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WO2021218102A1 - 一种含有酸酐基团的聚丙烯接枝物及其制备方法 - Google Patents

一种含有酸酐基团的聚丙烯接枝物及其制备方法 Download PDF

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Publication number
WO2021218102A1
WO2021218102A1 PCT/CN2020/127465 CN2020127465W WO2021218102A1 WO 2021218102 A1 WO2021218102 A1 WO 2021218102A1 CN 2020127465 W CN2020127465 W CN 2020127465W WO 2021218102 A1 WO2021218102 A1 WO 2021218102A1
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Prior art keywords
group
substituted
polypropylene
unsubstituted
acid anhydride
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PCT/CN2020/127465
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English (en)
French (fr)
Inventor
宋文波
何金良
袁浩
邵清
李琦
施红伟
张琦
李娟�
王宇韬
胡军
邹发生
周垚
Original Assignee
中国石油化工股份有限公司
中国石油化工股份有限公司北京化工研究院
清华大学
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Application filed by 中国石油化工股份有限公司, 中国石油化工股份有限公司北京化工研究院, 清华大学 filed Critical 中国石油化工股份有限公司
Priority to AU2020444841A priority Critical patent/AU2020444841A1/en
Priority to BR112022021981A priority patent/BR112022021981A2/pt
Priority to US17/997,402 priority patent/US20230174698A1/en
Priority to EP20933920.9A priority patent/EP4144776A4/en
Priority to CA3181482A priority patent/CA3181482A1/en
Priority to JP2022565816A priority patent/JP2023523069A/ja
Priority to KR1020227041980A priority patent/KR20230025392A/ko
Publication of WO2021218102A1 publication Critical patent/WO2021218102A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C08F255/04—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms on to ethene-propene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/02—Disposition of insulation

Definitions

  • the invention belongs to the field of polymers. Specifically, it relates to a polypropylene graft containing acid anhydride groups, and a method for preparing a polypropylene graft containing acid anhydride groups.
  • high molecular polymer materials have been widely used as insulation materials for power equipment in the field of electrical engineering and the power industry.
  • the simple structure polymer plastic insulation material represented by polyethylene is particularly widely used.
  • the cross-linked polyethylene, copolymerized polyolefin and rubber materials developed on this basis are widely used in motor and transformer insulation, and line insulation.
  • the circuit breaker is insulated.
  • Vinyl polymer insulation material has good mechanical properties and thermal properties, excellent electrical insulation properties and lower prices. It is a relatively mature insulation material developed in engineering.
  • polypropylene material As a simple structure of high molecular plastic, polypropylene material has all the advantages of polyethylene material. Compared with polyethylene, polypropylene has better electrical insulation properties and a higher melting point. As an insulating material, it is expected to adapt to more severe working environments. However, polypropylene has slightly worse mechanical properties than polyethylene, especially brittle at low temperatures, and cannot be used directly as an insulating material. Therefore, for polypropylene materials, it is necessary to modify the materials to achieve comprehensive regulation of electrical, mechanical, and thermal properties, in order to maintain better insulation properties at higher temperatures and electric fields.
  • the purpose of the present invention is to overcome the above-mentioned shortcomings of the prior art and provide a new type of polypropylene graft containing acid anhydride groups, which can take into account both mechanical and electrical properties at higher operating temperatures, and is suitable for high temperature and high operating fields. Strong working conditions.
  • the first aspect of the present invention provides an acid anhydride group-containing polypropylene graft for insulating materials, characterized in that the acid anhydride group-containing polypropylene graft includes structural units derived from copolymerized polypropylene, The structural unit derived from the acid anhydride monomer and the structural unit derived from the vinyl group-containing polymerized monomer; based on the weight of the polypropylene graft containing the acid anhydride group, the polypropylene graft containing the acid anhydride group
  • the content of the structural unit derived from the acid anhydride monomer and the vinyl group-containing polymer monomer and in the grafted state is 0.1 to 5 wt%, preferably 0.4 to 3 wt%; and, the polypropylene graft containing acid anhydride groups
  • the molar ratio of the structural unit derived from the acid anhydride monomer to the structural unit derived from the vinyl group-containing polymerizable monomer is 1:1-20, preferably 1:1-10
  • the second aspect of the present invention provides a method for preparing an acid anhydride group-containing polypropylene graft for insulating materials.
  • the reaction mixture of vinyl polymerized monomers undergoes a grafting reaction to obtain the polypropylene graft containing anhydride groups; wherein the conditions of the grafting reaction are such that: On a basis of weight, the content of structural units in the grafted state derived from acid anhydride monomers and vinyl group-containing polymerized monomers in the polypropylene grafts containing acid anhydride groups is 0.1 to 5 wt%, preferably 0.4 to 3 wt% And, the molar ratio of the structural unit derived from the acid anhydride monomer to the structural unit derived from the vinyl group-containing polymerized monomer in the polypropylene graft containing acid anhydride groups is 1:1-20, preferably 1: 1-10;
  • the copolymerized polypropylene has at least one of the following characteristics: the comonomer content
  • the third aspect of the present invention provides a polypropylene graft containing acid anhydride groups for insulating materials prepared by the above preparation method.
  • the fourth aspect of the present invention provides the application of the above-mentioned polypropylene graft containing acid anhydride groups as an insulating material.
  • a fifth aspect of the present invention provides a cable, characterized in that the cable comprises: at least one conductor and at least one electrical insulating layer surrounding the conductor; wherein the material of the electrical insulating layer is the above-mentioned acid anhydride group-containing material Polypropylene grafts.
  • the sixth aspect of the present invention provides an insulating material, characterized in that the insulating material comprises the above-mentioned polypropylene graft containing anhydride groups.
  • Fig. 1 is a schematic cross-sectional view of a cable according to an embodiment of the present invention.
  • the first aspect of the present invention provides an acid anhydride group-containing polypropylene graft for insulating materials.
  • the acid anhydride group-containing polypropylene graft includes structural units derived from copolymerized polypropylene and The structural unit of the body and the structural unit derived from the polymerized monomer containing the alkenyl group; based on the weight of the polypropylene graft containing the acid anhydride group, the polypropylene graft containing the acid anhydride group is derived from the acid anhydride monomer
  • the content of the structure unit in the grafted state and the polymer monomer containing alkenyl groups is 0.1 to 5 wt%, preferably 0.4 to 3 wt%; and the polypropylene graft containing acid anhydride groups is derived from the acid anhydride monomer
  • the molar ratio of the structural unit of the body to the structural unit derived from the vinyl group-containing polymerizable monomer is 1:1-20, preferably 1:1
  • the copolymerized polypropylene has at least one of the following characteristics: the comonomer content is 0.5-40 mol%, preferably 0.5-30 mol%, more preferably 4-25% by weight, further preferably 4-22% by weight; xylene can be The soluble content is 2 to 80% by weight, preferably 18 to 75% by weight, more preferably 30 to 70% by weight, further preferably 30 to 67% by weight; the comonomer content in solubles is 10 to 70% by weight, preferably 10 to 50 wt%, more preferably 20 to 35 wt%; the intrinsic viscosity ratio of soluble matter to polypropylene is 0.3 to 5, preferably 0.5 to 3, more preferably 0.8 to 1.3.
  • the content of the structural unit in the grafted state derived from the acid anhydride monomer in the polypropylene graft containing acid anhydride groups is 0.05 to 2 wt%, preferably 0.2 to 0.7 wt%.
  • the acid anhydride is selected from acid anhydrides having at least one degree of olefinic unsaturation.
  • the acid anhydride is selected from maleic anhydride and itaconic anhydride. Further preferably, the acid anhydride is maleic anhydride.
  • the present invention provides an acid anhydride group-containing polypropylene graft for insulating materials.
  • the acid anhydride group-containing polypropylene graft includes a structural unit derived from copolymerized polypropylene and is derived from maleic anhydride.
  • the content of the acid anhydride monomer and the polymerized monomer containing an ethylenic group and the structural unit in the grafted state is 0.1 to 5 wt%, preferably 0.4 to 3 wt%; and, the polypropylene graft containing an acid anhydride group is derived
  • the molar ratio of the structural unit derived from the maleic anhydride monomer to the structural unit derived from the vinyl group-containing polymerizable monomer is 1:1-20, preferably 1:1-10.
  • the copolymerized polypropylene has at least one of the following characteristics: the comonomer content is 0.5-40 mol%, preferably 0.5-30 mol%, more preferably 4-25% by weight, further preferably 4-22% by weight; xylene can be The soluble content is 2 to 80% by weight, preferably 18 to 75% by weight, more preferably 30 to 70% by weight, further preferably 30 to 67% by weight; the comonomer content in solubles is 10 to 70% by weight, preferably 10 to 50 wt%, more preferably 20 to 35 wt%; the intrinsic viscosity ratio of soluble matter to polypropylene is 0.3 to 5, preferably 0.5 to 3, more preferably 0.8 to 1.3.
  • the content of the structural unit in the grafted state derived from maleic anhydride monomer in the polypropylene graft containing acid anhydride groups is 0.05-2wt%, preferably 0.2-0.7wt%.
  • the "structural unit” means that it is a part of a polypropylene graft containing an acid anhydride group, and its form is not limited.
  • structural unit derived from copolymerized polypropylene refers to a product formed from copolymerized polypropylene, which includes both the “group” form and the “polymer” form.
  • structural unit derived from (male) anhydride monomer refers to a product formed from (male) anhydride, which includes both "group” and “monomer” forms, as well as “polymers” "Form.
  • Structural units derived from polymerized monomers containing alkenyl groups refer to products formed from polymerized monomers containing alkenyl groups, which include both “group” forms and “monomers” forms, as well as “polymers” "Form.
  • the "structural unit” may be a repeating unit or a non-repeating independent unit.
  • the structural unit derived from (male) anhydride monomer "in a grafted state” refers to a structural unit derived from (male) anhydride monomer that forms a covalent connection (graft) with copolymerized polypropylene .
  • the structural unit derived from an alkenyl group-containing polymerized monomer "in a grafted state” refers to a structural unit derived from an alkenyl group-containing polymerized monomer that forms a covalent connection (graft) with the copolymerized polypropylene.
  • the polypropylene graft containing acid anhydride groups is prepared by the grafting reaction of copolymerized polypropylene, (male) anhydride monomers and vinyl group-containing polymer monomers, preferably by solid phase bonding.
  • Branch reaction system preferably The grafting reaction of the present invention is a radical polymerization reaction. Therefore, the “in a grafted state” refers to a state where a reactant forms a connection with another reactant after undergoing radical polymerization.
  • the connection includes both direct connection and indirect connection.
  • polypropylene grafts containing acid anhydride groups in the present invention includes products (crude products) directly prepared by grafting reaction of copolymerized polypropylene, (male) anhydride monomers and polymerized monomers containing alkenyl groups. It also includes the graft-modified polypropylene pure product obtained by further purifying the product.
  • the copolymerized polypropylene (the base polypropylene in the present invention) is a propylene copolymer containing ethylene or higher ⁇ -olefin or a mixture thereof.
  • the C 2 -C 8 ⁇ -olefins other than propylene include, but are not limited to: ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene At least one of ene and 1-octene is preferably ethylene and/or 1-butene. More preferably, the copolymer polypropylene is composed of propylene and ethylene.
  • the copolymerized polypropylene of the present invention may be a heterophasic propylene copolymer.
  • the heterophasic propylene copolymer may contain a propylene homopolymer or propylene random copolymer matrix component (1), and another propylene copolymer component (2) dispersed therein.
  • the comonomer is randomly distributed on the main chain of the propylene polymer.
  • the copolymerized polypropylene of the present invention is a heterophasic propylene copolymer prepared in situ in a reactor by an existing process.
  • the heterophasic propylene copolymer contains a propylene homopolymer matrix or a random copolymer matrix (1), and dispersed therein contains one or more ethylene or higher alpha-olefin copolymer monomers.
  • the heterophasic propylene copolymer may be a sea-island structure or a bi-continuous structure.
  • the random copolymer matrix (1) is a copolymer in which comonomers are randomly distributed on the polymer chain. In other words, it is composed of two monomer units of random length (including single molecules) in an alternating sequence.
  • the comonomer in the matrix (1) is selected from ethylene or butene. It is particularly preferred that the comonomer in the matrix (1) is ethylene.
  • the propylene copolymer (2) dispersed in the homopolymer or copolymer matrix (1) of the heterophasic propylene copolymer is substantially amorphous.
  • the copolymerized polypropylene has at least one of the following characteristics: the comonomer content is 0.5-40 mol%, preferably 0.5-30 mol%, more preferably 4-25 wt%, and further Preferably it is 4-22wt%; the content of xylene solubles is 2-80wt%, preferably 18-75wt%, more preferably 30-70wt%, still more preferably 30-67wt%; comonomer content in solubles It is 10 to 70 wt%, preferably 10 to 50 wt%, more preferably 20 to 35 wt%; the intrinsic viscosity ratio of soluble matter to polypropylene is 0.3 to 5, preferably 0.5 to 3, and more preferably 0.8 to 1.3.
  • the copolymerized polypropylene further has at least one of the following characteristics: the melt flow rate at 230°C under a load of 2.16 kg is 0.01-60 g/10min, preferably 0.05-35 g/10min, More preferably, it is 0.5-15 g/10min.
  • the melting temperature Tm is 100°C or higher, preferably 110 to 180°C, more preferably 110 to 170°C, still more preferably 120 to 170°C, still more preferably 120 to 166°C.
  • the weight average molecular weight is preferably 20 ⁇ 10 4 to 60 ⁇ 10 4 g/mol.
  • the base polypropylene with high Tm has satisfactory impact strength and flexibility at both low temperature and high temperature.
  • the graft-modified polypropylene of the present invention can withstand higher Advantages of working temperature.
  • the copolymerized polypropylene of the present invention is preferably a porous granular or powdered resin.
  • the copolymerized polypropylene further has at least one of the following characteristics: the flexural modulus is 10 to 1000 MPa, preferably 50 to 600 MPa; the elongation at break is ⁇ 200%, preferably the elongation at break is ⁇ 300%.
  • the tensile strength of the copolymerized polypropylene is greater than 5 MPa, preferably 10-40 MPa.
  • the copolymerized polypropylene of the present invention can include, but is not limited to, any commercially available polypropylene powder suitable for the present invention, such as NS06 of Sinopec Wuhan Petrochemical, SPF179 of Sinopec Qilu Petrochemical, etc., and can also pass Chinese patents CN1081683, CN1108315, CN1228096, CN1281380, CN1132865C and CN102020733A are produced by polymerization process described in CN1228096, CN1281380, CN1132865C and CN102020733A.
  • the polypropylene graft containing acid anhydride groups has at least one of the following characteristics: the melt flow rate at 230° C. under a load of 2.16 kg is 0.01 to 30 g/10 min, preferably 0.05-20g/10min, more preferably 0.1-10g/10min, more preferably 0.2-8g/10min; flexural modulus is 10-1050MPa, preferably 20-1000MPa, more preferably 50-500MPa; elongation at break ⁇ 200%, preferably breaking elongation ⁇ 300%.
  • the tensile strength of the polypropylene graft containing acid anhydride groups is greater than 5 MPa, preferably 10-40 MPa.
  • the polypropylene graft containing anhydride groups has at least one of the following characteristics:
  • the working temperature of the polypropylene graft containing acid anhydride groups is ⁇ 90°C, preferably 90-160°C;
  • the breakdown field strength of the acid anhydride group-containing polypropylene graft at 90°C is E g ⁇ 210kV/mm, preferably 210-800kV/mm;
  • the breakdown field strength change rate ⁇ E/E obtained by the breakdown field strength E of polypropylene at 90°C is greater than 1.8%, preferably 2%-50%, more preferably 5%-35%, and still more preferably 8% ⁇ 28%;
  • the direct current volume resistivity ⁇ vg of the polypropylene graft containing acid anhydride groups at 90°C and 15kV/mm field strength and the direct current volume resistance of the copolymer polypropylene at 90°C and 15kV/mm field strength The ratio ⁇ vg/ ⁇ v of the rate ⁇ v is greater than 2, preferably 2.1-40, more preferably 2.3-20, and still more preferably 2.5-10.
  • the dielectric constant of the graft-modified polypropylene material at 90° C. and 50 Hz is greater than 2.0, preferably 2.1-2.5.
  • the vinyl group-containing polymerizable monomer of the present invention is preferably selected from at least one monomer having the structure represented by formula I,
  • R b, R c, R d are each independently selected from H, substituted or unsubstituted alkyl group;
  • R a is selected from substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy, substituted or Unsubstituted aryl group, substituted or unsubstituted ester group, substituted or unsubstituted carboxyl group, substituted or unsubstituted cycloalkyl or heterocyclic group, cyano group.
