Process for the preparation of olefin-functional polymers and use thereof

Abstract

The present application relates to a kind of preparation method of olefin functional polymer and its application, the preparation method includes the following steps: (1) mixing functional monomer, ethylene ester comonomer, initiator and solvent, to obtain raw material liquid;(2) under anaerobic condition, mixing olefin and the raw material liquid obtained in step (1), to carry out polymerization reaction, to obtain reaction material;(3) reaction material is separated and dried by solid-liquid, to obtain the olefin functional polymer;The anhydride value of the olefin functional polymer is 5-75%.The preparation method is mild, can realize the ternary random copolymerization of olefin, functional monomer and ethylene ester comonomer, and the content of functional group in the obtained olefin functional polymer is adjustable and controllable, to realize the regulation of the modification activity of olefin functional polymer.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of organic synthesis, and relates to a preparation method of a polymer, in particular to a preparation method of an olefin functional polymer and application thereof. BACKGROUND

[0002] The olefin functional polymer, as a kind of functional polymer material, has wide applications in chain extension of engineering plastics, high-performance composite materials, nylon infiltration, oil film dispersion, microencapsulation, and membrane formation of filter membranes.

[0003] CN101781387A discloses a method for maleic anhydride / conjugated diene copolymerization reaction, which comprises the following steps: under the condition of nitrogen protection, monomer maleic anhydride and initiator are added into a medium to be fully dissolved, then monomer conjugated diene is added into the system to be dissolved, and the system is reacted at 50-90℃ for 0.5-73h to obtain a dispersion system of maleic anhydride and conjugated diene copolymer microspheres, and then the dispersion system is centrifuged and vacuum dried to obtain white solid of maleic anhydride and conjugated diene copolymer.

[0004] The olefin functional polymer has an alternating copolymerization tendency, so that the content of anhydride groups (anhydride value) in the olefin functional polymer is high. Although high anhydride value makes the olefin functional polymer have higher activity in high polymer modification, too many active groups are not conducive to expanding the applicability. For example, in the process of nylon reinforcement modification, too many active groups will cause uncontrollable chain extension speed, and the screw extrusion process is prone to violent death defects, thereby affecting the modification effect.

[0005] CN102250273A discloses a preparation method of a styrene-maleic anhydride random copolymer, which comprises the following steps: under the condition of nitrogen protection, monomer maleic anhydride and initiator are added into a solvent to be fully dissolved, then monomer styrene is added into the system to be dissolved, and then the system is heated by oil bath to be reacted at 90-130℃ for 1.5-24h to obtain a metastable dispersion system of the copolymer, and after the reaction is completed, the system is centrifuged and filtered, and finally dried to obtain the styrene-maleic anhydride random copolymer. The preparation method realizes the regulation of anhydride value in the range of 5-50% by regulating the monomer feeding ratio.

[0006] CN107417840A discloses a multi-component copolymer micro-nano particle and a preparation method thereof. The multi-component copolymer micro-nano particle is composed of styrene monomers, maleic anhydride monomers and (meth)acrylate monomers. The multi-component copolymer micro-nano particle is prepared by self-stabilizing precipitation polymerization. The copolymerization reaction system is composed of styrene electron-donating monomers, maleic anhydride electron-accepting monomers and (meth)acrylate monomers. After the polymerization reaction is completed, the narrow-distribution multi-component copolymer microparticles are separated from the reaction system by centrifugation or filtration.

[0007] The prior art realizes the control of the acid anhydride value of the polymer and the control of the modification activity of the polymer chain segment by adjusting the monomer feeding ratio or the number of monomers, but the preparation method is not suitable for other olefins.

[0008] The existing olefin functional polymer on the market is mostly maleic anhydride grafted polyolefin. The acid anhydride group content (acid anhydride value) in the olefin functional polymer is less than 3%, and it is difficult to realize the chain extension of the polymer. Even if a certain chain extension effect can be achieved, the low reactivity cannot effectively improve the mechanical properties and hydrolysis stability of the composite material. In addition, some enterprises use a high-pressure reaction kettle to obtain an olefin functional polymer through free radical polymerization. The acid anhydride group content (acid anhydride value) of the polymer is greater than 75%. Although the high acid anhydride value makes the olefin functional polymer have higher activity in high polymer modification, too many active groups are not conducive to the expansion of its applicability. For example, in the process of reinforcing modification of nylon, too many active groups will cause uncontrollable chain extension speed, and the screw extrusion process is prone to die defects, thereby affecting the modification effect.

[0009] Therefore, it is necessary to provide a preparation method of an olefin functional polymer and application thereof, which can control the acid anhydride value and has mild reaction conditions and high production efficiency. SUMMARY

[0010] The purpose of the present application is to provide a preparation method of an olefin functional polymer and application thereof. The preparation method has mild conditions and can realize the ternary random copolymerization of olefin, functional monomer and ethylene ester comonomer. The content of the functional group in the obtained olefin functional polymer is adjustable and controllable.

[0011] To achieve the purpose of the present application, the following technical solutions are adopted:

[0012] In a first aspect, the present application provides a preparation method of an olefin functional polymer, which comprises the following steps:

[0013] (1) mixing a functional monomer, an ethylene ester comonomer, an initiator and a solvent to obtain a raw material solution;

[0014] (2) mixing an olefin and the raw material solution obtained in step (1) under anaerobic conditions to perform a polymerization reaction, thereby obtaining a reaction material;

[0015] (3) subjecting the reaction material to solid-liquid separation and drying to obtain the olefin functional polymer;

[0016] The acid anhydride value of the olefin functional polymer is 5-75%.

