CN112048116A - Polyolefin composition, polyolefin material and crosslinked polyolefin material - Google Patents
Polyolefin composition, polyolefin material and crosslinked polyolefin material Download PDFInfo
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- CN112048116A CN112048116A CN201910489879.3A CN201910489879A CN112048116A CN 112048116 A CN112048116 A CN 112048116A CN 201910489879 A CN201910489879 A CN 201910489879A CN 112048116 A CN112048116 A CN 112048116A
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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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
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Abstract
The invention relates to the field of polymer modification, in particular to a polyolefin composition, a polyolefin material prepared from the polyolefin composition, and a cross-linked polyolefin material prepared from the polyolefin composition. The polyolefin composition comprises polyolefin, a compatilizer, a peroxide crosslinking agent and a silane coupling agent, wherein the content of the compatilizer is 0.5-12 parts by weight, the content of the peroxide crosslinking agent is 0.2-6 parts by weight and the content of the silane coupling agent is 0.5-3 parts by weight relative to 100 parts by weight of the polyolefin. The polyolefin material or the cross-linked polyolefin material prepared from the polyolefin composition has strong adhesion with metal and environmental stress cracking resistance at high temperature.
Description
Technical Field
The invention relates to the field of polymer modification, in particular to a polyolefin composition, a polyolefin material prepared from the polyolefin composition, and a cross-linked polyolefin material prepared from the polyolefin composition.
Background
The crosslinkable polyethylene has excellent high temperature resistance, chemical corrosion resistance, good impact strength and the like, and has important application value in the aspects of chemical storage and transportation, oil and gas transportation, chemical anticorrosion and the like. However, the crosslinkable polyethylene as a low-polarity mixture has poor adhesion with a polar matrix (such as metal), so that the metal part and the polyethylene part in the prepared polyethylene and metal composite member are easy to peel off, and the service life of the polyethylene and metal composite member is greatly shortened.
Disclosure of Invention
The invention aims to improve the adhesion between crosslinked polyethylene and a polar matrix (such as metal), and provides a polyolefin composition, a polyolefin material prepared from the polyolefin composition, and a crosslinked polyolefin material prepared from the polyolefin composition. The polyolefin material or the cross-linked polyolefin material prepared from the polyolefin composition has strong adhesion with metal and environmental stress cracking resistance at high temperature.
In order to achieve the above object, a first aspect of the present invention provides a polyolefin composition comprising a polyolefin, a compatibilizing agent, a peroxide crosslinking agent and a silane coupling agent, the compatibilizing agent being contained in an amount of 0.5 to 12 parts by weight, the peroxide crosslinking agent being contained in an amount of 0.2 to 6 parts by weight and the silane coupling agent being contained in an amount of 0.5 to 3 parts by weight, relative to 100 parts by weight of the polyolefin.
In a second aspect, the present invention provides a polyolefin material, which is obtained by melt blending the polyolefin composition according to the first aspect of the present invention to obtain a mixed material, and then solidifying and molding the mixed material.
In a third aspect, the present invention provides a crosslinked polyolefin material obtained by subjecting the polyolefin composition according to the first aspect of the present invention to a crosslinking reaction.
The polyolefin composition of the invention firstly utilizes peroxide and silane to carry out 'double cross-linking', and the polyolefin material or the cross-linked polyolefin material has good metal adhesion and environmental stress cracking resistance at high temperature by matching with other components and contents of the composition.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a polyolefin composition comprising a polyolefin, a compatibilizing agent, a peroxide crosslinking agent and a silane coupling agent, wherein the content of the compatibilizing agent is 0.5 to 12 parts by weight, the content of the peroxide crosslinking agent is 0.2 to 6 parts by weight and the content of the silane coupling agent is 0.5 to 3 parts by weight, relative to 100 parts by weight of the polyolefin.
In the present invention, in order to further improve the metal adhesion of the polyolefin material or the crosslinked polyolefin material produced, it is preferable that the content of the compatibilizing agent is 1 to 5 parts by weight, the content of the peroxide crosslinking agent is 0.5 to 3 parts by weight, and the content of the silane coupling agent is 1 to 2 parts by weight, relative to 100 parts by weight of the polyolefin.
