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 commonly used in the art for preparing polyolefin materialsIn order to further improve the metal adhesion of the polyolefin material or the crosslinked polyolefin material obtained, 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 of olefins composition of polyethylene with ethylene propylene rubber and 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)3A melt index of 20.0g10 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.