  • R b , R c , R d are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl, preferably, R b , R c , and Rd are each independently selected from H, substituted unsubstituted C 1 -C 3 alkyl group;
  • R a is selected from substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 1 -C 20 alkoxy group, a substituted or unsubstituted C 6 -C 20 aryl group, substituted or unsubstituted C 1 -C 20 ester group, substituted or unsubstituted C 1 -C 20 carboxyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl or heterocyclic group, cyano group, the substituted group is halogen, hydroxy, amino, C 1 -C 6 alkyl, C 3 -C
  • the heterocyclic group is selected from imidazolyl, pyrazolyl, carbazolyl, pyrrolidone, pyridyl, piperidinyl, caprolactam, pyrazinyl, thiazolyl, purinyl, morpholinyl, oxazole Linyl.
  • R b , R c , R d are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl;
  • R a is selected from the group represented by formula 2, the group represented by formula 3, the group represented by formula 4, the group represented by formula 6, the combination of the group represented by formula 6 and the group represented by formula 7, heterocyclic ring Group
  • R 4 -R 8 are each independently selected from H, halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group ,
  • the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy , C 1 -C 12 ester group, C 1 -C 12 amine group; preferably, R 4 -R 8 are each independently selected from H, halogen, hydroxyl, amino, substituted or unsubstituted
  • R 4 -R 10 are each independently selected from H, halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group ,
  • the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy , C 1 -C 12 ester group, C 1 -C 12 amine group; preferably, R 4 -R 10 are each independently selected from H, halogen, hydroxyl, amino, substituted or unsubstituted
  • R 4 '-R 10' are each independently selected from H, halo, hydroxy, amino, phosphoric acid group, a sulfonic acid group, a substituted or unsubstituted C 1 -C 12 alkyl, substituted or non-substituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 An amino group, the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkane alkoxy, C 1 -C 12 ester group of, C 1 -C 12 group; preferably, R 4 '-R 10' are each independently selected from H, halo, hydroxy, amino, phospho
  • R m is selected from the following substituted or unsubstituted groups: C 1 -C 20 linear alkyl, C 3 -C 20 branched alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 epoxy alkyl group, C 3 -C 12 epoxy alkyl alkyl group, the substituted group is selected from at least one of halogen, amino group and hydroxyl group.
  • the vinyl group-containing polymerizable monomer is selected from vinyl acetate, styrene, ⁇ -methylstyrene, (meth)acrylate, vinyl alkyl ether, vinyl pyrrolidone, vinyl pyridine, vinyl At least one of methylimidazole and acrylonitrile; the (meth)acrylate is preferably at least one of methyl (meth)acrylate, ethyl (meth)acrylate, and glycidyl (meth)acrylate .
  • the vinyl group-containing polymerizable monomer is selected from vinyl acetate, styrene, and ⁇ -methylstyrene. Further preferably, the vinyl group-containing polymerizable monomer is styrene.
  • the acid anhydride group-containing polypropylene graft of the present invention can be prepared by a method including the following steps: in the presence of an inert gas, the copolymerization of polypropylene, (male) anhydride monomer and alkenyl-containing polymer monomer
  • the reaction mixture of the body undergoes a grafting reaction (preferably a solid-phase grafting reaction) to obtain the polypropylene graft containing acid anhydride groups.
  • the second aspect of the present invention provides a method for preparing an insulating material comprising a polypropylene graft containing an acid anhydride group.
  • the reaction mixture of base polymerized monomers undergoes a grafting reaction to obtain the polypropylene grafted product containing anhydride groups;
  • the grafting reaction conditions are such that: based on the weight of the polypropylene graft containing acid anhydride groups, the polypropylene graft containing acid anhydride groups is derived from acid anhydride monomers and vinyl group-containing polymerization
  • the content of the monomer and the structural unit in the grafted state is 0.1 to 5 wt%, preferably 0.4 to 3 wt%; and, the structural unit derived from the acid anhydride monomer in the polypropylene graft containing acid anhydride groups and the derivative
  • the molar ratio of the structural units of the self-contained alkenyl group polymerizable monomer is 1:1-20, preferably 1:1-10.
  • the copolymerized polypropylene has at least one of the following characteristics: the comonomer content is 0.5-40 mol%, preferably 0.5-30 mol%, more preferably 4-25% by weight, further preferably 4-22% by weight; xylene can be The soluble content is 2 to 80% by weight, preferably 18 to 75% by weight, more preferably 30 to 70% by weight, further preferably 30 to 67% by weight; the comonomer content in solubles is 10 to 70% by weight, preferably 10 to 50 wt%, more preferably 20 to 35 wt%; the intrinsic viscosity ratio of soluble matter to polypropylene is 0.3 to 5, preferably 0.5 to 3, more preferably 0.8 to 1.3.
  • the content of the structural unit in the grafted state derived from the acid anhydride monomer in the polypropylene graft containing acid anhydride groups is 0.05 to 2 wt%, preferably 0.2 to 0.7 wt%.
  • the acid anhydride is selected from acid anhydrides having at least one degree of olefinic unsaturation.
  • the acid anhydride is selected from maleic anhydride and itaconic anhydride. Further preferably, the acid anhydride is maleic anhydride.
  • the present invention provides a method for preparing an acid anhydride group-containing polypropylene graft for insulating materials, the preparation method comprising: copolymerizing polypropylene, maleic anhydride monomer and monomer in the presence of an inert gas The reaction mixture containing vinyl polymer monomers undergoes a grafting reaction to obtain the polypropylene graft containing acid anhydride groups;
  • the conditions of the grafting reaction are such that: based on the weight of the polypropylene graft containing acid anhydride groups, the polypropylene graft containing acid anhydride groups is derived from maleic anhydride monomers and olefin-containing monomers.
  • the content of the structural unit in the grafted state of the base polymerized monomer is 0.1 to 5 wt%, preferably 0.4 to 3 wt%; and the polypropylene graft containing acid anhydride groups is derived from maleic anhydride monomer
  • the molar ratio of the structural unit to the structural unit derived from the alkenyl group-containing polymerizable monomer is 1:1-20, preferably 1:1-10.
  • the copolymerized polypropylene has at least one of the following characteristics: the comonomer content is 0.5-40 mol%, preferably 0.5-30 mol%, more preferably 4-25% by weight, further preferably 4-22% by weight; xylene can be The soluble content is 2 to 80% by weight, preferably 18 to 75% by weight, more preferably 30 to 70% by weight, further preferably 30 to 67% by weight; the comonomer content in solubles is 10 to 70% by weight, preferably 10 to 50 wt%, more preferably 20 to 35 wt%; the intrinsic viscosity ratio of soluble matter to polypropylene is 0.3 to 5, preferably 0.5 to 3, more preferably 0.8 to 1.3.
  • the content of the structural unit in the grafted state derived from the maleic anhydride monomer in the polypropylene graft containing acid anhydride groups is 0.05-2wt%, preferably 0.2-0.7wt%.
  • the grafting reaction of the present invention can be carried out with reference to various methods conventional in the art, preferably a solid phase grafting reaction.
  • active grafting points are formed on copolymerized polypropylene, or active grafting points are formed on copolymerized polypropylene first, followed by grafting monomers.
  • the body is processed.
  • the graft points can be formed by treatment with a free radical initiator, or by high-energy ionizing radiation or microwave treatment. Free radicals generated in the polymer as a result of chemical or radiation treatment form graft points on the polymer and initiate monomer polymerization at these points.
  • the grafting point is initiated by a free radical initiator and the grafting reaction is further carried out.
  • the reaction mixture further includes a free radical initiator; further preferably, the free radical initiator is selected from peroxide radical initiators and/or azo radical initiators.
  • the peroxide radical initiator is preferably selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, lauroyl peroxide, and peroxide At least one of tert-butyl benzoate, diisopropyl peroxydicarbonate, tert-butyl peroxide (2-ethylhexanoic acid), and dicyclohexyl peroxydicarbonate; the azo group is free
  • the base initiator is preferably azobisisobutyronitrile and/or azobisisoheptonitrile.
  • the grafting point is initiated by a peroxide-based free radical initiator and the grafting reaction is further performed.
  • the grafting reaction of the present invention can also be carried out by the methods described in CN106543369A, CN104499281A, CN102108112A, CN109251270A, CN1884326A and CN101492517B.
  • the present invention does not specifically limit the amount of each component in the grafting reaction.
  • the mass of the free radical initiator is related to the (male) anhydride monomer and the The ratio of the total mass of the vinyl group-containing polymerizable monomers is 0.1-10:100, preferably 0.5-5:100.
  • the mass ratio of the total mass of the (male) anhydride monomer and the vinyl group-containing polymerizable monomer to the copolymerized polypropylene is 0.1-8:100, preferably 0.3-5:100.
  • the mass amount of the (male) anhydride monomer may be 5-100 wt%, preferably 10-100 wt% of the mass amount of the vinyl group-containing polymerizable monomer.
  • the process conditions of the grafting reaction in the present invention are also not particularly limited.
  • the temperature of the grafting reaction may be 30-130°C, preferably 60-120°C; the time may be 0.5-10h, preferably 1- 5h.
  • reaction mixture includes all the materials added to the grafting reaction system.
  • the materials can be added at one time or can be added at different stages of the reaction.
  • the reaction mixture of the present invention may also include a dispersant, and the dispersant is preferably water or an aqueous solution of sodium chloride.
  • the mass dosage of the dispersant is preferably 50-300% of the mass of the copolymerized polypropylene.
  • the reaction mixture of the present invention may also include an interface agent, which is an organic solvent having a swelling effect on polyolefin, preferably at least one of the following organic solvents having a swelling effect on copolymer polypropylene: ether solvent , Ketone solvent, aromatic hydrocarbon solvent, alkane solvent; more preferably at least one of the following organic solvents: chlorinated benzene, polychlorinated benzene, C 6 or more alkanes or cycloalkanes, benzene, C 1 -C 4- alkyl substituted benzene, C 2 -C 6 fatty ether, C 3 -C 6 fatty ketone, decalin; more preferably at least one of the following organic solvents: benzene, toluene, xylene, chlorobenzene, tetrahydrofuran , Ether, acetone, hexane, cyclohexane, decalin, heptane.
  • the reaction mixture of the present invention may also include an organic solvent as a solvent for dissolving the solid free radical initiator.
  • the organic solvent preferably includes C 2 -C 5 alcohols, C 2 -C 4 ethers and C 3 -C 5 ketones. At least one of C 2 -C 4 alcohols, C 2 -C 3 ethers and C 3 -C 5 ketones, and most preferably at least one of ethanol, ether and acetone A sort of.
  • the mass content of the organic solvent is preferably 1 to 35% of the mass of the copolymerized polypropylene.
  • the preparation method of the polypropylene graft containing acid anhydride groups can be selected from one of the following methods:
  • the preparation method includes the following steps:
  • the preparation method includes the following steps:
  • the method of the present invention if there are volatile components in the system after the reaction, the method of the present invention preferably includes a step of devolatilization.
  • the devolatilization can be carried out by any conventional method, including at the end of the grafting process. Vacuum extraction or use a stripping agent. Suitable stripping agents include, but are not limited to, inert gases.
  • the "polypropylene graft containing acid anhydride groups" of the present invention includes both the products (crude products) directly prepared by the grafting reaction of copolymerized polypropylene and acid anhydride monomers and vinyl group-containing polymerized monomers, as well as It includes the graft-modified polypropylene pure product obtained by further purifying the product. Therefore, the preparation method of the present invention may optionally include a step of purifying the crude product. Various methods conventional in the art can be used for the purification, such as extraction methods.
  • the present invention has no particular limitation on the grafting efficiency of the grafting reaction, but a higher grafting efficiency is more conducive to obtaining the desired properties of polypropylene grafts containing acid anhydride groups through a one-step grafting reaction. Therefore, it is preferable to control the grafting efficiency of the grafting reaction to 20 to 100%, more preferably 25 to 80%.
  • the concept of grafting efficiency is well known to those skilled in the art, and refers to the total amount of grafted acid anhydride monomers and vinyl group-containing polymerized monomers/the total amount of acid anhydride monomers and vinyl group-containing polymerized monomers in the reaction feed .
  • the inert gas of the present invention can be various inert gases commonly used in the field, including but not limited to nitrogen and argon.
  • the third aspect of the present invention provides a polypropylene graft containing acid anhydride groups for insulating materials prepared by the above preparation method.
  • the fourth aspect of the present invention provides the application of the above-mentioned polypropylene graft containing acid anhydride groups as an insulating material.
  • the insulating material is a cable insulating material; preferably a DC cable insulating material.
  • the insulating material is a cable insulating layer material.
  • the polypropylene graft containing acid anhydride groups used in the present invention can be directly used as the basic material of the insulating material without blending other polymers.
  • a fifth aspect of the present invention provides a cable, which includes:
  • the material of the electrical insulating layer is the polypropylene graft containing acid anhydride groups.
  • the core of the present invention is to use a new material as the electrical insulation layer of the cable. Therefore, the present invention does not specifically limit the form and specific structure of the cable, and various conventional cable forms (DC or AC, single core or Multi-core) and corresponding structures.
  • DC or AC, single core or Multi-core various conventional cable forms
  • other layer structures and other layer materials can be conventionally selected in the field.
  • the cable of the present invention may be a DC cable or an AC cable; preferably a DC cable; more preferably, the cable is a medium-high voltage DC cable or an ultra-high voltage DC cable.
  • low voltage (LV) means a voltage lower than 1kV
  • medium voltage (MV) means a voltage in the range of 1kV to 40kV
  • high voltage (HV) means a voltage higher than 40kV, preferably higher than 50kV
  • EHV ultra-high voltage
  • the cable has at least one cable core, and each of the cable cores sequentially includes a conductor, an optional conductor shielding layer, an electrical insulation layer, and an optional electrical insulation shielding from the inside to the outside. Layer, optional metal shielding layer.
  • the conductor shielding layer, the electrical insulation shielding layer, and the metal shielding layer can all be set as required, and generally, they are used in cables above 6kV.
  • the cable may also include an armor and/or sheath layer.
  • the cable of the present invention may be a single-core cable or a multi-core cable.
  • the cable may further include a filling layer and/or a tape layer.
  • the filling layer is formed of a filling material filled between the cores.
  • the wrapping layer covers the outer sides of all the wire cores to ensure that the wire core and the filling layer are round, prevent the wire core from being scratched by the armor, and play a flame retardant effect.
  • the conductor is a conductive element usually made of a metal material, preferably aluminum, copper or other alloys, and includes one or more metal wires.
  • the DC resistance and the number of filaments of the conductor must meet the requirements of GB/T 3956.
  • the preferred conductor adopts a compact and twisted circular structure with a nominal cross-sectional area less than or equal to 800 mm 2 ; or a split conductor structure with a nominal cross-sectional area greater than or equal to 1000 mm 2 and the number of conductors is not less than 170.
  • the conductor shielding layer may be a covering layer made of materials such as polypropylene, polyolefin elastomer, carbon black, etc.
  • the volume resistivity at 23°C is less than 1.0 ⁇ m, and the volume at 90°C is Resistivity ⁇ 3.5 ⁇ m, melt flow rate at 230°C under a load of 2.16kg is usually 0.01-30g/10min, preferably 0.05-20g/10min, more preferably 0.1-10g/10min, more preferably 0.2 ⁇ 8g/10min; tensile strength ⁇ 12.5MPa; elongation at break ⁇ 150%.
  • the thickness of the thinnest point of the conductor shielding layer is not less than 0.5mm, and the average thickness is not less than 1.0mm.
  • the material of the electrical insulating layer is at least one polypropylene graft containing acid anhydride groups means that the substrate constituting the electrical insulating layer is the polypropylene graft containing acid anhydride groups,
  • the polypropylene grafts containing acid anhydride groups can also contain additional components, such as polymer components or additives, preferably additives, such as antioxidants, stabilizers, processing aids, flame retardants, and water tree barriers. Any one or more of hysteresis additives, acid or ion scavengers, inorganic fillers, voltage stabilizers and anti-copper agents.
  • additives such as antioxidants, stabilizers, processing aids, flame retardants, and water tree barriers.
  • the types and amounts of additives used are conventional and known to those skilled in the art.
  • the preparation method of the electrical insulation layer of the present invention can also adopt conventional methods in the field of cable preparation, for example, mixing polypropylene grafts containing acid anhydride groups with optional various additives, and granulating with a twin-screw extruder. Then, the obtained pellets are extruded through an extruder to obtain an electrical insulation layer.
