming agent, triclosan, 2, the different peptide nitrile of 3,5,6- tetrachloros and 2- pyridol -1- sodium oxide molybdena, coupling agent and lubrication Agent, it is spare；
3) ultra-low density polyethylene VLDPE, metallocene PE mLDPE and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, 30 parts of ultra-low density polyethylene VLDPE, 10 parts of metallocene are gathered Ethylene mLDPE, 5 parts of ethylene copolymer, modified foaming agent, coupling agent and mix lubricant are granulated, and obtain spherolite A；
5) under the conditions of temperature is 90~120 DEG C, by the poly- second of ultra-low density polyethylene VLDPE, metallocene of remainder The different peptide nitrile of alkene mLDPE, the ethylene copolymer of remainder, triclosan, 2,3,5,6- tetrachloro and 2- pyridol -1- oxidation Sodium mixing granulation obtains spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is 90~125 DEG C of conditions of temperature in temperature Lower melting extrusion is at sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 65%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), it is poly- obtains crosslinking Alkene foamed material.
Note：√ shows to decompose, and X expression is not decomposed.
In above-described embodiment, foaming agent used does not decompose in the extrusion stage in foam sheet, and apparent smooth, is foaming Agent residual quantity≤0.11, in the case where antibacterial agent additive amount is seldom, with aspergillus niger (Aspergillus niger (ATCC# 6275), for Escherichia coli Escherichia coli (ATCC#8739), antibacterial effect is tested, wherein to aspergillus niger (antibacterial surface rate >=96% of Aspergillus niger (ATCC#6275), to Escherichia coli Escherichia coli (ATCC#8739) antibiotic rate >=97%.Wherein the effect of embodiment 2 is best.
Other unspecified parts are the prior art.Although above-described embodiment is made that the present invention and retouches in detail State, but it is only a part of the embodiment of the present invention, rather than whole embodiments, people can also according to the present embodiment without Other embodiments are obtained under the premise of creativeness, these embodiments belong to the scope of the present invention.

Claims (10)

