CN103865143A - Crosslinkable polyethylene blend composition - Google Patents
Crosslinkable polyethylene blend composition Download PDFInfo
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- CN103865143A CN103865143A CN201210532430.9A CN201210532430A CN103865143A CN 103865143 A CN103865143 A CN 103865143A CN 201210532430 A CN201210532430 A CN 201210532430A CN 103865143 A CN103865143 A CN 103865143A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92009—Measured parameter
- B29C2948/92266—Mechanical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92323—Location or phase of measurement
- B29C2948/92485—Start-up, shut-down or parameter setting phase; Emergency shut-down; Material change; Test or laboratory equipment or studies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
Abstract
The invention discloses a polyethylene blend composition, and concretely relates to a crosslinkable polyethylene blend composition. The crosslinkable polyethylene blend composition comprises, by weight, 70-90 parts of a crystalline or semi-crystalline polyethylene resin with the density of 0.910-0.970g/cm<3>, 10-30 parts of a polyolefin elastomer component with the density of 0.855-0.900g/cm<3> and/or the degree of crystallization of below 20%, and 0.1-5 parts of a peroxide crosslinking agent, and the total number of parts by weight of the polyethylene resin and the polyolefin elastomer is 100. The crosslinkable polyethylene blend composition has improved toughness and metal bonding property without adding any other function-modified polyethylene part.
Description
Technical field
The present invention relates to a kind of polyethylene composition, in particular to a kind of crosslinkable polyethylene blend composition, it has toughness and the metal bonding of raising.
Background technology
In recent years, polyethylene (PE) is as one of the most widely used thermoplastics, because it has excellent mechanical property, chemical-resistant, electrical insulating property, good processibility and has obtained fast development compared with low cost.But the weak metal bonding of polyethylene causes its application to be restricted, this is to be determined by its nonpolar chain structure.
Conventionally, to polyethylene main chain, be a kind of effective ways that improve its metal bonding by containing the monomer-grafted of polar functional group, described polar functional group comprises unsaturated dicarboxylic acid, acid amides, Sodium styrene sulfonate etc.In actual applications, by the polyethylene blend of polyethylene matrix and maleic anhydride (MAH) or vinylformic acid (AA) grafting, be the mode the most easily that improves polyethylene metal bonding (United States Patent (USP) discloses No. 2008/0163978A1, United States Patent (USP) and discloses No. 2004/0116602A1, No. 7687575B2nd, United States Patent (USP), No. 6835777B2nd, United States Patent (USP) and United States Patent (USP) No. 4298712).
In addition, can make polyethylene surface generation chemical transformation by methods such as high-temperature thermal oxidation, corona treatment, inscription acid etch, Cement Composite Treated by Plasma, produce oxy radical, can improve to a certain extent its metal bonding.Described in No. 3639189th, United States Patent (USP), binder composition prepared by oxidic polyethylene and common polythene blend has obtained excellent adhesive property under higher oxidic polyethylene content, but the toughness variation of material.
It should be noted that, can realize poly crosslinked by methods such as superoxide, silane or electron beam irradiations, due to the formation of fine and close network structure, can effectively improve poly thermal characteristics, resistance to impact shock, environmental stress crack resistance (ESCR), chemical resistance, ageing-resistant performance etc.But the material after being cross-linked still needs further to improve toughness.Therefore, select some copolymer elastomers, as terpolymer EP rubber (EPDM), polyolefin elastomer (POE) and ethylene-propylene rubber(EPR) (EPR) improve the toughness of the finished product.
The disclosure of above-mentioned all documents is introduced with for referencial use in full at this.
For solving the problem facing in above-mentioned prior art, the present invention is not introducing under the prerequisite of any added polarity functional group, utilize crosslinking reaction to realize the synergy of microstructure regulation and control to introduce elastomeric component, obtain and there is the physical and mechanical properties of raising simultaneously and the polyethylene composition of metal bonding.
Summary of the invention
The invention provides a kind of crosslinkable polyethylene blend composition, it has the toughness of raising and the cohesiveness of metal and without adding any other function modified polyethylene component.Described crosslinkable polyethylene blend composition is after being cross-linked, and its resistance to impact shock of measuring at-40 ℃ according to ASTM D256 is greater than 19KJ/m
2, and the stripping strength of the metallic surface of measuring according to ASTM-D 413 is 700-3500N/m, compared with the crosslinked polyethylene of single composition, improved respectively and has been greater than 670% and be greater than 1000%.The biological stripping strength of described crosslinkable polyethylene blend composition is compared in identical level or higher with some polyethylene adhesive that contains function modified polyethylene component.