  • the conductor shielding material can be co-extruded with the polypropylene graft pellets containing acid anhydride groups to form a conductor shielding layer + electrical insulation layer structure, or a conductor shielding layer + electrical insulation layer + electrical insulation shielding layer Structure. Conventional methods and process conditions in this field can be used for specific operations.
  • the thickness of the electrical insulating layer of the present invention can be only 50%-95% of the nominal thickness of the XLPE insulating layer in GB/T 12706.
  • the electrical The thickness of the insulating layer is 70% to 90% of the nominal thickness of the XLPE insulating layer in GB/T 12706; the eccentricity is not more than 10%.
  • the electrically insulating shielding layer may be a covering layer made of polypropylene, polyolefin elastomer, carbon black and other materials, and the volume resistivity at 23°C is less than 1.0 ⁇ m, and the temperature is less than 1.0 ⁇ m at 90°C.
  • the volume resistivity is less than 3.5 ⁇ m.
  • the melt flow rate under a load of 2.16kg at 230°C is 0.01-30g/10min, preferably 0.05-20g/10min, more preferably 0.1-10g/10min, more preferably 0.2-8g/10min; tensile strength ⁇ 12.5MPa; Elongation at break ⁇ 150%.
  • the thickness of the thinnest point of the electrical insulation shielding layer is not less than 0.5mm, and the average thickness is not less than 1.0mm.
  • the metal shielding layer may be a copper tape shielding layer or a copper wire shielding layer.
  • the filling layer may be a polymer material, such as PE/PP/PVC or recycled rubber materials.
  • the covering layer/armor layer is usually made of copper wire metal cage, lead or aluminum metal sheath, etc., and wraps the metal covering layer on the outer surface of the electrical insulation shielding layer, which has a direct current at room temperature.
  • the volume resistivity is less than or equal to 1000 ⁇ m.
  • the material of the sheath layer may be any of polyvinyl chloride, polyethylene, or low-smoke halogen-free materials.
  • the sheath layer includes both an inner sheath layer and an outer sheath layer.
  • the conductor shielding layer, the electrical insulation layer, and the sheath layer can be formed by extrusion coating by an extruder, and the metal shielding layer and the armor can be formed by wrapping.
  • the cable of the present invention can be prepared by various preparation processes conventional in the field, and the present invention is not particularly limited to this.
  • the method for preparing the cable is as follows:
  • the multiple monofilament conductors (such as aluminum) are pressed and twisted to obtain the conductor core; or the stranding operation is performed, and then the stranded monofilament conductors are twisted to obtain the conductor Inner core.
  • modified polypropylene particles the polypropylene grafts containing acid anhydride groups are mixed with optional additives, and pelletized with a twin-screw extruder.
  • conductor shielding layer and electrical insulation layer Preparation of conductor shielding layer and electrical insulation layer: the conductor shielding material and the above-mentioned modified polypropylene particles are co-extrusion coated outside the conductor core by an extruder to form a conductor shielding layer + electrical insulation layer, or to form a conductor shielding layer + Electrical insulation layer + electrical insulation shielding layer (outer shielding layer).
  • Preparation of the metal shielding layer Copper tape or copper wire is wrapped around the electrical insulation layer (electrical insulation shielding layer) to form a metal shielding layer.
  • the sheath layer pellets are extruded outside the metal shielding layer through an extruder to form the inner sheath layer.
  • Armour preparation use galvanized steel/stainless steel/aluminum alloy to make steel wire or steel tape armor, with single-layer armor left to the left or double armor inner layer to the right and outer layer to the left to wrap the inner sheath On the layer, the steel wire or steel tape should be tightly armored to minimize the gap between adjacent steel wires/steel tapes.
  • the sheath layer pellets are extruded outside the armor through an extruder to form the outer sheath layer. Finally, the cable is produced.
  • the polypropylene graft containing acid anhydride groups of the present invention can take into account both mechanical properties and electrical properties at a higher working temperature, and is suitable for high temperature and high operating field strength working conditions.
  • the polypropylene graft containing acid anhydride groups of the present invention avoids performance degradation caused by the migration of small molecules, and therefore has better stability.
  • the cable of the present invention can still maintain or even have a higher volume resistivity and stronger breakdown resistance at a higher working temperature, and its mechanical properties can also meet the requirements of cable use.
  • the electrical insulation layer made of the polypropylene graft containing acid anhydride groups has a thinner thickness, better heat dissipation, and a smaller weight than the electrical insulation layer of conventional cables. advantage. Therefore, the cable has a wider range of applications.
  • the sixth aspect of the present invention provides an insulating material, characterized in that the insulating material comprises at least one of the above-mentioned polypropylene grafts containing acid anhydride groups.
  • the content of the at least one polypropylene graft containing acid anhydride groups is 20-100% by weight, preferably 40-100% by weight, more preferably 60-100% by weight , More preferably 80-100wt%, still more preferably 90-100wt%.
  • the insulating material further contains additives, such as antioxidants, stabilizers, processing aids, flame retardants, water tree retarding additives, acid or ion scavengers, inorganic fillers, voltage stabilizers, and anti-copper agents.
  • additives such as antioxidants, stabilizers, processing aids, flame retardants, water tree retarding additives, acid or ion scavengers, inorganic fillers, voltage stabilizers, and anti-copper agents.
  • additives such as antioxidants, stabilizers, processing aids, flame retardants, water tree retarding additives, acid or ion scavengers, inorganic fillers, voltage stabilizers, and anti-copper agents.
  • the types and amounts of additives are conventional and known to those skilled in the art.
  • the present invention also includes the embodiments described in the following paragraphs.
  • Paragraph 1 A method for preparing insulating materials using graft-modified polypropylene materials, characterized in that the polypropylene grafts containing acid anhydride groups include structural units derived from copolymerized polypropylene and those derived from acid anhydride monomers.
  • Structural units and structural units derived from polymerized monomers containing alkenyl groups based on the weight of the polypropylene grafts containing acid anhydride groups, the polypropylene grafts containing acid anhydrides groups are derived from acid anhydride monomers and
  • the content of the structural unit in the grafted state containing an ethylenic polymer monomer is 0.1 to 5 wt%, preferably 0.4 to 3 wt%; and the polypropylene graft containing an acid anhydride group is derived from an acid anhydride monomer
  • the molar ratio of the structural unit to the structural unit derived from the vinyl group-containing polymerizable monomer is 1:1-20, preferably 1:1-10;
  • the copolymerized polypropylene has at least one of the following characteristics: the comonomer content is 0.5-40 mol%, preferably 0.5-30 mol%, more preferably 4-25% by weight, further preferably 4-22% by weight; xylene can be The soluble content is 2 to 80% by weight, preferably 18 to 75% by weight, more preferably 30 to 70% by weight, further preferably 30 to 67% by weight; the comonomer content in solubles is 10 to 70% by weight, preferably 10 to 50 wt%, more preferably 20 to 35 wt%; the intrinsic viscosity ratio of soluble matter to polypropylene is 0.3 to 5, preferably 0.5 to 3, more preferably 0.8 to 1.3.
  • Paragraph 2 The method according to paragraph 1, wherein the copolymerized polypropylene has at least one of the following characteristics: a melt flow rate at 230° C. under a load of 2.16 kg is 0.01 to 60 g/10 min, preferably 0.05 ⁇ 35g/10min, more preferably 0.5-15g/10min; melting temperature Tm is 100°C or higher, preferably 110-180°C, more preferably 110-170°C, still more preferably 120-170°C, still more preferably 120- 166°C; the weight average molecular weight is 20 ⁇ 10 4 ⁇ 60 ⁇ 10 4 g/mol.
  • Paragraph 3 The method according to paragraph 1 or 2, wherein the comonomer of the copolymerized polypropylene is selected from at least one of C 2 -C 8 ⁇ -olefins other than propylene; preferably, the The comonomer of copolymerized polypropylene is selected from at least one of ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene and 1-octene ; Further preferably, the comonomer of the copolymerized polypropylene is ethylene and/or 1-butene; further preferably, the copolymerized polypropylene is composed of propylene and ethylene.
  • Paragraph 4 The method according to any one of paragraphs 1 to 3, wherein the polypropylene graft containing acid anhydride groups is made of copolymerized polypropylene, acid anhydride monomers and vinyl group-containing polymer monomers through solid phase bonding. Branch reaction system.
  • Paragraph 5 The method according to any one of paragraphs 1 to 4, wherein the content of structural units in the grafted state derived from acid anhydride monomers in the polypropylene graft containing acid anhydride groups is 0.05 to 2wt%, preferably 0.2 to 0.7wt%.
  • Paragraph 6 The method according to any one of paragraphs 1-6, wherein the acid anhydride is selected from acid anhydrides having at least one olefinic unsaturation; preferably, the acid anhydride is selected from maleic anhydride and itaconic anhydride; Further preferably, the acid anhydride is maleic anhydride.
  • Paragraph 7 The method according to any one of paragraphs 1-7, wherein the polypropylene graft containing anhydride groups has at least one of the following characteristics: melting at 230°C under a load of 2.16 kg
  • the volume flow rate is 0.01-30 g/10min, preferably 0.05-20g/10min, more preferably 0.1-10g/10min, more preferably 0.2-8g/10min
  • flexural modulus is 10-1050MPa, preferably 20-1000MPa , More preferably 50-500MPa; breaking elongation ⁇ 200%, preferably breaking elongation ⁇ 300%.
  • Paragraph 8 The method according to any one of paragraphs 1-7, wherein the polypropylene graft containing anhydride groups has at least one of the following characteristics:
  • the working temperature of the polypropylene graft containing acid anhydride groups is ⁇ 90°C, preferably 90-160°C;
  • the breakdown field strength of the acid anhydride group-containing polypropylene graft at 90°C is E g ⁇ 210kV/mm, preferably 210-800kV/mm;
  • the breakdown field strength change rate ⁇ E/E obtained by the breakdown field strength E of polypropylene at 90°C is greater than 1.8%, preferably 2%-50%, more preferably 5%-35%, and still more preferably 8% ⁇ 28%;
  • the direct current volume resistivity ⁇ vg of the polypropylene graft containing acid anhydride groups at 90°C and 15kV/mm field strength and the direct current volume resistance of the copolymer polypropylene at 90°C and 15kV/mm field strength The ratio ⁇ vg/ ⁇ v of the rate ⁇ v is greater than 2, preferably 2.1-40, more preferably 2.3-20, and still more preferably 2.5-10.
  • Paragraph 9 The method according to any one of paragraphs 1-8, wherein the olefin group-containing polymerizable monomer is selected from at least one monomer having a structure represented by Formula 1,
  • R b, R c, R d are each independently selected from H, substituted or unsubstituted alkyl group;
  • R a is selected from substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy, substituted or Unsubstituted aryl group, substituted or unsubstituted ester group, substituted or unsubstituted carboxyl group, substituted or unsubstituted cycloalkyl or heterocyclic group, cyano group.
  • R b , R c , and Rd are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl, preferably R b , R c , R d are each independently selected from H, substituted or unsubstituted C 1 -C 3 alkyl;
  • R a is selected from substituted or unsubstituted C 1 -C 20 alkyl, substituted or unsubstituted C 1 -C 20 alkane Oxy group, substituted or unsubstituted C 6 -C 20 aryl group, substituted or unsubstituted C 1 -C 20 ester group, substituted or unsubstituted C 1 -C 20 carboxyl group, substituted or unsubstituted C 3 -C 20 cycloalkyl or a heterocyclic group, a cyano group, the substituted group is halogen, hydroxy, amino, C 1 -C 6 alkyl, preferably R b
  • Paragraph 11 The method according to paragraph 9, wherein R b , R c , and Rd are each independently selected from H, substituted or unsubstituted C 1 -C 6 alkyl;
  • R a is selected from the group represented by formula 2, the group represented by formula 3, the group represented by formula 4, the group represented by formula 6, the combination of the group represented by formula 6 and the group represented by formula 7, heterocyclic ring Group
  • R 4 -R 8 are each independently selected from H, halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group ,
  • the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy , C 1 -C 12 ester group, C 1 -C 12 amine group; preferably, R 4 -R 8 are each independently selected from H, halogen, hydroxyl, amino, substituted or unsubstituted
  • R 4 -R 10 are each independently selected from H, halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 amine group ,
  • the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkoxy , C 1 -C 12 ester group, C 1 -C 12 amine group; preferably, R 4 -R 10 are each independently selected from H, halogen, hydroxyl, amino, substituted or unsubstituted
  • R 4 '-R 10' are each independently selected from H, halo, hydroxy, amino, phosphoric acid group, a sulfonic acid group, a substituted or unsubstituted C 1 -C 12 alkyl, substituted or non-substituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 ester group, substituted or unsubstituted C 1 -C 12 An amino group, the substituted group is selected from halogen, hydroxyl, amino, phosphoric acid, sulfonic acid, C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 1 -C 12 alkane alkoxy, C 1 -C 12 ester group of, C 1 -C 12 group; preferably, R 4 '-R 10' are each independently selected from H, halo, hydroxy, amino, phospho
  • R m is selected from the following substituted or unsubstituted groups: C 1 -C 20 linear alkyl, C 3 -C 20 branched alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 epoxy alkyl group, C 3 -C 12 epoxy alkyl alkyl group, the substituted group is selected from at least one of halogen, amino group and hydroxyl group.
  • the alkenyl group-containing polymerizable monomer is selected from vinyl acetate, styrene, ⁇ -methylstyrene, (meth)acrylate, vinyl alkyl ether, At least one of vinylpyrrolidone, vinylpyridine, vinylimidazole and acrylonitrile;
  • the (meth)acrylate is preferably methyl (meth)acrylate, ethyl (meth)acrylate and (meth)acrylate At least one of glycidyl acrylate;
  • the alkenyl-containing polymerizable monomer is selected from vinyl acetate, styrene, and ⁇ -methylstyrene; further preferably, the alkenyl-containing polymerizable monomer is Styrene.
  • Paragraph 13 The method according to any one of paragraphs 1-12, wherein the insulating material is a cable insulating material; preferably a DC cable insulating material.
  • Paragraph 14 The method according to paragraph 13, wherein the insulating material is a cable insulating layer material.
  • the comonomer content was determined by quantitative Fourier transform infrared (FTIR) spectroscopy.
  • FTIR quantitative Fourier transform infrared
  • NMR quantitative nuclear magnetic resonance
  • Use Polymer Char's CRYST-EX instrument for testing Use trichlorobenzene solvent, heat up to 150°C for dissolution, keep constant temperature for 90 minutes, take samples for test, then cool down to 35°C, keep constant temperature for 70 minutes, take samples for test.
  • the CEAST 7026 melt index meter was used to measure at 230°C and a load of 2.16kg.
  • a differential scanning calorimeter was used to analyze the melting process and crystallization process of the material.
  • the specific operation is: under the protection of nitrogen, the 5-10 mg sample is measured from 20°C to 200°C using a three-stage temperature rise and fall measurement method, and the change in heat flow reflects the melting and crystallization process of the material, thereby calculating the melting temperature Tm.
  • Parameter M1 represents the content of structural units in the grafted state derived from maleic anhydride monomer and vinyl group-containing polymerized monomer in the polypropylene graft containing acid anhydride groups
  • parameter M2 represents the content of the acid anhydride group-containing structural units in the grafted state
  • the calculation formulas of M1, M2 and GE are as follows:
  • w 0 is the quality of the PP matrix
  • w 1 is the quality of the grafted product before extraction
  • w 2 is the quality of the grafted product after extraction
  • w 3 is the addition of maleic anhydride monomer and alkenyl-containing polymerization unit The total mass of the body.
  • the ratio of the electrical conductivity of the main insulation is equal to the electrical conductivity of the main insulation of the cable at 90°C divided by the electrical conductivity of the main insulation of the cable at 30°C.
  • the cable is continuously pressurized for 2 hours with 1.85 times the rated voltage of negative polarity. If there is no breakdown or discharge, it is passed, otherwise it is not passed.
  • the cable is heated to 90°C under the rated use temperature, and is first pressurized for 8 hours with 1.85 times the rated voltage, then cooled naturally and the voltage is removed for 16 hours, and the cycle is 12 days. Pass without breakdown.
  • Copolymer polypropylene 1* Refer to the method described in CN101679557A Copolypropylene 2* Refer to the method described in CN101679557A Copolymer polypropylene 3* Refer to the method described in CN101679557A Copolypropylene 4* Self-made according to the method described in CN101058654A Copolymer polypropylene 5* Self-made according to the method described in CN101058654A Copolypropylene 6* Self-made according to the method described in CN101058654A Polypropylene T30S Homopolymer polypropylene, Sinopec Zhenhai Refining & Chemical Dibenzoyl peroxide Bailingwei Technology Co., Ltd.