In the present invention, the weight ratio of the peroxide crosslinking agent to the silane coupling agent is preferably 1 (1.1-2.5), more preferably 1 (1.5-2). With this preferred weight ratio of peroxide crosslinking agent to silane coupling agent, a better "double crosslinking" can be achieved, resulting in a resulting polyolefin material or crosslinked polyolefin material with better metal adhesion.
In the present invention, preferably, the polyolefin is selected from polyethylene, ethylene and C4-C8One or more of copolymers of olefins and ethylene-propylene rubbers.
In the present invention, the polyolefin may be a polyolefin resin commonly used in the art for preparing polyolefin materials, and in order to further improve the metal adhesion of the prepared polyolefin material or crosslinked polyolefin material, it is preferable that the polyolefin has a density of 0.85 to 0.965g/cm3More preferably 0.87 to 0.92g/cm3。
In the present invention, the polyolefin may be a polyolefin resin commonly used in the art for preparing polyolefin materials, and in order to further improve the metal adhesion of the prepared polyolefin material or crosslinked polyolefin material, it is preferable that the polyolefin has a melt index of 0.01 to 50g/10min, more preferably 2 to 30g/10min, measured at 190 ℃ and under a 2.16kg load.
In the present invention, preferably, the polyolefin is composed of polyethylene and ethylene and C4-C8Copolymer of olefin and/or ethylene propylene rubber, wherein the content of the polyethylene is 80-90 wt% based on the total weight of the polyolefin, and the ethylene and the C are4-C8The content of the olefin copolymer and/or the ethylene-propylene rubber is 10-20 wt%. In the present invention, "polyethylene and ethylene and C4-C8Copolymers of olefins and/or ethylene-propylene rubbers "comprising" polyethylene with ethylene and C4-C8Copolymer composition of olefins"consisting of polyethylene and ethylene propylene rubber" and "consisting of polyethylene, ethylene and C4-C8Copolymers of olefins and ethylene-propylene rubbers "three cases, in the last case ethylene and C4-C8The ratio of the copolymer of olefin and the ethylene-propylene rubber is not particularly limited.
In order to further improve the metal adhesion of the obtained polyolefin material or crosslinked polyolefin material, according to a more preferred embodiment of the present invention, it is further preferred that the polyethylene is obtained from a combination of a first polyethylene, a second polyethylene and a third polyethylene; in this more preferred embodiment, preferably, the density ρ of the first polyethylene1Is 0.89-0.92g/cm3Density p of the third polyethylene3Is 0.94-0.965g/cm3Density p of the second polyethylene2Is 0.92g/cm3<ρ2<0.94g/cm3(ii) a Even more preferably, the polyethylene is obtained by combining a first polyethylene, a second polyethylene and a third polyethylene, the density ρ of the first polyethylene being1Is 0.915-0.92g/cm3Density p of the third polyethylene3Is 0.95 to 0.96g/cm3Density p of the second polyethylene2Is 0.92g/cm3<ρ2<0.935g/cm3。
In the above more preferred embodiment, preferably, the first polyethylene has a melt index MI measured at 190 ℃ under a load of 2.16kg1A melt index MI of the second polyethylene measured at 190 ℃ under a load of 2.16kg of 10 to 25g/10min2Is 3-15g/10min, and the melt index MI of the third polyethylene measured at 190 ℃ and under a load of 2.16kg315-25g/10 min; further preferably, the first polyethylene has a melt index MI measured at 190 ℃ and under a load of 2.16kg1A melt index MI of the second polyethylene measured at 190 ℃ under a load of 2.16kg of from 12 to 20g/10min2Is 4-6g/10min, and the melt index MI of the third polyethylene measured at 190 ℃ and under a load of 2.16kg3Is 15-20g/10 min.
In the above more preferred embodiment, preferably, the content of the first polyethylene is 50 to 60 wt%, the content of the second polyethylene is 20 to 25 wt%, and the content of the third polyethylene is 20 to 25 wt%, based on the total weight of the polyethylenes.
In the present invention, preferably, the compatibilizer is a polyolefin grafted with a polar monomer. The polar monomer grafted polyolefin can achieve better effects by adopting the polar monomer grafted polyolefin commonly used in the polyolefin composition in the field, and is commercially available.