According to an aspect of the present invention, a kind of crosslinkable polyethylene blend composition, it comprises:
(a) polyvinyl resin of 70～90 parts (weight), its density is at 0.910-0.970g/cm
3and there is crystallization or hypocrystalline;
(b) polyolefin elastomer of 10～30 parts (weight), its density is at 0.855-0.900g/cm
3, and/or there is 20% following degree of crystallinity; With
(c) peroxide cross-linking agent of 0.1～5 part (weight), the polyvinyl resin based on 100 parts (weight) and the gross weight of polyolefin elastomer.
The present invention's polyvinyl resin used is used as matrix resin, and it comprises Alathon, ethylene copolymer (for example ethene-C
4-8olefin copolymer), and their mixture.Preferably, described polyvinyl resin is selected from Low Density Polyethylene (LDPE), linear low density polyethylene (LLDPE), intermediate density polyethylene (MDPE) and high density polyethylene(HDPE) (HDPE).It is 0.910～0.930g/cm that LDPE and LLDPE are defined as density
3polyethylene in scope.It is 0.930～0.945g/cm that MDPE is defined as density
3polyethylene.It is polyethylene more than 0.945g/cm3 that HDPE is defined as density, is more typically the polyethylene of 0.945～0.969g/cm3.
More preferably, described polyvinyl resin is selected from HDPE and LLDPE.HDPE has the degree of crystallinity higher than 60% conventionally, and LLDPE has the degree of crystallinity higher than 40% conventionally.Preferably, the degree of crystallinity of described polyvinyl resin is more than 45%.The melt index of described polyvinyl resin is 1～100g/10min, and is preferably 2～20g/10min.
The polyolefin elastomer adopting in this manual refers to Toughening Effect of Ethylene Copolymer Elastomer, and it is for having the rubber performance of being similar to and little or non crystallized product almost.In crosslinkable polyethylene blend composition of the present invention, adding polyolefin elastomer is metal bonding and the toughness in order to be improved.The degree of crystallinity of preferred described polyolefin elastomer is below 20%.Ethylene-propylene rubber(EPR) (EPR), terpolymer EP rubber (EPDM), ethylene-butene copolymer (PEB) and ethylene-octene copolymer (PEOC) are all very useful elastomeric components for composition of the present invention.Therefore, preferably, described polyolefin elastomer is selected from EPR, EPDM, PEB, PEOC.Preferred described polyolefin elastomer has the melt index of 0.1～500g/10min, and more preferably has the melt index of 0.5～20g/10min.Described polyolefin elastomer comprises the ethylene content lower than 75wt% conventionally, and in a preferred embodiment, comprises the ethylene content lower than 60wt%.Preferably, the elastomeric molecular weight distribution of said polyolefins is less than 2.8.
It is the peroxide cross-linking agent of 0.004～0.25 weight part that the peroxide cross-linking agent using in the present invention can be selected its effective oxygen, and preferably its effective oxygen is the peroxide cross-linking agent of 0.02～0.125 weight part.
Superoxide effective oxygen claims again active o content, represents the free radical quantity producing after the peroxide breakdown of certain mass.The effective oxygen of each pure superoxide can find from the description of product, according to the umber of the purity of superoxide and use, can be regarded as to obtain the actual effective oxygen of superoxide used.
Described peroxide cross-linking agent can be selected from two (tertiary alkyl peroxy) paraffinic hydrocarbonss and two (tertiary alkyl peroxy) benzene.The example of described two (tertiary alkyl peroxy) paraffinic hydrocarbonss is 2, two (the tert-pentyl peroxies)-2 of 5-, 5-dimethylhexane, 2,5-bis(t-butylperoxy)-2,5-dimethylhexane, 3,6-bis(t-butylperoxy)-3,6-dimethyl octane, 2,7-bis(t-butylperoxy)-2,7-dimethyl octane and 8,11-bis(t-butylperoxy)-8,11-dimethyl octane.The example of described two (tertiary alkyl peroxy) benzene is α, α '-bis-(t-butylperoxy-sec.-propyl)-benzene and α, α '-bis-(tert-pentyl peroxy-sec.-propyl)-benzene.In these linking agents, preferably 2,5-bis(t-butylperoxy)-2,5-dimethylhexane and, α, α '-bis-(tert-pentyl peroxy-sec.-propyl)-benzene and their derivative.The consumption of described peroxide cross-linking agent is preferably 0.1～5 weight part, more preferably 0.5～2.5 weight part, the polyvinyl resin based on 100 weight parts and the gross weight of polyolefin elastomer.