  • T30S powder breakdown field strength (90°C): 347kV/mm, DC volume resistivity (90°C, 15kV/mm): 1.18E13 ⁇ m
  • a solution of 1.3 g of dibenzoyl peroxide, 10 g of maleic anhydride and 40 g of styrene was added, stirred and mixed for 60 minutes, swelled at 40°C for 2 hours, heated to 90°C, and reacted for 4 hours. After the reaction, the temperature was purged with nitrogen to obtain the polypropylene-g-styrene/maleic anhydride material product D1.
  • Example 1 Comparing the data of Example 1 and Comparative Example 1, it can be seen that using T30S powder as the base powder, the flexural modulus of the obtained polypropylene-g-styrene/maleic anhydride material product is too high, and the mechanical properties of the material are poor. Meet the needs of insulating material processing.
  • Example 1 Comparing the data of Example 1 and Comparative Example 3, it can be seen that the method of blending the styrene/maleic anhydride copolymer actually causes the breakdown field strength and volume resistivity of the product to drop significantly, which greatly affects the electrical performance of the product.
  • a plurality of aluminum monofilament conductors are subjected to a wire binding operation, and then the wires are bundled to form a conductor core.
  • Preparation of polypropylene graft particles containing acid anhydride groups blend the following components by mass: Example C1, Example C3, Example C5 and Example C7 obtained by Example C1, Example C3, Example C5 and Example C7 containing anhydride group polypropylene graft 100 parts of branches, 0.3 parts of antioxidant 1010/168/calcium stearate (mass ratio 2:2:1). Use twin-screw extruder to granulate, rotate speed 300r/min, and granulate temperature 210-230°C.
  • Conductor shielding material PSD_WMP-00012 Zhejiang Wanma Co., Ltd.
  • the above-mentioned polypropylene graft particles containing acid anhydride groups are co-extruded outside the conductor core through an extruder Coating to form a conductor shielding layer + electrical insulating layer, or forming a conductor shielding layer + electrical insulating layer + electrical insulating shielding layer (outer shielding layer), the extrusion temperature is 160-210°C.
  • T1 copper is used to wrap the copper tape outside the electrical insulation layer (electrical insulation shielding layer) to form a metal shielding layer.
  • PVC particles (Dongguan Haichuang Electronics Co., Ltd.) of the brand St-2 are extruded outside the metal shielding layer through an extruder to form an inner sheath layer.
  • Armour preparation Use 304 stainless steel to make a steel wire armor with a nominal diameter of 1.25mm. A single layer of armor is left-wrapped on the inner sheath layer. The armor is tight to minimize the gap between adjacent steel wires. .
  • PVC particles (Dongguan Haichuang Electronics Co., Ltd.) of the brand St-2 are extruded outside the armor through an extruder to form an outer sheath layer.
  • cables with energy levels in the range of 6 to 35 kV are prepared based on the materials of Example C1, Example C3, Example C5 and Example C7, with a cross-sectional area of the cable conductor of 240-400mm 2 and a thickness of the conductor shielding layer of 1- 3mm, the thickness of the electrical insulation layer is 2-8mm, the thickness of the electrical insulation shielding layer is 0.5-1.5mm, the thickness of the armor is 0.5-1mm, the thickness of the inner sheath layer is 1-2mm, and the thickness of the outer sheath layer is not less than 1.8mm.
  • Example B The cable prepared in Example B was tested.
  • the test results of the electrical conductivity of the main insulation of the cable the electrical conductivity ratio of each cable at 90°C and 30°C is less than 100.
  • Preparation of the conductor 76 aluminum monofilaments with a diameter of 2.5 mm are pressed and twisted to obtain an aluminum conductor inner core.
  • Preparation of polypropylene graft particles containing acid anhydride groups blend the following components by mass: 100 parts of polypropylene graft containing acid anhydride groups obtained in Example 2, antioxidant 1010/168/ 0.3 parts of calcium stearate (mass ratio 2:2:1). Use twin-screw extruder to pelletize, rotating speed 300r/min, pelletizing temperature 210 ⁇ 230°C.
  • Conductor shielding material PSD_WMP-00012 Zhejiang Wanma Co., Ltd.
  • the above-mentioned polypropylene graft particles containing acid anhydride groups are co-extruded outside the conductor core through an extruder Coated to form a conductor shielding layer + electrical insulation layer, or form a conductor shielding layer + electrical insulation layer + electrical insulation shielding layer (outer shielding layer), and the extrusion temperature is 190-210°C.
  • Preparation of the metal shielding layer 25 T1 copper wires with a diameter of 0.3mm are used to wrap the copper wire outside the electrical insulating layer (electrical insulating shielding layer) to form a metal shielding layer.
  • PVC particles (Dongguan Haichuang Electronics Co., Ltd.) of the brand St-2 are extruded outside the metal shielding layer through an extruder to form an inner sheath layer.
  • Armor preparation Use 50 304 stainless steel wires with a diameter of 6.0mm to make a single-layer steel wire armor. The gap is the smallest.
  • PVC particles (Dongguan Haichuang Electronics Co., Ltd.) of the brand St-2 are extruded outside the armor through an extruder to form an outer sheath layer.
  • a cable with an energy level of 10kV is prepared based on the material of Example 2.
  • the cross-sectional area of the cable conductor is about 400mm 2
  • the average thickness of the conductor shielding layer is 1.15mm
  • the average thickness of the electrical insulation layer is 2.60mm.
  • the average thickness is 1.06mm
  • the average thickness of the metal shielding layer is 1.00mm
  • the cable insulation eccentricity is 5.1%
  • the average thickness of the armor is 6.02mm
  • the average thickness of the inner sheath layer is 2.10mm
  • the average thickness of the outer sheath layer is 2.35mm .
  • the electrical conductivity test results of the main insulation of the cables the electrical conductivity ratio of each cable at 90°C and 30°C is 44.2.
  • the cable insulation space charge injection test result the electric field distortion of the cable is 15.4%.
  • DC withstand voltage test result the cable passed without breakdown and discharge.
  • Load cycle test result the cable passed without breakdown.
  • the cable of the present invention using polypropylene grafts containing acid anhydride groups as the main insulation layer has a higher working temperature than existing cables, and can still maintain or even have a higher working temperature. Higher volume resistivity and stronger breakdown resistance.
  • the electrical insulation layer made of the polypropylene graft containing acid anhydride groups has a thinner thickness, better heat dissipation and a smaller weight than the electrical insulation layer of conventional cables.

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Abstract

一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物及其制备方法。该含有酸酐基团的聚丙烯接枝物包括衍生自共聚聚丙烯的结构单元、衍生自酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元；以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20；所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％；二甲苯可溶物含量为2～80wt％；可溶物中共聚单体含量为10～70wt％；可溶物与聚丙烯的特性粘数比为0.3～5。所述含有酸酐基团的聚丙烯接枝物可在较高工作温度下兼顾机械性能和电性能。

Description

一种含有酸酐基团的聚丙烯接枝物及其制备方法 技术领域
本发明属于聚合物领域，具体地，涉及一种含有酸酐基团的聚丙烯接枝物，一种含有酸酐基团的聚丙烯接枝物的制备方法，由该制备方法制得的含有酸酐基团的聚丙烯接枝物，以及该含有酸酐基团的聚丙烯接枝物的应用和一种电缆。
背景技术
高分子聚合物材料因具有优良的电气绝缘性能与较低的制造成本，在电气工程领域和电力行业中作为电力设备的绝缘材料而得到了大量的应用。其中以聚乙烯为代表的简单结构高分子塑料绝缘材料的应用尤为广泛，在此基础上发展起来的交联型聚乙烯、共聚型聚烯烃与橡胶材料被广泛应用在电机与变压器绝缘、线路绝缘、断路器绝缘上。乙烯基高分子绝缘材料具有较好的机械性能与热性能，优良的电气绝缘性能与较低的价格，是一种工程上发展较为成熟的绝缘材料。
随着电力行业的迅猛发展，电网系统朝着更高电压等级与更大的电能输送容量迈进，对绝缘材料的性能提出了更高的要求。在这一趋势下，传统的聚乙烯类绝缘材料已无法满足更高的长期工作温度与电场(目前在运的交联聚乙烯的绝缘材料的最高长期使用温度为70℃)。因此迫切需要开发新型的电力设备绝缘材料以适应更高工作温度和场强下的使用要求。
聚丙烯材料作为一种简单结构的高分子塑料，具有聚乙烯材料的一切优点。而且相比聚乙烯，聚丙烯具有更好的电气绝缘性能和更高的熔点，作为绝缘材料有望适应更加严苛的工作环境。然而，聚丙烯的机械性能较聚乙烯稍差，尤其在低温下较脆，不能直接作为绝缘材料使用。因此对于聚丙烯材料，有必要对其进行材料改性以实现电气性能、机械性能和热性能的综合调控，以期在更高温度和电场下保持较好的绝缘性能。
大量文献和数据表明在聚丙烯材料中掺杂纳米颗粒进行改性是提升电气绝缘性能的一种有效途径。但是在实际制备中会遇到纳米颗粒掺杂行为难以控制的困难，从而导致纳米颗粒易于团聚反而使得绝缘性能下降的问题，限制了其在实际工程中的广泛应用。
因此有必要寻找一种绝缘性能调控能力明显、可兼顾机械性能和热性能、性能稳定、制备方便，贴合工程实际应用的新型改性聚丙烯材料。
发明内容
本发明的目的在于克服上述现有技术的缺陷，提供一种新型含有酸酐基团的聚丙烯接枝物，其可在较高工作温度下兼顾机械性能和电性能，适用于高温、高运行场强工况。
本发明的第一方面提供一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物，其特征在于，该含有酸酐基团的聚丙烯接枝物包括衍生自共聚聚丙烯的结构单元、衍生自酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元；以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10；所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
本发明的第二方面提供一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物的制备方法，该制备方法包括：在惰性气体存在下，使包括共聚聚丙烯、酸酐单体和含烯基聚合单体的反应混合物进行接枝反应，得到所述含有酸酐基团的聚丙烯接枝物；其中，所述接枝反应的条件使得：以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10；所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
本发明的第三方面提供由上述制备方法制得的用于绝缘材料的含有酸酐基团的聚丙烯接枝物。
本发明的第四方面提供上述含有酸酐基团的聚丙烯接枝物作为绝缘材料的应用。
本发明的第五方面提供一种电缆，其特征在于，该电缆包括：至少一个导体以及至少一个围绕所述导体的电绝缘层；其中，所述电绝缘层的材料为上述含有酸酐基团的聚丙烯接枝物。
本发明的第六方面提供一种绝缘材料，其特征在于，该绝缘材料包含上述含有酸酐基团的聚丙烯接枝物。
附图简要描述
图1是根据本发明一种实施方案的电缆的剖面示意图。
附图标记说明
1-导体；2-导体屏蔽层；3-电绝缘层；4-电绝缘屏蔽层；5-金属屏蔽层；6-内护套层；7-铠装；8-外护套层。
发明详述