In order to further improve the metal adhesion of the obtained polyolefin material or crosslinked polyolefin material, the grafting ratio of the polar monomer grafted polyolefin is preferably more than 0.1%, more preferably 0.5-2% by weight, most preferably 0.8-1.2% by weight.
Preferably, the polar monomer in the polar monomer grafted polyolefin is selected from one or more of acrylic acid and its esters, methacrylic acid and its esters, maleic anhydride and its esters, and isocyanates.
More preferably, the polar monomer in the polar monomer grafted polyolefin is selected from one or more of acrylic acid, methacrylic acid, methyl methacrylate, hydroxypropyl methyl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, N-dimethylaminoethyl methacrylate, maleic anhydride, toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
Preferably, the polyolefin of the polar monomer grafted polyolefin includes, but is not limited to, polyethylene, polypropylene, ethylene and C4-C8Copolymers of olefins and ethylene-propylene rubbers.
In the present invention, the polar monomer-grafted polyolefin may be used as it is.
In the present invention, the peroxide crosslinking agent may be a peroxide crosslinking agent which is conventional in the art, and the inventors of the present invention have found that a specific kind of peroxide crosslinking agent can be combined with other components of the polyolefin composition of the present invention to provide a polyolefin material or a crosslinked polyolefin material having better metal adhesion. Preferably, the peroxide crosslinking agent is selected from one or more of alkyl peroxides, aryl peroxides, acyl peroxides, and ketone peroxides. More preferably, the peroxide crosslinking agent is selected from the group consisting of 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 7-dimethyl-2, 7-bis (tert-butylperoxy) octadiyne-3, 5, 2, 7-dimethyl-2, 7-bis (ethyl peroxycarbonate) octadiyne-3, 5, 3, 6-dimethyl-3, 6-bis (ethyl peroxycarbonate) octyne-4, 3, 6-dimethyl-3, 6-bis (tert-butylperoxy) octyne-4, 2, 5-dimethyl-2, 5-bis (peroxybenzoate) hexyne-3, 2, 5-dimethyl-2, 5-bis (n-propyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-3, 5-bis (n-propyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (isobutyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (ethyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (alpha-cumylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (beta-chloroethyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne-3, butyl 4, 4-di (tert-butylperoxy) valerate, di (2, 4-dichlorobenzoyl) peroxide, di (4-methylbenzoyl) peroxide, di (tert-butylperoxyisopropyl) benzene, dibenzoyl peroxide, p, One or more of dicumyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, t-butylperoxy-3, 5,5 trimethyl hexanoate, t-butylperoxy benzoate and t-butylperoxy 2-ethylhexyl carbonate and derivatives thereof; further preferably, the peroxide crosslinking agent is selected from one or more of di-t-butyl peroxide, dicumyl peroxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyne-3, and dibenzoyl peroxide.
In order to further improve the metal adhesion of the polyolefin material or the crosslinked polyolefin material produced according to the polyolefin composition of the present invention, the peroxide crosslinking agent preferably has an available oxygen content of 0.8 to 30% by weight, more preferably 2 to 25% by weight.
In order to further improve the metal adhesion of the polyolefin material or the crosslinked polyolefin material produced according to the polyolefin composition of the present invention, the silane coupling agent may be a silane coupling agent that is conventional in the art, and is more preferably selected from one or more of alkyl silane, vinyl silane, amino silane, epoxy silane, methacryloxy silane, mercapto silane, ureido silane and cyano silane, and derivatives thereof; further preferably, the silane coupling agent is selected from one or more of vinyl silane, epoxy silane, methacryloxy silane, and cyano silane, and derivatives thereof; further preferably, the silane coupling agent is selected from one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
According to the polyolefin composition of the present invention, when the polyolefin composition is composed of the polyolefin, the compatibilizer, the peroxide crosslinking agent and the silane coupling agent, a good metal adhesion can be achieved, and in order to further improve the metal adhesion of the polyolefin material or the crosslinked polyolefin material produced, in a more preferable case, the polyolefin composition further comprises a crosslinking assistant in an amount of 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and still more preferably 1 to 3 parts by weight, relative to 100 parts by weight of the polyolefin.