In crosslinkable polyethylene blend composition according to the present invention, can also add as required a certain amount of auxiliary agent.Described auxiliary agent comprises crosslinking accelerator, scorch retarder, UV stablizer, pigment etc. without limitation.
The crosslinking accelerator using is in the present invention used for improving cross-linking efficiency, reduces dosage of crosslinking agent, its kind is not limited, but be preferably selected from 1,2-polyhutadiene, triallyl cyanate and triallyl isocyanate.In crosslinkable polyethylene blend composition according to the present invention, the consumption of crosslinking accelerator is 0.05～5 weight part, is preferably 0.1～2.5, the polyvinyl resin based on 100 weight parts and the gross weight of polyolefin elastomer.
In the course of processing, for fear of too early crosslinked (pre-scorch), can also select to add scorch retarder.The kind of described scorch retarder and consumption are those skilled in the art's routine and select, as long as can avoid crosslinked too early.The quinhydrones of the such as organic oxidation-resistant agent of described scorch retarder, quinhydrones and/or replacement etc., its consumption is generally 0.1～1 weight part, the polyvinyl resin based on 100 weight parts and the gross weight of polyolefin elastomer.
For most of purposes, crosslinkable composition will also comprise one or more stablizers, as, antioxidant, UV stablizer etc.The type of these stablizers and consumption are those skilled in the art's routine and select, and depend on final use.Described antioxidant is for example the mixture (IrganoxB, Irganox C) of high molecular weight hindered phenols class (antioxidant 1010,1076), hindered phenol and phosphorous acid ester, monothioester etc.Described UV stablizer is for example benzotriazole category, hindered amines, benzophenone etc.
Crosslinkable polyethylene blend composition of the present invention, the degree of crosslinking of the polyethylene blend composition after it is crosslinked is greater than 25%; Preferably, the degree of crosslinking of its polyethylene blend composition after crosslinked is greater than 35%.
The gel content that described degree of crosslinking can be measured by Soxhlet extraction process defines.According to the testing method of ASTM D2765, be W by quality
1the crosslinked polyethylene sample chopping of (being about 0.400 ± 0.015g) is placed in copper mesh, and by apparatus,Soxhlet's, in the xylene solution of 170 ℃, extracting is after 20 hours, and the vacuum-drying under 90 ℃ of conditions 6 hours, claims that its quality is W
2(gel section), degree of crosslinking can be calculated by following formula:
Degree of crosslinking=(W
2/ W
1) × 100%
Crosslinkable polyethylene blend composition according to the present invention can adopt blending means general in this area to prepare, for example carry out melt blending by twin screw extruder, by polyethylene matrix resin, polyolefin elastomer and binder component mixing granulation under 130-150 ℃ of condition, screw speed is 80rpm.
According to a further aspect in the invention, the invention provides a kind of goods, it comprises the product being prepared from after crosslinked by crosslinkable polyethylene blend composition according to the present invention.Preferably, described goods be comprise metal parts and crosslinked by crosslinkable polyethylene blend composition according to the present invention after the goods of the product that is prepared from, as, solar water heater liner, there is caisson and the aluminium plastic composite packaging material etc. of metal insert.Described metal can be aluminium, steel or copper etc.Described goods can be prepared by methods known in the art, especially, can pass through extrusion molding, compression moulding, rotational moulding method or blow moulding preparation.
Accompanying drawing explanation
Fig. 1 is in comparative example 1, embodiment 1 and embodiment 2, temperature (150～200 ℃) scanning under fixed frequency 1rad/s and fixing strain 3% condition and the time scan curve of 200 ℃, shown the dependency of storage modulus G ' to the time in figure;
Fig. 2 is the instrumentation plan of stripping strength;
Fig. 3 is stripping strength and the resistance to impact shock schematic diagram of comparative example 1, comparative example 3, embodiment 2, embodiment 5 and embodiment 6.
Embodiment
With reference to the following examples, present invention will be further described.Should be appreciated that the present invention is not limited to these embodiment.