本发明的第一方面提供一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物，该含有酸酐基团的聚丙烯接枝物包括衍生自共聚聚丙烯的结构单元、衍生自酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元；以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10。
所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
优选地，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体且处于接枝态的结构单元的含量为0.05～2wt％，优选为0.2～0.7wt％。
优选地，所述酸酐选自具有至少一个烯烃不饱和度的酸酐。优选地，所述酸酐选自马来酸酐和衣康酸酐。进一步优选地，所述酸酐为马来酸酐。
优选地，本发明提供一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物，该含有酸酐基团的聚丙烯接枝物包括衍生自共聚聚丙烯的结构单元、衍生自马来酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元；以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自马来酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接 枝物中衍生自马来酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10。所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
优选地，所述含有酸酐基团的聚丙烯接枝物中衍生自马来酸酐单体且处于接枝态的结构单元的含量为0.05～2wt％，优选为0.2～0.7wt％。
本发明中，所述“结构单元”意指其为含有酸酐基团的聚丙烯接枝物的一部分，其形式并不受限。具体地，“衍生自共聚聚丙烯的结构单元”是指由共聚聚丙烯形成的产物，其既包括“基团”形式的，也包括“聚合物”形式的。“衍生自(马来)酸酐单体的结构单元”是指由(马来)酸酐形成的产物，其既包括“基团”形式的，也包括“单体”形式的，还包括“聚合物”形式的。“衍生自含烯基聚合单体的结构单元”是指由含烯基聚合单体形成的产物，其既包括“基团”形式的，也包括“单体”形式的，还包括“聚合物”形式的。所述“结构单元”可以是重复的单元，也可以是非重复的独立单元。
本发明中，“处于接枝态”的衍生自(马来)酸酐单体的结构单元是指与共聚聚丙烯形成共价连接(接枝)的衍生自(马来)酸酐单体的结构单元。“处于接枝态”的衍生自含烯基聚合单体的结构单元是指与共聚聚丙烯形成共价连接(接枝)的衍生自含烯基聚合单体的结构单元。
本发明中，共聚聚丙烯的“共聚单体”的含义为本领域技术人员公知，是指与丙烯共聚的单体。
根据本发明，优选地，所述含有酸酐基团的聚丙烯接枝物由共聚聚丙烯、(马来)酸酐单体和含烯基聚合单体经接枝反应制得，优选经固相接枝反应制得。本发明的接枝反应是自由基聚合反应，因此，所述“处于接枝态”是指反应物经过自由基聚合后，与另一反应物形成连接的状态。所述连接既包括直接的连接，也包括间接的连接。
在接枝反应过程中，酸酐单体和含烯基聚合单体可能各自或相互聚合形成一定量的未接枝的聚合物。本发明的术语“含有酸酐基团的聚丙烯接枝物”既包括由共聚聚丙烯、(马来)酸酐单体和含烯基聚合单体经接枝反应直接制得的产物(粗品)，也包括将该产物进行进一步纯化得到的接枝改性聚丙烯纯品。
根据本发明，共聚聚丙烯(本发明中的基础聚丙烯)为含有乙烯或高级α-烯烃的丙烯共聚物或者其混合物。具体地，所述共聚聚丙烯的共聚单体选自除丙烯外的C 2-C 8的α-烯 烃中的至少一种。所述除丙烯外的C 2-C 8的α-烯烃包括但不限于：乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯和1-辛烯中的至少一种，优选为乙烯和/或1-丁烯，进一步优选地，所述共聚聚丙烯由丙烯和乙烯组成。
本发明的共聚聚丙烯可以为多相丙烯共聚物。多相丙烯共聚物可以含有丙烯均聚物或丙烯无规共聚物基质组分(1)，以及分散在其中的另一丙烯共聚物组分(2)。在丙烯无规共聚物中，共聚单体无规地分布在丙烯聚合物的主链上。优选地，本发明的共聚聚丙烯为通过现有工艺在反应器内原位(in situ)制备的多相丙烯共聚物。
根据一种优选的实施方式，所述多相丙烯共聚物含有丙烯均聚物基质或无规共聚物基质(1)，以及分散在其中的含有一种或多种乙烯或高级α-烯烃共聚单体的丙烯共聚物组分(2)。所述多相丙烯共聚物可以为海岛结构或双连续结构。
在本领域中已知有两种多相丙烯共聚物，含有丙烯无规共聚物作为基质相的多相丙烯共聚物或含有丙烯均聚物作为基质相的多相丙烯共聚物。无规共聚物基质(1)是共聚用单体部分无规地分布在聚合物链上形成的共聚物，换言之，由随机长度(包含单分子)的两种单体单元交替顺序组成。优选基质(1)中的共聚单体选自乙烯或丁烯。特别优选基质(1)中的共聚单体为乙烯。
优选地，分散在多相丙烯共聚物的均聚物或共聚物基质(1)中的丙烯共聚物(2)基本上是无定形的。术语“基本上是无定形的”在此是指丙烯共聚物(2)比均聚物或共聚物基质(1)具有更低的结晶度。
根据本发明，除上述组成特征以外，所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
根据本发明，优选地，所述共聚聚丙烯还具有以下特征中的至少一种：在230℃，2.16kg载荷下的熔体流动速率为0.01～60g/10min，优选为0.05～35g/10min，进一步优选为0.5～15g/10min。熔融温度Tm为100℃以上，优选为110～180℃，进一步优选为110～170℃，进一步优选为120～170℃，进一步优选为120～166℃。重均分子量优选为20×10 4～60×10 4g/mol。具有高Tm的基础聚丙烯在低温和高温下均具有令人满意的冲击强度和柔韧性，此外，在使用具有高Tm基础聚丙烯时，本发明的接枝改性聚丙烯具有能承受较高工作温度的优点。本发明所述共聚聚丙烯优选为多孔颗粒状或粉状树脂。
根据本发明，优选地，所述共聚聚丙烯还具有以下特征中的至少一种：弯曲模量为 10～1000MPa，优选为50～600MPa；断裂伸长率≥200％，优选断裂伸长率≥300％。优选地，所述共聚聚丙烯的拉伸强度大于5MPa，优选为10～40MPa。
本发明所述共聚聚丙烯可以包括但不限于中国石化武汉石化的NS06，中国石化齐鲁石化的SPF179等任意可商业获得的适于本发明的聚丙烯粉料，也可以通过中国专利CN1081683、CN1108315、CN1228096、CN1281380、CN1132865C和CN102020733A等中记载的聚合工艺生产得到。常用的聚合工艺包括Basell公司的Spheripol工艺，三井油化公司的Hypol工艺，Borealis公司的Borstar PP工艺，DOW化学公司的Unipol工艺，INEOS(原BP-Amoco)公司的Innovene气相法工艺等。
根据本发明，优选地，所述含有酸酐基团的聚丙烯接枝物具有以下特征中的至少一种：在230℃，2.16kg载荷下的熔体流动速率为0.01～30g/10min，优选为0.05～20g/10min，进一步优选为0.1～10g/10min，更优选为0.2～8g/10min；弯曲模量为10～1050MPa，优选为20～1000MPa，更优选为50～500MPa；断裂伸长率≥200％，优选断裂伸长率≥300％。优选地，所述含有酸酐基团的聚丙烯接枝物的拉伸强度大于5MPa，优选为10～40MPa。
根据本发明，优选地，所述含有酸酐基团的聚丙烯接枝物具有以下特征中的至少一种：
-所述含有酸酐基团的聚丙烯接枝物的工作温度≥90℃，优选为90～160℃；
-所述含有酸酐基团的聚丙烯接枝物在90℃下的击穿场强E g≥210kV/mm，优选为210～800kV/mm；
-所述含有酸酐基团的聚丙烯接枝物在90℃下的击穿场强E g与所述共聚聚丙烯在90℃下的击穿场强E的差值△E除以所述共聚聚丙烯在90℃下的击穿场强E所得的击穿场强变化率△E/E大于1.8％，优选为2％～50％，更优选为5％～35％，进一步优选为8％～28％；
-所述含有酸酐基团的聚丙烯接枝物在90℃、15kV/mm场强下的直流体积电阻率ρ vg≥1.5×10 13Ω·m，优选为1.5×10 13Ω·m～1.0×10 20Ω·m；
-所述含有酸酐基团的聚丙烯接枝物在90℃、15kV/mm场强下的直流体积电阻率ρ vg与所述共聚聚丙烯在90℃、15kV/mm场强下的直流体积电阻率ρ v的比值ρ vg/ρ v大于2，优选为2.1～40，更优选为2.3～20，进一步优选为2.5～10。
优选地，所述接枝改性聚丙烯材料在90℃、50Hz下的介电常数大于2.0，优选2.1～2.5。
本发明所述的含烯基聚合单体优选选自具有式I所示结构的单体中的至少一种，
Figure PCTCN2020127465-appb-000001
式1中，R b、R c、R d各自独立地选自H、取代或未取代的烷基；R a选自取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的酯基、取代或 未取代的羧基、取代或未取代的环烷基或杂环基、氰基。
优选地，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 6烷基，优选地，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 3烷基；R a选自取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20芳基、取代或未取代的C 1-C 20酯基、取代或未取代的C 1-C 20羧基、取代或未取代的C 3-C 20环烷基或杂环基、氰基，所述取代的基团为卤素、羟基、氨基、C 1-C 6烷基、C 3-C 6环烷基；优选地，R a选自取代或未取代的C 1-C 12烷基、取代或未取代的C 1-C 18烷氧基、取代或未取代的C 6-C 12芳基、取代或未取代的C 1-C 12酯基、取代或未取代的C 1-C 12羧基、取代或未取代的C 3-C 12环烷基或杂环基、氰基，所述取代的基团为卤素、C 1-C 6烷基、C 3-C 6环烷基；更优选地，R a选自取代或未取代的C 1-C 6烷基、取代或未取代的C 1-C 12烷氧基、取代或未取代的C 6-C 8芳基、取代或未取代的C 1-C 6酯基、取代或未取代的C 1-C 6羧基、取代或未取代的C 3-C 6环烷基或杂环基、氰基。优选地，所述杂环基选自咪唑基、吡唑基、咔唑基、吡咯烷酮基、吡啶基、哌啶基、己内酰胺基、吡嗪基、噻唑基、嘌呤基、吗啉基、噁唑啉基。
更优选地，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 6烷基；
R a选自式2所示基团、式3所示基团、式4所示基团、式6所示基团、式6所示基团和式7所示基团的组合、杂环基团；
Figure PCTCN2020127465-appb-000002
式2中，R 4-R 8各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 8各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基；
Figure PCTCN2020127465-appb-000003
式3中，R 4-R 10各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 10各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
Figure PCTCN2020127465-appb-000004
式4中，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
Figure PCTCN2020127465-appb-000005
式6中，R m选自取代或未取代的以下基团：C 1-C 20直链烷基、C 3-C 20支链烷基、C 3-C 12环烷基、C 3-C 12环氧烷基、C 3-C 12环氧烷基烷基，所述取代的基团选自卤素、氨基和羟基中的至少一种。
进一步优选地，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸酯、乙烯基烷基醚、乙烯基吡咯烷酮、乙烯基吡啶、乙烯基咪唑和丙烯腈中的至少一种；所述(甲基)丙烯酸酯优选为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯和(甲基)丙烯酸缩水甘油酯中的至少一种。优选地，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯。进一步优选地，所述含烯基聚合单体为苯乙烯。
本发明的所述含有酸酐基团的聚丙烯接枝物可通过包括以下步骤的方法制备得到：在惰性气体存在下，使包括共聚聚丙烯、(马来)酸酐单体和含烯基聚合单体的反应混合物进行接枝反应(优选固相接枝反应)，得到所述含有酸酐基团的聚丙烯接枝物。
本发明的第二方面提供一种包含含有酸酐基团的聚丙烯接枝物的绝缘材料的制备方法，该制备方法包括：在惰性气体存在下，使包括共聚聚丙烯、酸酐单体和含烯基聚合单体的反应混合物进行接枝反应，得到所述含有酸酐基团的聚丙烯接枝物；
其中，所述接枝反应的条件使得：以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10。
所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
优选地，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体且处于接枝态的结构单元的含量为0.05～2wt％，优选为0.2～0.7wt％。
优选地，所述酸酐选自具有至少一个烯烃不饱和度的酸酐。优选地，所述酸酐选自马来酸酐和衣康酸酐。进一步优选地，所述酸酐为马来酸酐。
优选地，本发明提供一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物的制备方法，该制备方法包括：在惰性气体存在下，使包括共聚聚丙烯、马来酸酐单体和含烯基聚合单体的反应混合物进行接枝反应，得到所述含有酸酐基团的聚丙烯接枝物；
其中，所述接枝反应的条件使得：以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自马来酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自马来酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10。
所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
优选地，所述含有酸酐基团的聚丙烯接枝物中衍生自马来酸酐单体且处于接枝态的结 构单元的含量为0.05～2wt％，优选为0.2～0.7wt％。
本发明的接枝反应可参考本领域常规的各种方法进行，优选为固相接枝反应。如，在接枝用(马来)酸酐、含烯基聚合单体的存在下在共聚聚丙烯上形成活性接枝点，或者先在共聚聚丙烯上形成活性接枝点接着用接枝用单体进行处理。接枝点可通过自由基引发剂处理形成，或进行高能电离辐射或微波处理来形成。在聚合物中作为化学或辐射处理的结果而产生的自由基在聚合物上形成接枝点并在这些点上引发单体聚合。
优选地，通过自由基引发剂引发接枝点并进一步进行接枝反应。在这种情况下，所述反应混合物还包括自由基引发剂；进一步优选地，所述自由基引发剂选自过氧化物类自由基引发剂和/或偶氮类自由基引发剂。
其中，所述过氧化物类自由基引发剂优选选自过氧化二苯甲酰、过氧化二异丙苯、二叔丁基过氧化物、过氧化月桂酰、过氧化十二酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙基酯、过氧化(2-乙基己酸)叔丁酯和过氧化二碳酸二环己基酯中的至少一种；所述偶氮类自由基引发剂优选为偶氮二异丁腈和/或偶氮二异庚腈。
更优选地，通过过氧化物类自由基引发剂引发接枝点并进一步进行接枝反应。
此外，本发明的接枝反应也可以通过CN106543369A、CN104499281A、CN102108112A、CN109251270A、CN1884326A和CN101492517B中描述的方法进行。
在满足上述产品特征的前提下，本发明对接枝反应中各组分的用量没有特别的限定，具体地，所述自由基引发剂的质量与所述(马来)酸酐单体和所述含烯基聚合单体的总质量的比为0.1～10:100，优选为0.5～5:100。所述(马来)酸酐单体和所述含烯基聚合单体的总质量与所述共聚聚丙烯的质量比为0.1～8:100，优选为0.3～5:100。所述(马来)酸酐单体的质量用量可以为所述含烯基聚合单体的质量用量的5～100wt％，优选为10～100wt％。
本发明对接枝反应的工艺条件也没有特别的限定，具体地，所述接枝反应的温度可以为30～130℃，优选为60～120℃；时间可以为0.5～10h，优选为1～5h。
本发明中，所述“反应混合物”包括加入到接枝反应体系中的所有物料，物料可以一次性加入，也可以在反应的不同阶段加入。
本发明的反应混合物中还可以包括分散剂，所述分散剂优选为水或氯化钠的水溶液。所述分散剂的质量用量优选为共聚聚丙烯质量的50～300％。
本发明的反应混合物中还可以包括界面剂，所述界面剂为对聚烯烃具有溶胀作用的有机溶剂，优选为对共聚聚丙烯具有溶胀作用的下述有机溶剂中的至少一种：醚类溶剂、酮类溶剂、芳烃类溶剂、烷烃类溶剂；更优选为下述有机溶剂中的至少一种：氯代苯、多氯代苯、C 6以上的烷烃或环烷烃、苯、C 1-C 4烷基取代苯、C 2-C 6脂肪醚、C 3-C 6脂肪酮、十 氢萘；进一步优选为下述有机溶剂中的至少一种：苯、甲苯、二甲苯、氯苯、四氢呋喃、乙醚、丙酮、己烷、环己烷、十氢萘、庚烷。所述界面剂的质量含量优选为共聚聚丙烯质量的1～30％，进一步优选为10～25％。
本发明的反应混合物中还可以包括有机溶剂，作为溶解固体自由基引发剂的溶剂，所述有机溶剂优选包括C 2-C 5醇类、C 2-C 4醚类和C 3-C 5酮类中的至少一种，更优选包括C 2-C 4醇类、C 2-C 3醚类和C 3-C 5酮类中的至少一种，最优选为乙醇、乙醚和丙酮中的至少一种。所述有机溶剂的质量含量优选为共聚聚丙烯质量的1～35％。
本发明的含有酸酐基团的聚丙烯接枝物的制备方法中，对于含烯基聚合单体和共聚聚丙烯的限定与前述相同，在此不再赘述。
根据本发明，所述含有酸酐基团的聚丙烯接枝物的制备方法可选自以下方式之一：
方式一，所述制备方法包括以下步骤：
a.将共聚聚丙烯置于密闭反应器中，进行惰性气体置换；
b.将自由基引发剂与酸酐单体和含烯基聚合单体加入到所述密闭反应器中，搅拌混合；
c.任选地加入界面剂，并任选地使反应体系进行溶胀；
d.任选地加入分散剂，使反应体系升温至接枝反应温度，进行接枝反应；
e.反应结束后，任选地进行过滤(使用水相分散剂情况下)、干燥，得到所述含有酸酐基团的聚丙烯接枝物。
更具体地，所述制备方法包括以下步骤：
a.将共聚聚丙烯置于密闭反应器中，进行惰性气体置换；
b.将自由基引发剂溶解于酸酐单体和含烯基聚合单体中，配制成溶液，加入到装有共聚聚丙烯的密闭反应器中，搅拌混合；
c.加入界面剂0～30份，并任选地使反应体系在20～60℃下溶胀0～24小时；
d.加入分散剂0～300份，体系升温至接枝聚合温度30～130℃，反应0.5～10小时；
e.反应结束后，任选地进行过滤(使用水相分散剂情况下)、干燥，得到所述含有酸酐基团的聚丙烯接枝物。
方式二，所述制备方法包括以下步骤：
a.将共聚聚丙烯置于密闭反应器中，进行惰性气体置换；
b.将有机溶剂和自由基引发剂混合，加入到所述密闭反应器中；
c.除去所述有机溶剂；
d.加入酸酐单体和含烯基聚合单体，任选地加入界面剂，并任选地使反应体系进行溶胀；
e.任选地加入分散剂，使反应体系升温至接枝反应温度，进行接枝反应；
f.反应结束后，任选地进行过滤(使用水相分散剂情况下)、干燥，得到所述含有酸酐基团的聚丙烯接枝物。
更具体地，所述制备方法包括以下步骤：
a.将共聚聚丙烯置于密闭反应器中，进行惰性气体置换；
b.将有机溶剂和自由基引发剂混合，配制成溶液加入到装有共聚聚丙烯的密闭反应器中；
c.惰性气体吹扫或通过真空除去所述有机溶剂；
d.加入酸酐单体和含烯基聚合单体，加入界面剂0～30份，并任选地使反应体系在20～60℃下溶胀0～24小时；
e.加入分散剂0～300份，体系升温至接枝聚合温度30～130℃，反应0.5～10小时；
f.反应结束后，任选地进行过滤(使用水相分散剂情况下)、干燥，得到所述含有酸酐基团的聚丙烯接枝物。
根据本发明的方法，若反应结束后体系中存在挥发性组分，则本发明的方法优选包括脱挥发份的步骤，所述脱挥发份可以通过任何常规方法进行，包括在接枝工艺结束时真空提取或使用汽提剂。合适的汽提剂包括但不限于惰性气体。
如上所述，本发明的“含有酸酐基团的聚丙烯接枝物”既包括由共聚聚丙烯和酸酐单体、含烯基聚合单体经接枝反应直接制得的产物(粗品)，也包括将该产物进行进一步纯化得到的接枝改性聚丙烯纯品，因此，本发明的制备方法中，可任选的包括对粗品进行纯化的步骤。所述纯化可采用本领域常规的各种方法，如抽提法。