In order to better cooperate with other ingredients in the polyolefin composition of the present invention to further improve the metal adhesion of the polyolefin material or the crosslinked polyolefin material obtained, the crosslinking assistant according to the present invention may be a conventional crosslinking assistant in the art, and preferably is selected from one or more of 1,2 polybutadiene, diallyl terephthalate (DATP), Divinylbenzene (DVB), triallyl cyanurate (TAC), triallyl cyanurate (TAP), triallyl isocyanate (TAIC), and derivatives thereof; more preferably, the crosslinking coagent is selected from one or more of triallyl cyanurate, diallyl terephthalate, divinylbenzene, triallyl isocyanate and triallyl cyanurate.
The polyolefin composition according to the present invention preferably further comprises a flame retardant in an amount of 0.01 to 2 parts by weight, relative to 100 parts by weight of the polyolefin. The flame retardant is selected according to the conventional selection in the field.
The polyolefin composition according to the present invention preferably further comprises an antioxidant in an amount of 0.01 to 2 parts by weight, relative to 100 parts by weight of the polyolefin. The antioxidant is selected according to the routine choice in the field.
In a second aspect, the present invention provides a polyolefin material, which is obtained by melt blending the polyolefin composition according to the first aspect of the present invention to obtain a mixed material, and then solidifying and molding the mixed material.
Preferably, the temperature of the melt blending is 130-200 ℃, more preferably 140-160 ℃.
In the present invention, the curing molding may be performed by various conventional means in the art, such as powder coating, extrusion/flow winding, thermal roll coating, electrostatic spraying, thermal dip molding, and the like. The specific parameters of the above modes can be performed according to the conventional parameters in the field, and are not described herein again.
In a third aspect, the present invention provides a crosslinked polyolefin material obtained by subjecting the polyolefin composition according to the first aspect of the present invention to a crosslinking reaction.
Preferably, the temperature of the crosslinking reaction is 180-230 ℃, and the time of the crosslinking reaction is 5-30 min; more preferably, the temperature of the crosslinking reaction is 190-210 ℃, and the time of the crosslinking reaction is 10-20 min.
Preferably, the cross-linked polyolefin material has a degree of cross-linking of greater than 25%, more preferably from 40% to 80%.
The polyolefin material according to the second aspect of the present invention or the modified crosslinked polyolefin material according to the third aspect of the present invention can be obtained as desired by those skilled in the art.
The present invention will be described in detail below by way of examples. In the following examples, 1 part by weight represents 1 g.
The relevant data were obtained as follows:
(1) melt index MI: the measurement is carried out according to the method specified in GB/T3682-2000, wherein the test temperature is 190 ℃, and the load is 2.16 kg;
(2) density of polyethylene and composition: the measurement was carried out according to the method specified in GB/T1033.2-2010 and by the density gradient column method.
Example 1
Preparing a polyolefin composition comprising the following ingredients:
(1) the polyolefin comprises the following components in parts by weight, wherein the total parts by weight are 100:
polyethylene, 88 parts by weight in total, was prepared from 44 parts by weight of 1 st-1 st polyethylene (Islam chemical Co., Ltd., trade name 811, density 0.915g/cm320g/10min), 22 parts by weight of 1-2 polyethylene (Korea Dadall R902S, density 0.935g/cm36g/10min) and 22 parts by weight of 1-3 polyethylene (monoliths DAMA2911, density 0.960 g/cm)3And the melt index is 20g/10 min);
copolymer of ethylene and octene (Dupont Dow, ENGAGE8200), 12 parts by weight;
(2) a compatilizer: maleic anhydride monomer grafted polyethylene (manufacturer is Jiayi company, brand FB16E5, grafting rate 0.8%), 3 weight portions;
(3) peroxide crosslinking agent: di-tert-butyl peroxide (from J & K Scientific), 0.6 parts by weight;
(4) silane coupling agent: 1 part by weight of gamma-aminopropyltriethoxysilane (manufactured by Shandong Chenguang company, trade name KH 550);
(5) crosslinking assistant agent: 1 part by weight of diallyl terephthalate (manufactured by J & K Scientific, brand number DATP);
(6) antioxidant: available from Shanghai Ciba Gaoqiao Chemicals Inc. under the designation IRGANOX1010, 0.05 parts by weight.
The polyolefin composition is denoted as S1.