HDPE is the trade(brand)name DGDA8007 that provided by company of Shenhua (fusing point=122.6 ℃, density=0.932g/cm
3, MI=10g/10min) high density polyethylene(HDPE).
Polyolefin elastomer comprises POE, EPDM, wherein POE be commodity ENGAGE8100 by name ethylene-octene copolymer (purchased from Dow Chemical, fusing point=60 ℃, density=0.870g/cm
3, MI=1g/10min); EPDM is commodity NORDEL IP 4570 (purchased from Dow Chemical, density is 0.860, ethylene content 50%) by name.
The preparation method of crosslinkable polyethylene blend composition
In Hakka single screw extrusion machine, be that under 80rpm, melting mixing is prepared crosslinkable polyethylene composition as shown in table 1 at 140 ℃, slewing rate.The mixture of extruding is cut to granulation so that follow-up use.
Evaluation test
(1) rheological property is measured
Use TA Discovery HR-2 shear rheology instrument to carry out rheological experiment to detect cross-linking process.Embodiment 1-7 and the prepared crosslinkable polyethylene blend composition hot pressing at 150 ℃ of comparative example 1, comparative example 2 and comparative example 3 are made to the circular piece that diameter to 25mm and thickness is 1mm for subsequent use.First, under the frequency of fixing 3% strain and 1rad/s, carry out dynamic temperature scanning at 150 ℃ to 200 ℃, then under identical strain and frequency, carry out dynamic time scanning.Be illustrated in figure 1 the test result of comparative example 1 and embodiment 1 and 2.
(2) measurement of resistance to impact shock
Use Dynatap 8230 equipment to measure resistance to impact shock at-40 ℃ according to ASTM D256.Standard model is of a size of 63.5 × 12.7 × 3.2mm, and notch depth is 2mm.In accordance with the following steps embodiment 1-7 and the prepared crosslinkable polyethylene blend composition of comparative example 1, comparative example 2 and comparative example 3 are prepared into standard model: first by the hot pressing 2 minutes on vacuum film pressing machine at 150 ℃ of the pellet of preparation, then temperature is risen to 200 ℃, pressure rises to 10MPa, solidify 10 minutes, by water coolant, sample is cooled to room temperature subsequently, finally the impact sample of die-cut desired size from the crosslinked plate of hot pressing.Before Impact Test, sample at least leaves standstill 24 hours to discharge unrelieved stress.Test result is listed in table 2.
(3) cohesiveness is measured
As described below, with reference to ASTM-D 413, measure stripping strength (cohesiveness test).In accordance with the following steps for the preparation of the sample of peel strength test: select one deck aluminium sheet as metal substrate, at 150 ℃, distinguish hot pressing embodiment 1-7 and the prepared crosslinkable polyethylene blend composition film (40mm × 25mm × 1mm) of comparative example 1, comparative example 2 and comparative example 3 first thereon, then under 200 ℃ and 10MPa, solidify 10 minutes, then described film is cooled to room temperature.The schematic diagram of test technology as shown in Figure 2.In the stripping strength of 180 ° of Instron pulling force aircraft measurements.Rate of extension is 2mm/min.
As shown in Figure 1, compared with comparative example 1, embodiment 1 and the degree of crosslinking of 2 prepared crosslinkable polyethylene blend compositions and the impact that kinetics is not added by polyolefin elastomer component.
Embodiment 1
HDPE, the POE of 10wt% that preparation comprises 90wt%, HDPE based on 100 weight parts and the gross weight of POE, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the crosslinkable polyethylene composition of the crosslinking accelerator TAIC of 5-dimethylhexane, 1.0 weight parts, said composition shows the toughness and the stripping strength that improve a little.As shown in table 3, after adding the POE of 10wt%, compared with comparative example 1,180 ° of stripping strengths and the low temperature impact intensity of the prepared crosslinkable ethene blend composition of embodiment 1 have improved respectively 288% and 167%.
Embodiment 2
HDPE, the POE of 20wt% that preparation comprises 80wt%, HDPE based on 100 weight parts and the gross weight of POE, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the crosslinkable polyethylene of the crosslinking accelerator TAIC of 5-dimethylhexane, 1.0 weight parts.As shown in table 2, after adding the POE of 20wt%, compared with comparative example 1, the stripping strength of 180 ° of the prepared crosslinkable polyethylene blend composition of embodiment 2 and low temperature impact intensity have improved respectively 995% and be greater than 670%.