本发明对所述接枝反应的接枝效率没有特别的限定，但是较高的接枝效率更有利于通过一步接枝反应即得到所需性能的含有酸酐基团的聚丙烯接枝物。因此，优选控制所述接枝反应的接枝效率为20～100％，进一步优选为25～80％。所述接枝效率的概念为本领域技术人员公知，是指接枝上的酸酐单体和含烯基聚合单体的总量/反应投料的酸酐单体和含烯基聚合单体的总量。
本发明的所述惰性气体可以为本领域常用的各种惰性气体，包括但不限于氮气、氩气。
本发明的第三方面提供由上述制备方法制得的用于绝缘材料的含有酸酐基团的聚丙烯接枝物。
本发明的第四方面提供上述含有酸酐基团的聚丙烯接枝物作为绝缘材料的应用。
进一步优选地，所述绝缘材料为电缆绝缘材料；优选为直流电缆绝缘材料。
更优选地，所述绝缘材料为电缆绝缘层材料。
本发明所用含有酸酐基团的聚丙烯接枝物可直接作为绝缘材料的基础材料，无需共混其他聚合物。
本发明的第五方面提供一种电缆，该电缆包括：
至少一个导体以及至少一个围绕所述导体的电绝缘层；
其中，所述电绝缘层的材料为所述的含有酸酐基团的聚丙烯接枝物。
本发明的核心在于采用一种新材料作为电缆的电绝缘层，因此，本发明对于电缆的形式和具体结构没有特别限定，可采用本领域常规的各种电缆形式(直流或交流、单芯或多芯)及所对应各种结构。本发明的电缆中，除电绝缘层采用新型接枝改性聚丙烯材料外，其他层结构、其他层材质均可以为本领域常规选择。
本发明的所述电缆可以为直流电缆或交流电缆；优选为直流电缆；更优选地，所述电缆为中高压直流电缆或超高压直流电缆。本发明中，低压(LV)表示低于1kV的电压，中压(MV)表示在1kV至40kV范围内的电压，高压(HV)表示高于40kV、优选高于50kV的电压，超高压(EHV)表示至少230kV的电压。
根据本发明一种优选实施方式，所述电缆具有至少一个缆芯，每个所述缆芯由内至外依次包括：导体、任选的导体屏蔽层、电绝缘层、任选的电绝缘屏蔽层、任选的金属屏蔽层。其中，所述导体屏蔽层、电绝缘屏蔽层和金属屏蔽层均可根据需要设置，一般地，在6kV以上的电缆中使用。
除上述结构外，所述电缆还可以包括铠装和/或护套层。
本发明的所述电缆可为单芯电缆或多芯电缆，对于多芯电缆，所述电缆还可以包括填充层和/或包带层。所述填充层由填充于各线芯之间的填充材料形成。所述包带层包覆于所有线芯的外侧，保证线芯及填充层呈圆形，防止线芯被铠装划伤，并起到阻燃作用。
本发明的电缆中，所述导体是通常由金属材料，优选铝、铜或其它合金制成的导电元件，包括一种或多种金属导线。所述导体的直流电阻和单丝根数需符合GB/T 3956的要求。优选的导体采用紧压绞合圆形结构，标称截面积小于等于800mm 2；或采用分割导体结构，标称截面积大于等于1000mm 2，导体根数不少于170根。
本发明的电缆中，所述导体屏蔽层可以是由聚丙烯、聚烯烃弹性体和炭黑等材料制成的覆盖层，23℃下的体积电阻率＜1.0Ω·m，90℃下的体积电阻率＜3.5Ω·m，在230℃，2.16kg载荷下的熔体流动速率通常为0.01～30g/10min，优选为0.05～20g/10min，进一步 优选为0.1～10g/10min，更优选为0.2～8g/10min；拉伸强度≥12.5MPa；断裂伸长率≥150％。所述导体屏蔽层最薄点的厚度不小于0.5mm，平均厚度不低于1.0mm。
本发明的电缆中，所述电绝缘层的材料为至少一种含有酸酐基团的聚丙烯接枝物是指构成电绝缘层的基材为所述含有酸酐基团的聚丙烯接枝物，除含有酸酐基团的聚丙烯接枝物外还可包含另外的组分，如聚合物组分或添加剂，优选包含添加剂，如抗氧化剂、稳定剂、加工助剂、阻燃剂、水树阻滞添加剂、酸或离子清除剂、无机填料、电压稳定剂和抗铜剂中的任一种或多种。添加剂的种类和使用量为常规且为本领域技术人员已知的。
本发明的电绝缘层的制备方法也可以采用电缆制备领域的常规方法，例如，将含有酸酐基团的聚丙烯接枝物与任选的各种添加剂混合，用双螺杆挤出机造粒，再将所得粒料通过挤出机挤出，制得电绝缘层。通常地，可将导体屏蔽料与含有酸酐基团的聚丙烯接枝物粒料共挤出，形成导体屏蔽层+电绝缘层的结构，或形成导体屏蔽层+电绝缘层+电绝缘屏蔽层的结构。具体操作均可采用本领域常规方法和工艺条件。
由于采用所述含有酸酐基团的聚丙烯接枝物，本发明所述电绝缘层的厚度可以仅为GB/T 12706中XLPE绝缘层标称厚度值的50％～95％，优选地，电绝缘层的厚度为GB/T 12706中XLPE绝缘层标称厚度值的70％～90％；偏心度不大于10％。
本发明的电缆中，所述电绝缘屏蔽层可以为由聚丙烯、聚烯烃弹性体和炭黑等材料制成的覆盖层，23℃下的体积电阻率＜1.0Ω·m，90℃下的体积电阻率＜3.5Ω·m。在230℃，2.16kg载荷下的熔体流动速率为0.01～30g/10min，优选为0.05～20g/10min，进一步优选为0.1～10g/10min，更优选为0.2～8g/10min；拉伸强度≥12.5MPa；断裂伸长率≥150％。所述电绝缘屏蔽层的最薄点厚度不小于0.5mm，平均厚度不低于1.0mm。
本发明的电缆中，所述金属屏蔽层可以为铜带屏蔽层或铜丝屏蔽层。
本发明的电缆中，所述填充层可以为高分子材料，如PE/PP/PVC或回收的橡胶材料等。
本发明的电缆中，所述包带层/铠装层通常是由铜丝金属笼、铅或铝制金属套等制成的、包裹电绝缘屏蔽层外表面的金属覆盖层，其室温下直流体积电阻率≤1000Ω·m。
本发明的电缆中，所述护套层的材质可以为聚氯乙烯、聚乙烯或低烟无卤材料中的任一种。所述护套层既包括内护套层，也包括外护套层。
以上各层结构均可采用本领域的常规方法制得。例如，所述导体屏蔽层、电绝缘层、护套层可通过挤出机挤出包覆形成，所述金属屏蔽层和铠装可通过绕包形成。
本发明的所述电缆可通过本领域常规的各种制备工艺制得，本发明对此没有特别限定。
根据本发明一种具体实施方式，所述电缆的制备方法如下：
导体的制备：将多条单丝导体(如铝制)进行紧压绞合操作，得到导体内芯；或进行 束丝操作，然后将束丝后的各单丝导体进行绞合操作，得到导体内芯。
改性聚丙烯颗粒的制备：将含有酸酐基团的聚丙烯接枝物与任选的添加剂混合，用双螺杆挤出机造粒。
导体屏蔽层和电绝缘层的制备：导体屏蔽料和上述改性聚丙烯颗粒，在导体内芯外通过挤出机共挤出包覆形成导体屏蔽层+电绝缘层，或形成导体屏蔽层+电绝缘层+电绝缘屏蔽层(外屏蔽层)。
金属屏蔽层的制备：在电绝缘层(电绝缘屏蔽层)外进行铜带或铜丝绕包，形成金属屏蔽层。
内护套层的制备：将护套层粒料在金属屏蔽层外通过挤出机挤出形成内护套层。
铠装的制备：使用镀锌钢/不锈钢/铝合金制成钢丝或钢带铠装，由单层铠装左向或双层铠装内层右向、外层左向绕包在内护套层上，钢丝或钢带铠装应紧密，使相邻钢丝/钢带间的间隙为最小。
外护套层的制备：将护套层粒料在铠装外通过挤出机挤出形成外护套层。最终制得所述电缆。
本发明的含有酸酐基团的聚丙烯接枝物可在较高工作温度下兼顾机械性能和电性能，适用于高温、高运行场强工况。此外，与加入小分子添加剂的材料相比，本发明的含有酸酐基团的聚丙烯接枝物避免了小分子迁移导致的性能下降，因此具有更好的稳定性。
相比现有电缆，本发明的电缆在更高工作温度下依然能够保持甚至具有更高的体积电阻率和更强的耐击穿性能，同时其机械性能亦能满足电缆使用要求。在保证相同电压等级和绝缘水平条件下，所述含有酸酐基团的聚丙烯接枝物所制的电绝缘层相比常规电缆的电绝缘层具有厚度更薄、散热更好和重量更小等优点。因此，该电缆具有更宽的应用范围。
本发明的第六方面提供一种绝缘材料，其特征在于，该绝缘材料包含至少一种上述含有酸酐基团的聚丙烯接枝物。
优选地，以所述绝缘材料的重量为基准，所述至少一种含有酸酐基团的聚丙烯接枝物的含量为20-100wt％，优选为40-100wt％，更优选为60-100wt％，进一步优选为80-100wt％，更进一步优选为90-100wt％。
优选地，所述绝缘材料还包含添加剂，例如抗氧化剂、稳定剂、加工助剂、阻燃剂、水树阻滞添加剂、酸或离子清除剂、无机填料、电压稳定剂和抗铜剂中的一种或多种。添加剂的种类和用量是常规的并且是本领域技术人员已知的。
另外地，本发明还包括以下段落中记载的实施方案。
段落1、一种使用接枝改性聚丙烯材料制备绝缘材料的方法，其特征在于，该含有酸酐基团的聚丙烯接枝物包括衍生自共聚聚丙烯的结构单元、衍生自酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元；以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10；
所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
段落2、根据段落1所述的方法，其中，所述共聚聚丙烯具有以下特征中的至少一种：在230℃，2.16kg载荷下的熔体流动速率为0.01～60g/10min，优选为0.05～35g/10min，进一步优选为0.5～15g/10min；熔融温度Tm为100℃以上，优选为110～180℃，进一步优选为110～170℃，进一步优选为120～170℃，进一步优选为120～166℃；重均分子量为20×10 4～60×10 4g/mol。
段落3、根据段落1或2所述的方法，其中，所述共聚聚丙烯的共聚单体选自除丙烯外的C 2-C 8的α-烯烃中的至少一种；优选地，所述共聚聚丙烯的共聚单体选自乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯和1-辛烯中的至少一种；进一步优选地，所述共聚聚丙烯的共聚单体为乙烯和/或1-丁烯；进一步优选地，所述共聚聚丙烯由丙烯和乙烯组成。
段落4、根据段落1-3中任意一项所述的方法，其中，所述含有酸酐基团的聚丙烯接枝物由共聚聚丙烯、酸酐单体和含烯基聚合单体经固相接枝反应制得。
段落5、根据段落1-4中任意一项所述的方法，其中，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体且处于接枝态的结构单元的含量为0.05～2wt％，优选为0.2～0.7wt％。
段落6、根据段落1-6中任意一项所述的方法，其中，所述酸酐选自具有至少一个烯烃不饱和度的酸酐；优选地，所述酸酐选自马来酸酐和衣康酸酐；进一步优选地，所述酸酐为马来酸酐。
段落7、根据段落1-7中任意一项所述的方法，其中，所述含有酸酐基团的聚丙烯接枝物具有以下特征中的至少一种：在230℃，2.16kg载荷下的熔体流动速率为0.01～30 g/10min，优选为0.05～20g/10min，进一步优选为0.1～10g/10min，更优选为0.2～8g/10min；弯曲模量为10～1050MPa，优选为20～1000MPa，更优选为50～500MPa；断裂伸长率≥200％，优选断裂伸长率≥300％。
段落8、根据段落1-7中任意一项所述的方法，其中，所述含有酸酐基团的聚丙烯接枝物具有以下特征中的至少一种：
-所述含有酸酐基团的聚丙烯接枝物的工作温度≥90℃，优选为90～160℃；
-所述含有酸酐基团的聚丙烯接枝物在90℃下的击穿场强E g≥210kV/mm，优选为210～800kV/mm；
-所述含有酸酐基团的聚丙烯接枝物在90℃下的击穿场强E g与所述共聚聚丙烯在90℃下的击穿场强E的差值△E除以所述共聚聚丙烯在90℃下的击穿场强E所得的击穿场强变化率△E/E大于1.8％，优选为2％～50％，更优选为5％～35％，进一步优选为8％～28％；
-所述含有酸酐基团的聚丙烯接枝物在90℃、15kV/mm场强下的直流体积电阻率ρ vg≥1.5×10 13Ω·m，优选为1.5×10 13Ω·m～1.0×10 20Ω·m；
-所述含有酸酐基团的聚丙烯接枝物在90℃、15kV/mm场强下的直流体积电阻率ρ vg与所述共聚聚丙烯在90℃、15kV/mm场强下的直流体积电阻率ρ v的比值ρ vg/ρ v大于2，优选为2.1～40，更优选为2.3～20，进一步优选为2.5～10。
段落9、根据段落1-8中任意一项所述的方法，其中，所述含烯烃基聚合单体选自具有式1所示结构的单体中的至少一种，
Figure PCTCN2020127465-appb-000006
式1中，R b、R c、R d各自独立地选自H、取代或未取代的烷基；R a选自取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的酯基、取代或未取代的羧基、取代或未取代的环烷基或杂环基、氰基。
段落10、根据段落9所述的方法，其中，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 6烷基，优选地，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 3烷基；R a选自取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20芳基、取代或未取代的C 1-C 20酯基、取代或未取代的C 1-C 20羧基、取代或未取代的C 3-C 20环烷基或杂环基、氰基，所述取代的基团为卤素、羟基、氨基、C 1-C 6烷基、C 3-C 6环烷基；优选地，R a选自取代或未取代的C 1-C 12烷基、取代或未取代的C 1-C 18烷氧基、取代或未取代的C 6-C 12芳基、取代或未取代的C 1-C 12酯基、取代或未取代的C 1-C 12羧基、取代或未取代的C 3-C 12环烷基或杂环基、氰基，所述取代的基团为卤素、C 1-C 6烷基、C 3-C 6环烷基； 更优选地，R a选自取代或未取代的C 1-C 6烷基、取代或未取代的C 1-C 12烷氧基、取代或未取代的C 6-C 8芳基、取代或未取代的C 1-C 6酯基、取代或未取代的C 1-C 6羧基、取代或未取代的C 3-C 6环烷基或杂环基、氰基；优选地，所述杂环基选自咪唑基、吡唑基、咔唑基、吡咯烷酮基、吡啶基、哌啶基、己内酰胺基、吡嗪基、噻唑基、嘌呤基、吗啉基、噁唑啉基。
段落11、根据段落9所述的方法，其中，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 6烷基；
R a选自式2所示基团、式3所示基团、式4所示基团、式6所示基团、式6所示基团和式7所示基团的组合、杂环基团；
Figure PCTCN2020127465-appb-000007
式2中，R 4-R 8各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 8各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基；
Figure PCTCN2020127465-appb-000008
式3中，R 4-R 10各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 10各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
Figure PCTCN2020127465-appb-000009
式4中，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
Figure PCTCN2020127465-appb-000010
式6中，R m选自取代或未取代的以下基团：C 1-C 20直链烷基、C 3-C 20支链烷基、C 3-C 12环烷基、C 3-C 12环氧烷基、C 3-C 12环氧烷基烷基，所述取代的基团选自卤素、氨基和羟基中的至少一种。
段落12、根据段落9所述的方法，其中，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸酯、乙烯基烷基醚、乙烯基吡咯烷酮、乙烯基吡啶、乙烯基咪唑和丙烯腈中的至少一种；所述(甲基)丙烯酸酯优选为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯和(甲基)丙烯酸缩水甘油酯中的至少一种；优选地，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯；进一步优选地，所述含烯基聚合单体为苯乙烯。
段落13、根据段落1-12中任意一项所述的方法，其中，所述绝缘材料为电缆绝缘材料；优选为直流电缆绝缘材料。
段落14、根据段落13所述的方法，其中，所述绝缘材料为电缆绝缘层材料。
本发明的其它特征和优点将在随后具体实施方式部分予以详细说明。
具体实施方式
以下对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。
以下实施例和对比例中：
1、共聚聚丙烯中共聚单体含量的测定：
通过定量傅里叶变换红外(FTIR)光谱测定共聚单体的含量。通过定量核磁共振(NMR)光谱对确定的共聚单体含量的相关性进行校准。所述基于定量 13C-NMR光谱所得结果的校准方法按照本领域的常规方法进行。
2、共聚聚丙烯中二甲苯可溶物含量、可溶物中共聚单体含量及可溶物/共聚聚丙烯的特性粘数比的测定：
用Polymer Char公司的CRYST-EX仪器进行测试。使用三氯苯溶剂，升温至150℃进行溶解，恒温90min，取样测试，再降温至35℃，恒温70min，取样测试。
3、共聚聚丙烯重均分子量的测定：
用高温GPC测定，采用Polymer Laboratory公司的PL-GPC 220型凝胶渗透色谱，试样用1,2,4-三氯苯溶解，浓度为1.0mg/ml。测试温度150℃，溶液流速为1.0ml/min。以聚苯乙烯的分子量作为内参来制定标准曲线，根据流出时间计算样品的分子量及分子量分布。
4、熔体流动速率MFR的测定：
按GB/T 3682-2018中规定的方法，用CEAST公司7026型熔融指数仪，在230℃，2.16kg载荷下测定。
5、熔融温度Tm的测定：
采用差示扫描量热仪对材料的熔融过程和结晶过程进行分析。具体操作为：在氮气保护下，将5～10mg样品从20℃至200℃采用三段式升降温测量方法进行测量，以热流量的变化反映材料的熔融和结晶过程，从而计算熔融温度Tm。
6、接枝效率GE、参数M1、参数M2的测定：
将2～4g接枝产物放入索氏提取器中，用乙酸乙酯抽提24小时，除去未反应的单体及其均聚物，得到纯的接枝产物，烘干称重，计算参数M1、M2及接枝效率GE。
根据文献(张广平，螺带反应器中聚丙烯固相接枝马来酸酐，中国塑料，2002年2月第16卷第2期，69-71)中所描述的方法测试并计算马来酸酐的质量含量％G MAH。
参数M1代表所述含有酸酐基团的聚丙烯接枝物中衍生自马来酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量；参数M2代表所述含有酸酐基团的聚丙烯接枝物中衍生自马来酸酐单体且处于接枝态的结构单元的含量。本发明中，M1、M2和GE的计算公式如下：
Figure PCTCN2020127465-appb-000011
Figure PCTCN2020127465-appb-000012
Figure PCTCN2020127465-appb-000013
以上公式中，w 0是PP基体的质量；w 1是接枝产物抽提前的质量；w 2是接枝产物抽提后的质量；w 3是加入马来酸酐单体和含烯基聚合单体的总质量。
7、直流体积电阻率的测定：
按照GB/T 1410-2006中规定的方法进行测定。
8、击穿场强的测定：
按照GB/T 1408-2006中规定的方法进行测定。
9、拉伸强度的测定：
按照GB/T 1040.2-2006中规定的方法进行测定。
10、弯曲模量的测定：
按照GB/T 9341-2008中规定的方法进行测定。
11、断裂伸长率的测定：
按照GB/T 1040-2006中规定的方法进行测定。
12、介电常数与介电损耗因数的测定：
按照GB/T 1409-2006中规定的方法进行测定。
13、电缆的主绝缘电导率(电阻率)比值的测定：
按照TICW 7.1-2012附录A中规定的方法进行试验。主绝缘电导率比值等于90℃下电缆的主绝缘电导率除以30℃下电缆的主绝缘电导率。
14、电场畸变率的测定：
按照TICW 7.1-2012附录B中规定的方法进行电缆绝缘空间电荷注入试验。
15、直流耐压测试：
常温下采用1.85倍负极性额定电压持续对电缆加压2小时。无击穿和放电现象即为通过，否则不通过。
16、负荷循环测试：
电缆在额定使用温度下加热到90℃，并加1.85倍额定电压先加压8h，然后自然冷却并撤去电压16h，循环12天。无击穿现象发生即为通过。
实施例中所用的原料描述于下表A中。
表A
名称 描述
共聚聚丙烯1* 参考CN101679557A所述方法自制
共聚聚丙烯2* 参考CN101679557A所述方法自制
共聚聚丙烯3* 参考CN101679557A所述方法自制
共聚聚丙烯4* 参考CN101058654A所述方法自制
共聚聚丙烯5* 参考CN101058654A所述方法自制
共聚聚丙烯6* 参考CN101058654A所述方法自制
聚丙烯T30S 均聚聚丙烯，中国石化镇海炼化
过氧化二苯甲酰 百灵威科技有限公司J&K Chemicals
过氧化月桂酰 百灵威科技有限公司J&K Chemicals
过氧化(2-乙基己酸)叔丁酯 阿达玛斯试剂有限公司adamas-beta
马来酸酐 国药集团化学试剂有限公司
苯乙烯 百灵威科技有限公司J&K Chemicals
对甲基苯乙烯 百灵威科技有限公司J&K Chemicals
醋酸乙烯酯 国药集团化学试剂有限公司
苯乙烯/马来酸酐共聚物 Sigma-Aldrich贸易有限公司Sigma-Aldrich LLC.