Example 2
Preparing a polyolefin composition comprising the following ingredients:
(1) the polyolefin comprises the following components in parts by weight, wherein the total parts by weight are 100:
polyethylene, 90 parts by weight in total, was prepared from 50 parts by weight of 1 st-2 nd polyethylene (DuPont Dow., trademark 4012, density 0.918g/cm3A melt index of 12g/10min), 20 parts by weight of 2-2 polyethylene (Yangzhi Passion Limited, Inc., No. 2420K, density of 0.924g/cm34.0g/10min) and 20 parts by weight of 2-3 polyethylene (Tianjin Union Chemicals Co., Ltd., trade name DMDA8920, density 0.954 g/cm)3And the melt index is 20.0g/10 min);
ethylene propylene rubber (Dupont Dow company, manufacturer, designation 3660), 10 parts by weight;
(2) a compatilizer: 5 parts by weight of maleic anhydride grafted ethylene octene copolymer (the manufacturer is Dow chemical, the brand is GR216, the grafting rate is 1.2 percent);
(3) peroxide crosslinking agent: dicumyl peroxide (from J & K Scientific), 1 part by weight;
(4) silane coupling agent: 2 parts by weight of vinyltriethoxysilane (manufactured by Shandong Chenguang company, trade name A171);
(5) crosslinking assistant agent: 2 parts by weight of triallyl isocyanurate (J & K Scientific, brand TAIC);
(6) flame retardant: antimony trioxide (from national pharmaceutical group), 2 parts by weight;
(7) antioxidant: available from Shanghai Ciba Gaoqiao Chemicals Inc. under the designation IRGANOX1010, 0.05 parts by weight.
The polyolefin composition is denoted as S2.
Example 3
Preparing a polyolefin composition comprising the following ingredients:
(1) the polyolefin comprises the following components in parts by weight, wherein the total parts by weight are 100:
polyethylene, 80 parts by weight in total, was prepared from 48 parts by weight of 3-1 st polyethylene (DuPont Dow., trademark 4016, density 0.918g/cm316g/10min, 16 parts by weight of 3-2 polyethylene (Tianjin Co., Ltd., trade name DNDC7149, density 0.934 g/cm)35g/10min) and 16 parts by weight of a 3 rd to 3 rd polyethylene (stringy stonecrop DMDA6143, density 0.952 g/cm)3And the melt index is 16g/10 min);
20 parts by weight of a copolymer of ethylene and octene (Dupont Dow, ENGAGE 8200);
ethylene propylene rubber (Dupont Dow, Inc., designation 3660), 20 parts by weight;
(2) a compatilizer: 5 parts by weight of glycidyl methacrylate grafted polyethylene (the manufacturer is Jiayi company, the brand is SOG-02, the grafting rate is 0.8 percent);
(3) peroxide crosslinking agent: 1, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, 1 part by weight;
(4) silane coupling agent: gamma-methacryloxypropyltrimethoxysilane (manufactured by Shandong Chenguang Co., Ltd., trade name KH570) in an amount of 1.5 parts by weight;
(5) crosslinking assistant agent: 3 parts by weight of divinylbenzene (the trade name is DVB, and the manufacturer is J & K Scientific);
(6) flame retardant: antimony trioxide (from national pharmaceutical group), 0.52 parts by weight;
(7) antioxidant: available from Shanghai Ciba Gaoqiao Chemicals Inc. under the designation IRGANOX1010, 0.05 parts by weight.
The polyolefin composition is denoted as S3.
Example 4
The method is carried out by referring to the method of example 1, except that the mixture ratio of the polyolefin of the (1) th component is changed, and the method specifically comprises the following steps: 60 parts by weight of the polyethylene (same polyethylene as in example 1, wherein the composition of the different density polyethylenes is the same), 40 parts by weight of the copolymer of ethylene and octene.
The polyolefin composition is denoted as S4.
Example 5
The process was carried out with reference to example 1, except that the compounding ratio of the polyethylene in the polyolefin of the (1) th component was changed, specifically, the polyethylene was composed of the following components: 25 parts by weight of 1 st to 1 st polyethylene, 25 parts by weight of 1 st to 2 nd polyethylene and 38 parts by weight of 1 st to 3 rd polyethylene.
The polyolefin composition is denoted as S5.
Example 6
The process was carried out with reference to example 1, except that 88 parts by weight of the polyethylene in the component polyolefin (1) was all the 1 st to 1 st polyethylene.