Embodiment 3
HDPE, the POE of 30wt% that preparation comprises 70wt%, HDPE based on 100 weight parts and the gross weight of POE, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the crosslinkable polyethylene of the crosslinking accelerator TAIC of 5-dimethylhexane, 1.0 weight parts.As shown in table 2, after adding the POE of 30wt%, compared with comparative example 1, the stripping strength of 180 ° of the prepared crosslinkable polyethylene blend composition of embodiment 3 and low temperature impact intensity have improved respectively 1687% and be greater than 670%.
Embodiment 4
In the course of processing, be cross-linked for fear of too early, obtain better metal bonding and toughness simultaneously, HDPE, the POE of 20wt% that preparation comprises 80wt%, HDPE based on 100 weight parts and the gross weight of POE, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the composition of the crosslinking accelerator TAIC of 5-dimethylhexane, 1.0 weight parts, the scorch retarder TEMPO of 0.3 weight part.Along with adding a small amount of scorch retarder, the processing characteristics that crosslinkable composition exhibiting improves, smooth surface and there is no bubble formation.Along with the increase of POE concentration, as shown in table 3, the prepared crosslinkable ethene blend composition of embodiment 4 has obtained good low temperature impact intensity and 180 ° of stripping strengths.
Comparative example 1
For relatively, also prepare the crosslinkable polyethylene composition that does not comprise POE, the HDPE that it comprises 100wt%, and HDPE based on 100 weight parts, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the auxiliary agent TAIC of 5-dimethylhexane, 1.0 weight parts.From said composition, can find out, stripping strength and resistance to impact shock all significantly decline.For uncrosslinked polyethylene composition, stripping strength is less than 10N/m.
Comparative example 2
For relatively, also prepare the cross-linkable composition of 100wt%POE, the POE that it comprises 100wt%, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the auxiliary agent TAIC of 5-dimethylhexane, 1.0 weight parts.For crosslinked POE sample, its stripping strength is 1041N/m, far below the stripping strength of HDPE/POE blended cross linking composition in embodiment 2 and embodiment 3, the synergistic effect between blend components is described.
Comparative example 3
HDPE, the LLDPE of 20wt% that preparation comprises 80wt%, HDPE based on 100 weight parts and the gross weight of LLDPE, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the crosslinkable polyethylene of the crosslinking accelerator TAIC of 5-dimethylhexane, 1.0 weight parts.As shown in table 2, after adding the LLDPE of 20wt%, compared with comparative example 1, the low temperature impact intensity of the prepared crosslinkable polyethylene blend composition of comparative example 2 and the stripping strength of 180 ° all show small size decline, and this explanation elastomerics is huge for the cohesiveness of HDPE own and impact property impact.
Embodiment 5
HDPE, the EPDM of 10wt% that preparation comprises 90wt%, HDPE based on 100 weight parts and the gross weight of EPDM, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the crosslinkable polyethylene of the crosslinking accelerator TAIC of 5-dimethylhexane, 1.0 weight parts.As shown in table 2, after adding the EPDM of 10wt%, compared with comparative example 1, the stripping strength of 180 ° and the low temperature impact intensity of the prepared crosslinkable polyethylene blend composition of embodiment 5 have improved respectively 977% and 670%.
Embodiment 6
HDPE, the EPDM of 20wt% that preparation comprises 80wt%, HDPE based on 100 weight parts and the gross weight of EPDM, the linking agent 2 of 1.0 weight parts, 5-bis(t-butylperoxy)-2, the crosslinkable polyethylene of the crosslinking accelerator TAIC of 5 dimethylhexanes, 1.0 weight parts.As shown in table 2, after adding the EPDM of 20wt%, compared with comparative example 1, the low temperature impact intensity of the prepared crosslinkable polyethylene blend composition of embodiment 6 and the stripping strength of 180 ° have improved respectively 1363% and be greater than 670%.Under same elastomer content, EPDM is more obvious to the raising of HDPE metal bonding and toughness.
Embodiment 7
HDPE, the EPDM of 20wt% that preparation comprises 80wt%, HDPE based on 100 weight parts and the gross weight of EPDM, the linking agent 2 of 0.5 weight part, 5-bis(t-butylperoxy)-2, the crosslinkable polyethylene of the crosslinking accelerator TAIC of 5 dimethylhexanes, 0.5 weight part.As shown in table 2, after adding the EPDM of 20wt%, compared with comparative example 1, the low temperature impact intensity of the prepared crosslinkable polyethylene blend composition of embodiment 7 and the stripping strength of 180 ° have improved respectively 881% and be greater than 670%.The minimizing of linking agent and crosslinking accelerator content can weaken the metal bonding of cross-linked polyethylene composition.