*共聚聚丙烯1：实施例1、对比例2、对比例3中所用的共聚聚丙烯。
*共聚聚丙烯2：实施例2中所用的共聚聚丙烯。
*共聚聚丙烯3：实施例3中所用的共聚聚丙烯。
*共聚聚丙烯4：实施例4中所用的共聚聚丙烯。
*共聚聚丙烯5：实施例5中所用的共聚聚丙烯。
*共聚聚丙烯6：实施例6中所用的共聚聚丙烯。
实施例1
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1wt％，二甲苯可溶物含量48.7wt％，可溶物中共聚单体含量31.9wt％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃，击穿场强(90℃)为236kV/mm，直流体积电阻率(90℃，15kV/mm)为1.16E13Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入1.3g过氧化二苯甲酰、10g马来酸酐和40g苯乙烯的溶液，搅拌混合30min，40℃溶胀2小时，升温至90℃， 反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐材料产品C1。
测试所得产品的各项性能参数，结果如表1所示。
实施例2
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量14.7wt％，二甲苯可溶物含量41.7wt％，可溶物中共聚单体含量34.5wt％，可溶物/共聚聚丙烯特性粘数比0.91，重均分子量为36.6×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.54g/10min，Tm＝164.9℃，击穿场强(90℃)为248kV/mm，直流体积电阻率(90℃，15kV/mm)为7.25E12Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入0.6g过氧化二苯甲酰、5g马来酸酐和22g苯乙烯的溶液，搅拌混合30min，40℃溶胀3小时，升温至95℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐材料产品C2。
测试所得产品的各项性能参数，结果如表1所示。
实施例3
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量20.1wt％，二甲苯可溶物含量66.1wt％，可溶物中共聚单体含量29.5wt％，可溶物/共聚聚丙烯特性粘数比1.23，重均分子量为53.8×10 4g/mol，在230℃，2.16kg载荷下的MFR为0.51g/10min，Tm＝142.5℃，击穿场强(90℃)为176kV/mm，直流体积电阻率(90℃，15kV/mm)为5.63E12Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入2.6g过氧化二苯甲酰、12g马来酸酐和88g苯乙烯的溶液，搅拌混合30min，40℃溶胀2小时，升温至90℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐材料产品C3。
测试所得产品的各项性能参数，结果如表1所示。
实施例4
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量9.3wt％，二甲苯可溶物含量21.0wt％，可溶物中共聚单体含量35.4wt％，可溶物/共聚聚丙烯特性粘数比1.68，重均分子量为30.4×10 4g/mol，在230℃，2.16kg载荷下的MFR为5.69g/10min，Tm＝163.0℃，击穿场强(90℃)为288kV/mm，直流体积电阻率(90℃，15kV/mm)为1.32E13Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到 带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入5.0g过氧化(2-乙基己酸)叔丁酯、25g马来酸酐、50g醋酸乙烯酯和100g甲苯的溶液，搅拌混合30min，升温至95℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-醋酸乙烯酯/马来酸酐材料产品C4。
测试所得产品的各项性能参数，结果如表1所示。
实施例5
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量4.8wt％，二甲苯可溶物含量19.2wt％，可溶物中共聚单体含量17.6wt％，可溶物/共聚聚丙烯特性粘数比1.04，重均分子量为29.2×10 4g/mol，在230℃，2.16kg载荷下的MFR为5.37g/10min，Tm＝163.3℃，击穿场强(90℃)为322kV/mm，直流体积电阻率(90℃，15kV/mm)为1.36E13Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入0.6g过氧化二苯甲酰、10g马来酸酐、11g苯乙烯和50g甲苯的溶液，搅拌混合30min，50℃溶胀2h，升温至100℃，反应1小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐材料产品C5。
测试所得产品的各项性能参数，结果如表1所示。
实施例6
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量12.6wt％，二甲苯可溶物含量30.6wt％，可溶物中共聚单体含量43.6wt％，可溶物/共聚聚丙烯特性粘数比1.84，重均分子量为27.1×10 4g/mol，在230℃，2.16kg载荷下的MFR为8.46g/10min，Tm＝162.0℃，击穿场强(90℃)为261kV/mm，直流体积电阻率(90℃，15kV/mm)为9E12Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。将2g过氧化月桂酰和20g马来酸酐溶解于150g丙酮中，将所得丙酮溶液加入到反应体系中，升温至50℃，氮气吹扫30min除去丙酮，将α-甲基苯乙烯60g滴加入反应釜中，将溶液搅拌混合30min，40℃溶胀2h，升温至85℃，加入85℃的分散剂水4kg，反应2h。反应结束后，冷却降温，过滤除去分散剂水，70℃下真空干燥10小时，得到聚丙烯-g-α-甲基苯乙烯/马来酸酐材料产品C6。
测试所得产品的各项性能参数，结果如表1所示。
实施例7
称取实施例1的基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入4.0g过氧化二苯甲酰、30g马来酸酐和120g苯乙烯的溶液，搅拌混合30min，40℃溶胀2小时，升温至90℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐产品C7。
测试所得产品的各项性能参数，结果如表1所示。
对比例1
称取筛分除去小于40目的细粉的T30S粉料(击穿场强(90℃)为347kV/mm，直流体积电阻率(90℃，15kV/mm)为1.18E13Ω·m)2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入1.3g过氧化二苯甲酰、10g马来酸酐和40g苯乙烯的溶液，搅拌混合60min，40℃溶胀2小时，升温至90℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐材料产品D1。
测试所得产品的各项性能参数，结果如表1所示。
对比例2
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1wt％，二甲苯可溶物含量48.7wt％，可溶物中共聚单体含量31.9wt％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃，击穿场强(90℃)为236kV/mm，直流体积电阻率(90℃，15kV/mm)为1.16E13Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2.0kg，加入到带有机械搅拌的10L反应釜中，密闭反应系统，氮气置换除氧。加入5g过氧化二苯甲酰、40g马来酸酐和160g苯乙烯的溶液，搅拌混合60min，40℃溶胀2小时，升温至90℃，反应4小时。反应结束后，氮气吹扫降温，得到聚丙烯-g-苯乙烯/马来酸酐材料产品D2。
测试所得产品的各项性能参数，结果如表1所示。
对比例3
选取具有以下特征的基础共聚聚丙烯粉料：共聚单体乙烯含量18.1wt％，二甲苯可溶物含量48.7wt％，可溶物中共聚单体含量31.9wt％，可溶物/共聚聚丙烯特性粘数比0.89，重均分子量为34.3×10 4g/mol，在230℃，2.16kg载荷下的MFR为1.21g/10min，Tm＝143.4℃， 击穿场强(90℃)为236kV/mm，直流体积电阻率(90℃，15kV/mm)为1.16E13Ω·m，筛分除去小于40目的细粉。称取上述基础共聚聚丙烯粉料2000g，和50g苯乙烯/马来酸酐共聚物混合，使用螺杆挤出机混合，得到共混物D3。
测试所得产品的各项性能参数，结果如表1所示。
Figure PCTCN2020127465-appb-000014
比较实施例1和对比例1的数据可以看出，采用T30S粉料作为基础粉料，所得聚丙烯-g-苯乙烯/马来酸酐材料产品的弯曲模量过高，材料机械性能差，无法满足绝缘材料加工需要。
比较实施例1和对比例2的数据可以看出，马来酸酐单体/含烯基聚合单体的加入量过高(M1值过高)会导致所得聚丙烯-g-苯乙烯/马来酸酐材料产品击穿场强和体积电阻率下降，影响产品的电性能。
比较实施例1和对比例3的数据可以看出，采用共混苯乙烯/马来酸酐共聚物的方式反而导致产品的击穿场强和体积电阻率大幅下降，极大影响产品的电性能。
综上，由表1数据可以看出，弯曲模量的大幅下降使得本发明的含有酸酐基团的聚丙烯接枝物具有良好的机械性能，并且，相比未接枝马来酸酐/含烯基聚合单体的共聚聚丙烯，接枝产物的击穿场强均得以提高，说明本发明的含有酸酐基团的聚丙烯接枝物同时具有良好的电性能。
此外，由介电常数和介电损耗数据可以看出，接枝改性并不影响材料的介电常数和介电损耗，本发明的材料满足绝缘所需必要条件。
实施例A
导体的制备：将多条铝制单丝导体进行束丝操作，接着，将束丝后制导体内芯。
含有酸酐基团的聚丙烯接枝物颗粒的制备：将如下质量份的各组份共混：实施例C1、实施例C3、实施例C5和实施例C7得到的含有酸酐基团的聚丙烯接枝物100份，抗氧剂1010/168/硬脂酸钙(质量比2:2:1)0.3份。用双螺杆挤出机造粒，转速300r/min，造粒温度210-230℃。
导体屏蔽层和绝缘层的制备：导体屏蔽料PSD_WMP-00012(浙江万马股份有限公司)和上述含有酸酐基团的聚丙烯接枝物颗粒，在导体内芯外通过挤出机共挤出包覆形成导体屏蔽层+电绝缘层，或形成导体屏蔽层+电绝缘层+电绝缘屏蔽层(外屏蔽层)，挤出温度为160-210℃。
金属屏蔽层的制备：在电绝缘层(电绝缘屏蔽层)外采用T1铜进行铜带绕包，形成金属屏蔽层。
内护套层的制备：将牌号St-2的PVC颗粒(东莞海创电子有限公司)在金属屏蔽层外通过挤出机挤出形成内护套层。
铠装的制备：使用304不锈钢制成标称直径为1.25mm的钢丝铠装，由单层铠装左向绕包在内护套层上，铠装紧密，使相邻钢丝间的间隙为最小。
外护套层的制备：将牌号St-2的PVC颗粒(东莞海创电子有限公司)在铠装外通过挤出机挤出形成外护套层。
最终得到所述高性能聚丙烯电缆。该电缆的剖面结构示意图如图1所示。
根据上述方法分别基于实施例C1、实施例C3、实施例C5和实施例C7的材料制得能级在6～35kV范围内的电缆，电缆导体截面积240～400mm 2，导体屏蔽层厚度1～3mm，电绝缘层厚度2～8mm，电绝缘屏蔽层厚度0.5～1.5mm，铠装厚度0.5～1mm，内护套层厚度1～2mm，外护套层厚度不小于1.8mm。
测试例A
对实施例B制得的电缆进行测试。电缆的主绝缘电导率测试结果：各电缆在90℃和30℃下电导率比值均小于100。电缆绝缘空间电荷注入测试结果：各电缆的电场畸变均小于20％。直流耐压测试结果：各电缆均无击穿和放电现象，通过。负荷循环测试结果：各电缆均无击穿现象，通过。
实施例A1
导体的制备：将76根直径为2.5mm的铝制单丝进行紧压绞合操作，得到铝制导体内芯。
含有酸酐基团的聚丙烯接枝物颗粒的制备：将如下质量份的各组份共混：实施例2得到的含有酸酐基团的聚丙烯接枝物100份，抗氧剂1010/168/硬脂酸钙(质量比2:2:1)0.3份。用双螺杆挤出机造粒，转速300r/min，造粒温度210～230℃。
导体屏蔽层和绝缘层的制备：导体屏蔽料PSD_WMP-00012(浙江万马股份有限公司)和上述含有酸酐基团的聚丙烯接枝物颗粒，在导体内芯外通过挤出机共挤出包覆形成导体屏蔽层+电绝缘层，或形成导体屏蔽层+电绝缘层+电绝缘屏蔽层(外屏蔽层)，挤出温度为190～210℃。
金属屏蔽层的制备：在电绝缘层(电绝缘屏蔽层)外采用25根直径为0.3mm的T1铜进行铜丝绕包，形成金属屏蔽层。
内护套层的制备：将牌号St-2的PVC颗粒(东莞海创电子有限公司)在金属屏蔽层外通过挤出机挤出形成内护套层。
铠装的制备：使用50根直径6.0mm的304不锈钢丝制成单层钢丝铠装，将单层钢丝铠装左向绕包在内护套层上，铠装紧密，使相邻钢丝间的间隙为最小。
外护套层的制备：将牌号St-2的PVC颗粒(东莞海创电子有限公司)在铠装外通过 挤出机挤出形成外护套层。
最终得到所述高性能聚丙烯电缆。该电缆的剖面结构示意图如图1所示。
根据上述方法分别基于实施例2的材料制得能级在10kV的电缆，电缆导体截面积约400mm 2，导体屏蔽层的平均厚度1.15mm，电绝缘层的平均厚度2.60mm，电绝缘屏蔽层的平均厚度1.06mm，金属屏蔽层的平均厚度为1.00mm，电缆绝缘偏心度为5.1％，铠装的平均厚度6.02mm，内护套层的平均厚度2.10mm，外护套层的平均厚度2.35mm。
测试例A1
对所制得的电缆进行测试。电缆的主绝缘电导率测试结果：各电缆在90℃和30℃下电导率比值为44.2。电缆绝缘空间电荷注入测试结果：电缆的电场畸变为15.4％。直流耐压测试结果：电缆无击穿和放电现象，通过。负荷循环测试结果：电缆无击穿现象，通过。
由此可见，本发明的采用含有酸酐基团的聚丙烯接枝物作为主绝缘层的电缆，相比现有电缆，具有更高的工作温度，并且在更高工作温度下依然能够保持甚至具有更高的体积电阻率和更强的耐击穿性能。在保证相同电压等级和绝缘水平条件下，由所述含有酸酐基团的聚丙烯接枝物所制的电绝缘层相比常规电缆的电绝缘层具有厚度更薄、散热更好和重量更小的优点。
以上已经描述了本发明的各实施例，上述说明是示例性的，并非穷尽性的，并且也不限于所披露的各实施例。在不偏离所说明的各实施例的范围和精神的情况下，对于本技术领域的普通技术人员来说许多修改和变更都是显而易见的。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值，这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说，各个范围的端点值之间、各个范围的端点值和单独的点值之间，以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围，这些数值范围应被视为在本文中具体公开。

Claims (37)

  1. 一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物，其特征在于，该含有酸酐基团的聚丙烯接枝物包括衍生自共聚聚丙烯的结构单元、衍生自酸酐单体的结构单元和衍生自含烯基聚合单体的结构单元；以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10；
    所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
  2. 根据权利要求1所述的含有酸酐基团的聚丙烯接枝物，其中，所述共聚聚丙烯具有以下特征中的至少一种：在230℃，2.16kg载荷下的熔体流动速率为0.01～60g/10min，优选为0.05～35g/10min，进一步优选为0.5～15g/10min；熔融温度Tm为100℃以上，优选为110～180℃，更优选为110～170℃，进一步优选为120～170℃，更进一步优选为120～166℃；重均分子量为20×10 4～60×10 4g/mol。