The polyolefin composition is denoted as S6.
Example 7
The process was carried out with reference to example 1, except that 88 parts by weight of the polyethylene in the component polyolefin (1) was all the 1 st to 3 rd polyethylenes.
The polyolefin composition is denoted as S7.
Example 8
The procedure of example 1 was repeated, except that the content of the silane coupling agent was adjusted to 1.8 parts by weight so that the weight ratio of the peroxide crosslinking agent to the silane coupling agent was 1: 3.
The polyolefin composition is denoted as S8.
Example 9
The procedure of example 1 was repeated, except that the content of the peroxide crosslinking agent was adjusted to 1 part by weight so that the weight ratio of the peroxide crosslinking agent to the silane coupling agent was 1: 1.
The polyolefin composition is denoted as S9.
Comparative example 1
The procedure of example 1 was followed, except that 0.6 parts by weight of the peroxide crosslinking agent and 1 part by weight of the silane coupling agent were replaced with 1.6 parts by weight of the same peroxide crosslinking agent as in example 1.
The polyolefin composition is designated as D1.
Comparative example 2
The procedure of example 1 was repeated, except that 0.6 parts by weight of the peroxide crosslinking agent and 1 part by weight of the silane coupling agent were replaced with 1.6 parts by weight of the same silane coupling agent as in example 1.
The polyolefin composition is designated as D2.
Comparative example 3
The procedure of example 1 was repeated, except that the compatibilizer was not provided and was replaced with 3 parts by weight of the same polyethylene as in example 1 (the internal ratio was not changed).
The polyolefin composition is designated as D3.
Test example
(1) The polyolefin compositions prepared above were subjected to the following operations, respectively:
the polyolefin composition prepared above was added to a high speed mixer to mix for 3min, and the resulting mixture was melt-blended at 140 ℃ by means of a twin screw extruder, extrusion-pelletized at 120rpm, and dried at 80 ℃ for 2 h. The polyolefin particles obtained by drying were ground into a powder having a particle size of 50 mesh by a plastic mill. Melting the powder at 200 deg.C, coating the surface of the steel plate, heating at 200 deg.C for 10min to crosslink, and cooling to obtain the composite material.
(2) The resulting composite of polyolefin and steel sheets was tested as follows:
degree of crosslinking (%): the method is carried out according to the method specified in ASTM D2765, and the specific test method comprises the following steps: a plastic block having a mass of W1 (about 0.300 ± 0.015g) was cut from the polyolefin, chopped and placed into a 100ml stainless steel mesh bag (the mesh bag specification refers to astm d 2765 requirements); after the sample is extracted in xylene solution at 170 ℃ for 20 hours, the sample is taken out and dried in a vacuum drying oven at 90 ℃ for 6 hours, and then the mass of the sample is weighed as W2; the degree of crosslinking is (W2/W1) × 100%.
Peel strength (N/cm): the method is carried out according to the method specified by GBT23257-2009, and the specific test method comprises the following steps: a1 cm wide strip is scribed on the polyolefin, the length is more than 20cm, and the depth of the scratch is up to the steel plate. Stripping one end of a cross-linked polyethylene strip by at least 2cm from a steel plate, pulling the stripped cross-linked polyethylene by using a tensile machine, fixing the steel plate by using the other end of the cross-linked polyethylene strip, pulling the cross-linked polyethylene at the speed of 10mm/min, reading the stress value of the tensile machine, and taking the average value of the stable tensile force as the peeling strength after the stable tensile force is achieved.
Environmental stress crack resistance at 100 ℃ (ESCR, unit h): the method is determined according to the method specified in GB/T1842-2008, and the specific test method comprises the following steps: a polyethylene sheet was pressed to a thickness of 2mm and a depth of notch of 0.3mm, and then fixed to a bending apparatus, and placed in a 10% F20 solution at 100 ℃ to count the time (h) for which more than half of the specimens broke.
TABLE 1
As can be seen from the table, the polyolefin obtained from the polyolefin composition of the present invention has a high degree of crosslinking and a high peel strength with metal, and it is proved that the polyolefin obtained from the polyolefin composition of the present invention has a strong adhesion with metal, and at the same time, has an excellent environmental stress cracking resistance at high temperature, which is significantly better than that of the comparative example.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A polyolefin composition comprising a polyolefin, a compatibilizing agent, a peroxide crosslinking agent and a silane coupling agent, wherein the content of the compatibilizing agent is 0.5 to 12 parts by weight, the content of the peroxide crosslinking agent is 0.2 to 6 parts by weight and the content of the silane coupling agent is 0.5 to 3 parts by weight, relative to 100 parts by weight of the polyolefin.