Table 1
Table 2
The term that this specification sheets is used and form of presentation are only used as descriptive and nonrestrictive term and form of presentation, in the time using these terms and form of presentation, are not intended to any equivalent exclusion of the feature representing and describe or its integral part.
Although represented and described several embodiment of the present invention, the present invention is not restricted to described embodiment.On the contrary, those of ordinary skills should recognize in the situation that not departing from principle of the present invention and spirit can carry out any accommodation and improvement to these embodiments, and protection scope of the present invention is determined by appended claim and equivalent thereof.
Claims (24)
1. a crosslinkable polyethylene blend composition, it comprises:
(a) polyvinyl resin of 70～90 parts (weight), its density is at 0.910-0.970g/cm
3and there is crystallization or hypocrystalline;
(b) the polyolefin elastomer component of 10～30 parts (weight), its density is at 0.855-0.900g/cm
3and/or there is 20% following degree of crystallinity; With
(c) peroxide cross-linking agent of 0.1～5 part (weight), the polyvinyl resin based on 100 parts (weight) and the gross weight of polyolefin elastomer.
2. crosslinkable polyethylene blend composition according to claim 1, wherein, described polyvinyl resin is selected from Alathon, ethene-C
4-8one or more in olefin copolymer.
3. crosslinkable polyethylene blend composition according to claim 1 and 2, wherein, described polyvinyl resin is linear low density polyethylene and/or high density polyethylene(HDPE).
4. crosslinkable polyethylene blend composition according to claim 1 and 2, wherein, the degree of crystallinity of described polyvinyl resin is more than 45%, and its melt index is 1～100g/10min.
5. crosslinkable polyethylene blend composition according to claim 4, wherein, the melt index of described polyvinyl resin is 2～20g/10min.
6. crosslinkable polyethylene blend composition according to claim 1, wherein, described polyolefin elastomer is selected from ethylene-propylene rubber(EPR), terpolymer EP rubber, ethene-C
4-8one or more in olefin copolymer.
7. according to the crosslinkable polyethylene blend composition described in claim 1 or 6, wherein, the molecular weight distribution of described polyolefin elastomer is less than 2.8.
8. according to the crosslinkable polyethylene blend composition described in claim 1,6 or 7, wherein, the melt index of described polyolefin elastomer is 0.1～500g/10min.
9. crosslinkable polyethylene blend composition according to claim 8, wherein, the melt index of described polyolefin elastomer is 0.5～20g/10min.
10. according to the crosslinkable polyethylene blend composition described in claim 1,6 or 7, wherein, the ethylene content of described polyolefin elastomer is less than 75wt%.
11. crosslinkable polyethylene blend compositions according to claim 10, wherein, the ethylene content of described polyolefin elastomer is less than 60wt%.
12. crosslinkable polyethylene blend compositions according to claim 1, wherein, described peroxide cross-linking agent is that effective oxygen is the peroxide cross-linking agent of 0.004～0.25 part (weight); Preferably effective oxygen is the peroxide cross-linking agent of 0.02～0.125 weight part.
13. according to the crosslinkable polyethylene blend composition described in claim 1 or 12, and wherein, described peroxide cross-linking agent is two (tertiary alkyl peroxy) paraffinic hydrocarbonss and/or two (tertiary alkyl peroxy) benzene.
14. according to claim 1, crosslinkable polyethylene blend composition described in 12 or 13, wherein, described peroxide cross-linking agent is selected from 2, two (the tert-pentyl peroxies)-2 of 5-, 5-dimethylhexane, 2, 5-bis(t-butylperoxy)-2, 5-dimethylhexane, 3, 6-bis(t-butylperoxy)-3, 6-dimethyl octane, 2, 7-bis(t-butylperoxy)-2, 7-dimethyl octane, 8, 11-bis(t-butylperoxy)-8, 11-dimethyl octane, α, α '-bis-(t-butylperoxy-sec.-propyl)-benzene, α, one or more in α '-bis-(tert-pentyl peroxy-sec.-propyl)-benzene and their derivative.