  3. 根据权利要求1或2所述的含有酸酐基团的聚丙烯接枝物，其中，所述共聚聚丙烯的共聚单体选自除丙烯外的C 2-C 8的α-烯烃中的至少一种；优选地，所述共聚聚丙烯的共聚单体选自乙烯、1-丁烯、1-戊烯、4-甲基-1-戊烯、1-己烯、1-庚烯和1-辛烯中的至少一种；进一步优选地，所述共聚聚丙烯的共聚单体为乙烯和/或1-丁烯；进一步优选地，所述共聚聚丙烯由丙烯和乙烯组成。
  4. 根据权利要求1-3中任意一项所述的含有酸酐基团的聚丙烯接枝物，其中，所述含有酸酐基团的聚丙烯接枝物由共聚聚丙烯、酸酐单体和含烯基聚合单体经固相接枝反应制得。
  5. 根据权利要求1-4中任意一项所述的含有酸酐基团的聚丙烯接枝物，其中，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体且处于接枝态的结构单元的含量为0.05～2wt％，优选为0.2～0.7wt％。
  6. 根据权利要求1-5中任意一项所述的含有酸酐基团的聚丙烯接枝物，其中，所述酸酐选自具有至少一个烯烃不饱和度的酸酐；优选地，所述酸酐选自马来酸酐和衣康酸酐；进一步优选地，所述酸酐为马来酸酐。
  7. 根据权利要求1-6中任意一项所述的含有酸酐基团的聚丙烯接枝物，其中，所述含有酸酐基团的聚丙烯接枝物具有以下特征中的至少一种：在230℃，2.16kg载荷下的熔体流动速率为0.01～30g/10min，优选为0.05～20g/10min，进一步优选为0.1～10g/10min，更优选为0.2～8g/10min；弯曲模量为10～1050MPa，优选为20～1000MPa，更优选为50～500MPa；断裂伸长率≥200％，优选断裂伸长率≥300％。
  8. 根据权利要求1-7中任意一项所述的含有酸酐基团的聚丙烯接枝物，其中，所述含有酸酐基团的聚丙烯接枝物具有以下特征中的至少一种：
    -所述含有酸酐基团的聚丙烯接枝物的工作温度≥90℃，优选为90～160℃；
    -所述含有酸酐基团的聚丙烯接枝物在90℃下的击穿场强E g≥210kV/mm，优选为210～800kV/mm；
    -所述含有酸酐基团的聚丙烯接枝物在90℃下的击穿场强E g与所述共聚聚丙烯在90℃下的击穿场强E的差值△E除以所述共聚聚丙烯在90℃下的击穿场强E所得的击穿场强变化率△E/E大于1.8％，优选为2％～50％，更优选为5％～35％，进一步优选为8％～28％；
    -所述含有酸酐基团的聚丙烯接枝物在90℃、15kV/mm场强下的直流体积电阻率ρ vg≥1.5×10 13Ω·m，优选为1.5×10 13Ω·m～1.0×10 20Ω·m；
    -所述含有酸酐基团的聚丙烯接枝物在90℃、15kV/mm场强下的直流体积电阻率ρ vg与所述共聚聚丙烯在90℃、15kV/mm场强下的直流体积电阻率ρ v的比值ρ vg/ρ v大于2，优选为2.1～40，更优选为2.3～20，进一步优选为2.5～10。
  9. 根据权利要求1-8中任意一项所述的含有酸酐基团的聚丙烯接枝物，其中，所述含烯烃基聚合单体选自具有式1所示结构的单体中的至少一种，
    Figure PCTCN2020127465-appb-100001
    式1中，R b、R c、R d各自独立地选自H、取代或未取代的烷基；R a选自取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的酯基、取代或未取代的羧基、取代或未取代的环烷基或杂环基、氰基。
  10. 根据权利要求9所述的含有酸酐基团的聚丙烯接枝物，其中，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 6烷基，优选地，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 3烷基；R a选自取代或未取代的C 1-C 20烷基、取代或未取代的C 1-C 20烷氧基、取代或未取代的C 6-C 20芳基、取代或未取代的C 1-C 20酯基、取代或未取代的C 1-C 20羧基、取代或未取代的C 3-C 20环烷基或杂环基、氰基，所述取代的基团为卤素、羟基、氨基、C 1-C 6烷基、C 3-C 6环烷基；优选地，R a选自取代或未取代的C 1-C 12烷基、取代或未取代的C 1-C 18烷氧基、取代或未取代的C 6-C 12芳基、取代或未取代的C 1-C 12酯基、取代或未取代的C 1-C 12羧基、取代或未取代的C 3-C 12环烷基或杂环基、氰基，所述取代的基团为卤素、C 1-C 6烷基、C 3-C 6环烷基；更优选地，R a选自取代或未取代的C 1-C 6烷基、取代或未取代的C 1-C 12烷氧基、取代或未取代的C 6-C 8芳基、取代或未取代的C 1-C 6酯基、取代或未取代的C 1-C 6羧基、取代或未取代的C 3-C 6环烷基或杂环基、氰基；优选地，所述杂环基选自咪唑基、吡唑基、咔唑基、吡咯烷酮基、吡啶基、哌啶基、己内酰胺基、吡嗪基、噻唑基、嘌呤基、吗啉基、噁唑啉基。
  11. 根据权利要求9所述的含有酸酐基团的聚丙烯接枝物，其中，R b、R c、R d各自独立地选自H、取代或未取代的C 1-C 6烷基；
    R a选自式2所示基团、式3所示基团、式4所示基团、式6所示基团、式6所示基团和式7所示基团的组合、杂环基团；
    Figure PCTCN2020127465-appb-100002
    式2中，R 4-R 8各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、 羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 8各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基；
    Figure PCTCN2020127465-appb-100003
    式3中，R 4-R 10各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4-R 10各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
    Figure PCTCN2020127465-appb-100004
    式4中，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、磷酸基、磺酸基、取代或未取代的C 1-C 12的烷基、取代或未取代的C 3-C 12的环烷基、取代或未取代的C 1-C 12的烷氧基、取代或未取代的C 1-C 12的酯基、取代或未取代的C 1-C 12的胺基，所述取代的基团选自卤素、羟基、氨基、磷酸基、磺酸基、C 1-C 12的烷基、C 3-C 12的环烷基、C 1-C 12的烷氧基、C 1-C 12的酯基、C 1-C 12的胺基；优选地，R 4’-R 10’各自独立地选自H、卤素、羟基、氨基、取代或未取代的C 1-C 6的烷基、取代或未取代的C 1-C 6的烷氧基，所述取代的基团选自卤素、羟基、氨基、C 1-C 6的烷基、C 1-C 6的烷氧基；
    Figure PCTCN2020127465-appb-100005
    式6中，R m选自取代或未取代的以下基团：C 1-C 20直链烷基、C 3-C 20支链烷基、C 3-C 12环烷基、C 3-C 12环氧烷基、C 3-C 12环氧烷基烷基，所述取代的基团选自卤素、氨基和羟基中的至少一种。
  12. 根据权利要求9所述的含有酸酐基团的聚丙烯接枝物，其中，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸酯、乙烯基烷基醚、乙烯基吡咯烷酮、乙烯基吡啶、乙烯基咪唑和丙烯腈中的至少一种；所述(甲基)丙烯酸酯优选为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯和(甲基)丙烯酸缩水甘油酯中的至少一种；优选地，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯；进一步优选地，所述含烯基聚合单体为苯乙烯。
  13. 一种用于绝缘材料的含有酸酐基团的聚丙烯接枝物的制备方法，该制备方法包括：在惰性气体存在下，使包括共聚聚丙烯、酸酐单体和含烯基聚合单体的反应混合物进行接枝反应，得到所述含有酸酐基团的聚丙烯接枝物；
    其中，所述接枝反应的条件使得：以含有酸酐基团的聚丙烯接枝物的重量为基准，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体和含烯基聚合单体且处于接枝态的结构单元的含量为0.1～5wt％，优选为0.4～3wt％；并且，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体的结构单元与衍生自含烯基聚合单体的结构单元的摩尔比为1：1～20，优选为1：1～10；
    所述共聚聚丙烯具有以下特征中的至少一种：共聚单体含量为0.5～40mol％，优选为0.5～30mol％，更优选为4～25wt％，进一步优选为4～22wt％；二甲苯可溶物含量为2～80wt％，优选为18～75wt％，更优选为30～70wt％，进一步优选为30～67wt％；可溶物中共聚单体含量为10～70wt％，优选为10～50wt％，更优选为20～35wt％；可溶物与聚丙烯的特性粘数比为0.3～5，优选为0.5～3，更优选为0.8～1.3。
  14. 根据权利要求13所述的制备方法，其中，所述共聚聚丙烯具有以下特征中的至少一种：在230℃，2.16kg载荷下的熔体流动速率为0.01～60g/10min，优选为0.05～35g/10min，进一步优选为0.5～15g/10min；熔融温度Tm为100℃以上，优选为110～180℃，进一步优选为110～170℃，进一步优选为120～170℃，进一步优选为120～166℃；重均分子量为20×10 4～60×10 4g/mol。
  15. 根据权利要求13或14所述的制备方法，其中，所述含有酸酐基团的聚丙烯接枝物中衍生自酸酐单体且处于接枝态的结构单元的含量为0.05～2wt％，优选为0.2～0.7wt％。
  16. 根据权利要求13-15中任意一项所述的制备方法，其中，所述酸酐选自具有至少 一个烯烃不饱和度的酸酐；优选地，所述酸酐选自马来酸酐和衣康酸酐；进一步优选地，所述酸酐为马来酸酐。
  17. 根据权利要求13-16中任意一项所述的制备方法，其中，所述反应混合物还包括自由基引发剂；
    优选地，所述自由基引发剂选自过氧化物类自由基引发剂和/或偶氮类自由基引发剂；
    所述过氧化物类自由基引发剂优选选自过氧化二苯甲酰、过氧化二异丙苯、二叔丁基过氧化物、过氧化月桂酰、过氧化十二酰、过氧化苯甲酸叔丁酯、过氧化二碳酸二异丙基酯、过氧化(2-乙基己酸)叔丁酯和过氧化二碳酸二环己基酯中的至少一种；所述偶氮类自由基引发剂优选为偶氮二异丁腈和/或偶氮二异庚腈。
  18. 根据权利要求17所述的制备方法，其中，所述自由基引发剂的质量与所述酸酐单体和所述含烯基聚合单体的总质量的比为0.1～10:100，优选为0.5～5:100。
  19. 根据权利要求13-18中任意一项所述的制备方法，其中，所述酸酐单体和所述含烯基聚合单体的总质量与所述共聚聚丙烯的质量比为0.1～8:100，优选为0.3～5:100。
  20. 根据权利要求13-19中任意一项所述的制备方法，其中，所述接枝反应的温度为30～130℃，优选为60～120℃；时间为0.5～10h，优选为1～5h。
  21. 根据权利要求13-20中任意一项所述的制备方法，其中，所述反应混合物还包括以下组分中的至少一种：分散剂、界面剂和有机溶剂，所述分散剂的质量含量为共聚聚丙烯质量的50～300％，所述界面剂的质量含量为共聚聚丙烯质量的1～30％，所述有机溶剂的质量含量为共聚聚丙烯质量的1～35％。
  22. 根据权利要求13-20中任意一项所述的制备方法，其中，所述制备方法包括以下步骤：
    a.将共聚聚丙烯置于密闭反应器中，进行惰性气体置换；
    b.将自由基引发剂与酸酐单体和含烯基聚合单体加入到所述密闭反应器中，搅拌混合；
    c.任选地加入界面剂，并任选地使反应体系进行溶胀；
    d.任选地加入分散剂，使反应体系升温至接枝反应温度，进行接枝反应；
    e.反应结束后，任选地进行过滤，干燥后得到所述含有酸酐基团的聚丙烯接枝物。
  23. 根据权利要求13-20中任意一项所述的制备方法，其中，所述制备方法包括以下步骤：
    a.将共聚聚丙烯置于密闭反应器中，进行惰性气体置换；
    b.将有机溶剂和自由基引发剂混合，加入到所述密闭反应器中；
    c.除去所述有机溶剂；
    d.加入酸酐单体和含烯基聚合单体，任选地加入界面剂，并任选地使反应体系进行溶胀；
    e.任选地加入分散剂，使反应体系升温至接枝反应温度，进行接枝反应；
    f.反应结束后，任选地进行过滤，干燥后得到所述含有酸酐基团的聚丙烯接枝物。
  24. 根据权利要求13-23中任意一项所述的制备方法，其中，所述含烯烃基聚合单体选自具有式1所示结构的单体中的至少一种，
    Figure PCTCN2020127465-appb-100006
    式1中，R b、R c、R d各自独立地选自H、取代或未取代的烷基；R a选自取代或未取代的烷基、取代或未取代的烷氧基、取代或未取代的芳基、取代或未取代的酯基、取代或未取代的羧基、取代或未取代的环烷基或杂环基、氰基。
  25. 根据权利要求24所述的制备方法，其中，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯、(甲基)丙烯酸酯、乙烯基烷基醚、乙烯基吡咯烷酮、乙烯基吡啶、乙烯基咪唑和丙烯腈中的至少一种；所述(甲基)丙烯酸酯优选为(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯和(甲基)丙烯酸缩水甘油酯中的至少一种；优选地，所述含烯基聚合单体选自乙酸乙烯酯、苯乙烯、α-甲基苯乙烯；进一步优选地，所述含烯基聚合单体为苯乙烯。
  26. 由权利要求13-25中任意一项所述的制备方法制得的用于绝缘材料的含有酸酐基团的聚丙烯接枝物。
  27. 权利要求1-12中任意一项所述的和由权利要求13-25中任意一项所述的制备方法制得的含有酸酐基团的聚丙烯接枝物作为绝缘材料的应用。
  28. 根据权利要求1-12和26中任意一项所述的用于绝缘材料的含有酸酐基团的聚丙烯接枝物或根据权利要求27所述的应用，其中，所述绝缘材料为电缆绝缘材料；优选为直流电缆绝缘材料。
  29. 根据权利要求1-12和26中任意一项所述的用于绝缘材料的含有酸酐基团的聚丙烯接枝物或根据权利要求27所述的应用，其中，所述绝缘材料为电缆绝缘层材料。
  30. 一种电缆，其特征在于，该电缆包括：
    至少一个导体以及至少一个围绕所述导体的电绝缘层；
    其中，所述电绝缘层的材料为至少一种权利要求1-12和26中任意一项所述的含有酸酐基团的聚丙烯接枝物。
  31. 根据权利要求30所述的电缆，其中，所述电缆具有至少一个缆芯，每个所述缆芯由内至外依次包括：导体、任选的导体屏蔽层、电绝缘层、任选的电绝缘屏蔽层、任选的金属屏蔽层。
  32. 根据权利要求31所述的电缆，其中，所述电缆还包括铠装和/或护套层。
  33. 根据权利要求31所述的电缆，其中，所述电缆还包括填充层和/或包带层。
  34. 根据权利要求30所述的电缆，其中，所述电缆为直流电缆或交流电缆；优选地，所述电缆为直流电缆。
  35. 一种绝缘材料，其特征在于，该绝缘材料包含至少一种权利要求1-12和26中任意一项所述的含有酸酐基团的聚丙烯接枝物。
  36. 根据权利要求35所述的绝缘材料，其中，以所述绝缘材料的重量为基准，所述至少一种含有酸酐基团的聚丙烯接枝物的含量为20-100wt％，优选为40-100wt％，更优选为60-100wt％，进一步优选为80-100wt％，更进一步优选为90-100wt％。
  37. 根据权利要求35或36所述的绝缘材料，其中，所述绝缘材料还包含抗氧化剂、 稳定剂、加工助剂、阻燃剂、水树阻滞添加剂、酸或离子清除剂、无机填料、电压稳定剂和抗铜剂中的一种或多种。
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