1. a kind of cross-linked foam polyolefin material with antibacterial functions, it is characterised in that：The cross-linked foam polyolefin material Raw material count by ratio of weight and the number of copies include 45~91.5 parts of polythylene resin, 5~30 parts of ethylene copolymer, 2~20 parts Modified foaming agent, 0.05~0.8 part of antibacterial agent and 0.4~3 part of processing aid；Wherein, the modified foaming agent is by sending out Infusion and catalyst composition, the 0.5~15% of catalyst accounting modified foaming agent weight.
2. according to claim 1 with the cross-linked foam polyolefin material of antibacterial functions, it is characterised in that：The crosslinking is poly- The raw material weight number of alkene foamed material includes 60~80 parts of polythylene resin, 10~20 parts of ethylene copolymer than meter Object, 2~20 parts of modified foaming agent, 0.05~0.8 part of antibacterial agent and 0.5~3 part of processing aid；Wherein, the catalysis The 4~10% of agent accounting modified foaming agent weight.
3. the cross-linked foam polyolefin material according to claim 1 or claim 2 with antibacterial functions, it is characterised in that：The hair Infusion is selected from azodicarbonamide, OBSH foaming agent and N, N- dinitrosopentamethylene tetramine；It is oxygen that the catalyst, which is selected from, Change zinc, zinc stearate, citric acid, zinc carbonate, zinc acetate and malic acid；Wherein, the partial size D of foaming agent50：1μm≤D50≤100μ M, and catalyst particle size：0.1 μm≤catalyst particle size≤1/10 foaming agent partial size.
4. the cross-linked foam polyolefin material according to claim 1 or claim 2 with antibacterial functions, it is characterised in that：The hair Infusion is azodicarbonamide；The partial size D of foaming agent50：1μm≤D50≤40μm；
The catalyst is zinc oxide.
5. according to claim 1 with the cross-linked foam polyolefin material of antibacterial functions, it is characterised in that：The processing helps Agent is selected from coupling agent, antioxidant, colorant and lubricant.
6. according to claim 5 with the cross-linked foam polyolefin material of antibacterial functions, it is characterised in that：The processing helps Agent is by including 0.2~0.8 part of coupling agent, 0.1~1.2 part of antioxidant, 0~0.4 part of colorant and 0.1~1.5 part Lubricant composition.
7. the cross-linked foam polyolefin material according to claim 1 or claim 2 with antibacterial functions, it is characterised in that：It is described poly- Vinyl resins is selected from low density polyethylene (LDPE), metallocene PE, linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and ultralow close Spend polyethylene；
The antibacterial agent is selected from triclosan, N- octylisothiazolinone, 2- (4- pyridine) benzimidazole, 2,3,5,6- tetra- The different peptide nitrile of chlorine, 2- pyridol -1- sodium oxide molybdena；Wherein, the antibacterial agent partial size D50≤10μm。
8. according to claim 7 with the cross-linked foam polyolefin material of antibacterial functions, it is characterised in that：The polyethylene Resinoid is made of low density polyethylene (LDPE), metallocene PE, linear low density polyethylene (LLDPE), wherein low density polyethylene (LDPE), cyclopentadienyl gold Belong to polyethylene, the weight ratio of linear low density polyethylene (LLDPE) is 1:0.5~2:0.2~1；
The antibacterial agent is made of triclosan and N- octylisothiazolinone, wherein triclosan and N- octyl Isothiazolinone weight ratio is 1:0.5~2.
9. the cross-linked foam polyolefin material according to claim 1 or claim 2 with antibacterial functions, it is characterised in that：The friendship It includes 25 parts of low density polyethylene (LDPE), the poly- second of 20 parts of metallocene that the raw material of connection foam polyolefin material is counted by ratio of weight and the number of copies Alkene, 25 parts of linear low density polyethylene (LLDPE), 15 parts of ethylene copolymer, 5 parts of modified foaming agent, 0.1 part of Dichlorophenoxy chlorine Phenol, 0.1 part of N- octylisothiazolinone, 0.5 part of coupling agent, 0.8 part of antioxidant, 0.1 part of colorant and 1.2 parts Lubricant；Wherein, the modified foaming agent is by partial size D50The zinc oxide group for being 1 μm for 20 μm of azodicarbonamides and partial size At the 6% of zinc oxide accounting modified foaming agent weight；The partial size of triclosan and N- octylisothiazolinone is 5 μm.
10. a kind of method for preparing the cross-linked foam polyolefin material described in claim 1 with antibacterial functions, including following step Suddenly：
1) foaming agent and catalyst are mixed with to obtain modified foaming agent, wherein catalyst accounting modified foaming agent weight 0.5~15%；
2) polythylene resin, ethylene copolymer are weighed by above-mentioned weight fraction ratio, modified foaming agent, antibacterial agent and processing help Agent, it is spare；
3) polythylene resin and ethylene copolymer are divided into two parts；
4) under the conditions of temperature is 90~120 DEG C, by a part of polythylene resin, the ethylene copolymer of a part, modification Foaming agent and processing aid mixing granulation, obtain spherolite A；
5) temperature be 90~120 DEG C under the conditions of, by the polythylene resin of remainder, remainder ethylene copolymer, Antibacterial agent mixing granulation obtains spherolite B；
6) the spherolite A and spherolite B obtained step 4) and step 5) is mixed, and is melted under the conditions of being 90~125 DEG C of temperature in temperature Melt and is extruded into sheet material；
7) sheet material in step 6) is passed through into high-energy electron irradiation crosslinking Treatment, the degree of cross linking of the sheet material is that X is 10~70%；
8) it is 140~185 DEG C of progress foam process processing in temperature by the sheet material after irradiation in step 7), obtains cross-linked polyolefin Foamed material.
CN201810517348.6A 2018-05-25 2018-05-25 Cross-linked foam polyolefin material and preparation method thereof with antibacterial functions Pending CN108822378A (en)

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Application publication date: 20181116