15. crosslinkable polyethylene blend compositions according to claim 14, wherein, described peroxide cross-linking agent is 2,5-bis(t-butylperoxy)-2,5-dimethylhexane and/or α, α '-bis-(tert-pentyl peroxy-sec.-propyl)-benzene.
16. according to the crosslinkable polyethylene blend composition described in claim 1-15 any one, comprises peroxide cross-linking agent, the polyvinyl resin based on 100 parts (weight) and the gross weight of polyolefin elastomer of 0.5～2.5 part (weight).
17. according to the crosslinkable polyethylene blend composition described in claim 1-16 any one, further comprise the stablizer of the scorch retarder of the crosslinking accelerator of 0.05～5 part (weight), 0.1～1 part (weight), 0.05～5 part (weight) and/or the pigment of 0.05～5 part (weight), the polyvinyl resin based on 100 parts (weight) and the gross weight of polyolefin elastomer.
18. crosslinkable polyethylene blend compositions according to claim 17, wherein, described crosslinking accelerator is selected from one or more in 1,2-polyhutadiene, triallyl cyanate, triallyl isocyanate.
19. crosslinkable polyethylene blend compositions according to claim 17, wherein, described scorch retarder be selected from organic oxidation-resistant agent, quinhydrones and/or the quinhydrones that replaces in one or more.
20. crosslinkable polyethylene blend compositions according to claim 1, the degree of crosslinking of the polyethylene blend composition after it is crosslinked is greater than 25%.
21. crosslinkable polyethylene blend compositions according to claim 20, the degree of crosslinking of the polyethylene blend composition after it is crosslinked is greater than 35%.
Prepare the method for the crosslinkable polyethylene blend composition described in claim 1-21 any one for 22. 1 kinds, comprise described polyvinyl resin, polyolefin elastomer and peroxide cross-linking agent twin screw extruder is carried out to melt blending, granulation under 130～150 ℃ of conditions.
23. 1 kinds comprise the goods of the crosslinkable polyethylene blend composition described in claim 1-21 any one, and it comprises at least one metal parts.
Prepare the method for goods described in claim 23 for 24. 1 kinds, it is by extrusion molding, compression moulding, rotational moulding method or blow moulding preparation.
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| CN107286854A (en) * | 2017-07-26 | 2017-10-24 | 广州市白云化工实业有限公司 | Polyolefin packaging adhesive film and its preparation method and application |
| CN108034104A (en) * | 2017-11-17 | 2018-05-15 | 神华集团有限责任公司 | Polyethylene injection composition and polyethylene injection moulded products and preparation method thereof |
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| CN106478887A (en) * | 2016-10-18 | 2017-03-08 | 神华集团有限责任公司 | A kind of cross-linking grafted polyethylene composition, cross-linked graft polyethylene products and preparation method and product |
| CN106478887B (en) * | 2016-10-18 | 2019-12-10 | 神华集团有限责任公司 | cross-linked grafted polyethylene composition, cross-linked grafted polyethylene product, preparation method and product |
| CN107286854A (en) * | 2017-07-26 | 2017-10-24 | 广州市白云化工实业有限公司 | Polyolefin packaging adhesive film and its preparation method and application |
| CN109627539A (en) * | 2017-10-09 | 2019-04-16 | 中国石油化工股份有限公司 | Polyethylene composition and preparation method thereof with excellent resistance to cracking energy |
| CN109627539B (en) * | 2017-10-09 | 2021-08-10 | 中国石油化工股份有限公司 | Polyethylene composition having excellent crack resistance and method for preparing the same |
| CN108034104A (en) * | 2017-11-17 | 2018-05-15 | 神华集团有限责任公司 | Polyethylene injection composition and polyethylene injection moulded products and preparation method thereof |
| US20210079176A1 (en) * | 2018-02-01 | 2021-03-18 | Down Global Technologies LLC | Masterbatch with semi-crystalline polyolefin carrier resin |
| CN113915423A (en) * | 2020-07-10 | 2022-01-11 | 国家能源投资集团有限责任公司 | Corrosion-resistant pipeline and application |
| CN112321932A (en) * | 2020-12-05 | 2021-02-05 | 江苏中通管业有限公司 | Production process of environment-friendly high-toughness polyethylene drainage pipeline |
| CN115895093A (en) * | 2023-02-16 | 2023-04-04 | 天津华德科技有限公司 | Antistatic breathable film and preparation method thereof |
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