2. The polyolefin composition according to claim 1, wherein the content of the compatibilizing agent is 1 to 5 parts by weight, the content of the peroxide crosslinking agent is 0.5 to 3 parts by weight, and the content of the silane coupling agent is 1 to 2 parts by weight, relative to 100 parts by weight of the polyolefin;
preferably, the weight ratio of the peroxide crosslinking agent to the silane coupling agent is 1 (1.1-2.5), more preferably 1 (1.5-2).
3. Polyolefin composition according to claim 1 or 2, wherein the polyolefin is selected from polyethylene, ethylene and C4-C8One or more of a copolymer of an olefin and an ethylene-propylene rubber;
preferably, the polyolefin has a density of from 0.85 to 0.965g/cm3More preferably 0.87 to 0.92g/cm3；
Preferably, the polyolefin has a melt index, measured at 190 ℃ and under a 2.16kg load, of from 0.01 to 50g/10min, more preferably from 2 to 30g/10 min.
4. The polyolefin composition according to any of claims 1-3, wherein the polyolefin is formed from polyethylene and ethylene and C4-C8Copolymer of olefin and/or ethylene propylene rubber, wherein the content of the polyethylene is 80-90 wt% based on the total weight of the polyolefin, and the ethylene and the C are4-C8The content of olefin copolymer and/or ethylene-propylene rubber is 10-20 wt%;
preferably, the polyethylene is obtained by combining a first polyethylene, a second polyethylene and a third polyethylene, the density ρ of the first polyethylene1Is 0.89-0.92g/cm3Density p of the third polyethylene3Is 0.94-0.965g/cm3Density p of the second polyethylene2Is 0.92g/cm3<ρ2<0.94g/cm3；
Preferably, the first polyethylene has a melt index MI measured at 190 ℃ and under a load of 2.16kg1A melt index MI of 15 to 25g/10min, measured at 190 ℃ and under a load of 2.16kg, of said second polyethylene2Is 3-15g/10min, and the melt index MI of the third polyethylene measured at 190 ℃ and under a load of 2.16kg315-25g/10 min;
preferably, the first polyethylene is present in an amount of 50 to 60 wt%, the second polyethylene is present in an amount of 20 to 25 wt%, and the third polyethylene is present in an amount of 20 to 25 wt%, based on the total weight of the polyethylenes.
5. Polyolefin composition according to claim 1 or 2, wherein the compatibilizer is a polar monomer grafted polyolefin having a grafting degree of more than 0.5 to 2% by weight;
preferably, the polar monomer is selected from one or more of acrylic acid and esters thereof, methacrylic acid and esters thereof, maleic anhydride and esters thereof, and isocyanates; preferably, the polar monomer is selected from one or more of acrylic acid, methacrylic acid, methyl methacrylate, hydroxypropyl methyl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, N-dimethylaminoethyl methacrylate, maleic anhydride, toluene diisocyanate, diphenylmethane diisocyanate and hexamethylene diisocyanate.
6. Polyolefin composition according to claim 1 or 2, wherein the peroxide crosslinking agent is selected from one or more of alkyl peroxides, aryl peroxides, acyl peroxides and ketone peroxides;
preferably, the peroxide crosslinking agent is selected from the group consisting of 1, 1-bis (tert-butylperoxy) -3,3,5 trimethylcyclohexane, 2, 7-dimethyl-2, 7-bis (tert-butylperoxy) octadiyne-3, 5, 2, 7-dimethyl-2, 7-bis (ethyl peroxycarbonate) octadiyne-3, 5, 3, 6-dimethyl-3, 6-bis (ethyl peroxycarbonate) octyne-4, 3, 6-dimethyl-3, 6-bis (tert-butylperoxy) octyne-4, 2, 5-dimethyl-2, 5-bis (peroxybenzoate) hexyne-3, 2, 5-dimethyl-2, 5-bis (n-propyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-3, 5-bis (n-propyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (isobutyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (ethyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (alpha-cumylperoxy) hexyne-3, 2, 5-dimethyl-2, 5-di (beta-chloroethyl peroxycarbonate) hexyne-3, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexyne-3, butyl 4, 4-di (tert-butylperoxy) valerate, di (2, 4-dichlorobenzoyl) peroxide, di (4-methylbenzoyl) peroxide, di (tert-butylperoxyisopropyl) benzene, dibenzoyl peroxide, p, One or more of dicumyl peroxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, tert-butylperoxy-3, 5,5 trimethyl hexanoate, tert-butylperoxy benzoate and tert-butylperoxy 2-ethylhexyl carbonate;
preferably, the peroxide crosslinking agent has an available oxygen content of 0.8 to 30 wt.%.
7. Polyolefin composition according to claim 1 or 2, wherein the silane coupling agent is selected from one or more of alkylsilanes, vinylsilanes, aminosilanes, epoxysilanes, methacryloxysilanes, mercaptosilanes, ureidosilanes and cyanosilanes;
preferably, the silane coupling agent is selected from one or more of vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β -methoxyethoxy) silane, 3-glycidoxypropyltrimethoxysilane, 3- [ (2,3) -glycidoxy ] propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane, γ -methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane and 3-isocyanatopropyltriethoxysilane.
8. The polyolefin composition according to any of claims 1-7, wherein the polyolefin composition further comprises a crosslinking coagent in an amount of 0.01 to 10 parts by weight relative to 100 parts by weight of the polyolefin;
preferably, the polyolefin composition further comprises a flame retardant in an amount of 0.01 to 2 parts by weight, relative to 100 parts by weight of the polyolefin;
preferably, the polyolefin composition further comprises an antioxidant in an amount of 0.01 to 2 parts by weight, relative to 100 parts by weight of the polyolefin.
9. A polyolefin material obtained by melt-blending the polyolefin composition according to any one of claims 1 to 8 to obtain a mixed material, and then subjecting the mixed material to solidification molding;
preferably, the temperature of the melt blending is 130-200 ℃, more preferably 140-160 ℃.
10. A crosslinked polyolefin material obtained by subjecting the polyolefin composition according to any one of claims 1 to 8 to a crosslinking reaction;
preferably, the temperature of the crosslinking reaction is 180-230 ℃, and the time of the crosslinking reaction is 5-30 min;
preferably, the crosslinked polyethylene has a degree of crosslinking of greater than 25%, more preferably from 40% to 80%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012940A (en) * | 2012-09-29 | 2013-04-03 | 深圳市沃尔核材股份有限公司 | High temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material and method for preparing high temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material |
| CN103865142A (en) * | 2012-12-11 | 2014-06-18 | 神华集团有限责任公司 | Crosslinkable polyethylene co-mixed composition |
| CN104327367A (en) * | 2014-10-17 | 2015-02-04 | 上海至正道化高分子材料股份有限公司 | Low-smoke low-halogen flame retardant irradiation crosslinking material for great-section wires and cables |
| CN109181083A (en) * | 2018-07-17 | 2019-01-11 | 合肥嘉仕诚能源科技有限公司 | A kind of enhanced cable material of polyolefin |
-
2019
- 2019-06-06 CN CN201910489879.3A patent/CN112048116B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103012940A (en) * | 2012-09-29 | 2013-04-03 | 深圳市沃尔核材股份有限公司 | High temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material and method for preparing high temperature self-crosslinking halogen-free flame retardant cable insulation material or sheath material |
| CN103865142A (en) * | 2012-12-11 | 2014-06-18 | 神华集团有限责任公司 | Crosslinkable polyethylene co-mixed composition |
| CN104327367A (en) * | 2014-10-17 | 2015-02-04 | 上海至正道化高分子材料股份有限公司 | Low-smoke low-halogen flame retardant irradiation crosslinking material for great-section wires and cables |
| CN109181083A (en) * | 2018-07-17 | 2019-01-11 | 合肥嘉仕诚能源科技有限公司 | A kind of enhanced cable material of polyolefin |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102312662B1 (en) * | 2021-03-25 | 2021-10-15 | 김대승 | Injection Molded composition for buoy with excellent Environmental Stress Crack Resistance and Impact Resistance |
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