[0017] The preparation method provided by the present application realizes the regulation of the anhydride value of the olefin functional polymer in the range of 5-75% by adjusting the feeding amount of the vinyl ester comonomer, for example, it can be 5%, 10%, 20%, 25%, 30%, 35%, 40%, 50%, 60%, 65%, 70% or 75%, but is not limited to the listed values, and other values not listed in the value range are also applicable, and preferably 50-75%. At the same time, by introducing the vinyl ester comonomer, the content of ester groups in the olefin functional polymer is increased, the compatibility with the polyester material matrix is increased, and the obtained olefin functional polymer is suitable for the modification of the polyester material.

[0018] Preferably, the chemical formula of the vinyl ester comonomer in step (1) is C 3+a H 4+2a O2, wherein a is a positive integer ≥1, for example, it can be 1, 2, 3, 4, 5, 6, 7 or 8, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0019] Preferably, the vinyl ester comonomer in step (1) includes any one or a combination of at least two of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate or vinyl decanoate, and typical but non-limiting combinations include a combination of vinyl acetate and vinyl propionate, a combination of vinyl butyrate and vinyl hexanoate, a combination of vinyl propionate and vinyl hexanoate, a combination of vinyl acetate, vinyl propionate and vinyl butyrate, a combination of vinyl butyrate, vinyl hexanoate and vinyl decanoate, or a combination of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate and vinyl decanoate.

[0020] The present application uses vinyl ester comonomer to make the obtained olefin functional polymer have strong hydrophilicity, especially vinyl acetate, which can make the olefin functional polymer have anti-aging property, weather resistance, discoloration resistance and excellent mechanical property; and the cost of the vinyl ester comonomer is low, green and environmentally friendly, and has excellent processing performance.

[0021] Preferably, the molar ratio of the functional monomer to the vinyl ester comonomer in step (1) is 1:(0.1-5), for example, it can be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5 or 1:5, but is not limited to the listed values, and other values not listed in the value range are also applicable.

[0022] Preferably, the functional monomer in step (1) includes maleic anhydride and / or maleimide.

[0023] Preferably, the initiator of step (1) comprises any one or a combination of at least two of azo-based initiator, peroxide-based initiator or photoinitiator, typical but non-limiting combinations include a combination of azo-based initiator and peroxide-based initiator, a combination of peroxide-based initiator and photoinitiator, a combination of azo-based initiator and photoinitiator, or a combination of azo-based initiator, peroxide-based initiator and photoinitiator.

[0024] Preferably, the azo-based initiator comprises azobisisobutyronitrile and / or azobisisoheptanitrile.

[0025] Preferably, the peroxide-based initiator comprises any one or a combination of at least two of benzoyl peroxide, dodecanoyl peroxide, dicumyl peroxide or diisopropyl peroxydicarbonate, typical but non-limiting combinations include a combination of benzoyl peroxide and dodecanoyl peroxide, a combination of dicumyl peroxide and diisopropyl peroxydicarbonate, a combination of dodecanoyl peroxide and dicumyl peroxide, a combination of benzoyl peroxide, dodecanoyl peroxide and dicumyl peroxide, or a combination of benzoyl peroxide, dodecanoyl peroxide, dicumyl peroxide and diisopropyl peroxydicarbonate.

[0026] Preferably, the molar ratio of the functional monomer to initiator of step (1) is 1 : (0.001-0.2), for example, it can be 1 :0.001, 1 :0.005, 1 :0.01, 1 :0.05, 1 :0.1, 1 :0.15 or 1 :0.2, but is not limited to the listed values, other values not listed in the value range are also applicable.

[0027] Preferably, the solvent of step (1) comprises any one or a combination of at least two of organic alkanoate-based solvent, alkane-based compound or aromatic hydrocarbon-based compound, typical but non-limiting combinations include a combination of organic alkanoate-based solvent and alkane-based compound, a combination of alkane-based compound and aromatic hydrocarbon-based compound, a combination of organic alkanoate-based solvent and aromatic hydrocarbon-based compound, or a combination of organic alkanoate-based solvent, alkane-based compound and aromatic hydrocarbon-based compound.

[0028] Preferably, the alkane-based compound comprises any one or a combination of at least two of n-hexane, cyclohexane, n-heptane, n-octane or n-decane, typical but non-limiting combinations include a combination of n-hexane and cyclohexane, a combination of n-hexane and n-heptane, a combination of cyclohexane and n-heptane, a combination of n-octane and n-decane, a combination of n-hexane, cyclohexane and n-heptane, a combination of n-heptane, n-octane and n-decane, or a combination of n-hexane, cyclohexane, n-heptane, n-octane and n-decane.

[0029] Preferably, the aromatic hydrocarbon compound includes any one of benzene, toluene, ethylbenzene, or xylene, or a combination of at least two, and a typical but non-limiting combination includes a combination of benzene and toluene, a combination of toluene and ethylbenzene, a combination of ethylbenzene and xylene, a combination of benzene, toluene, and ethylbenzene, or a combination of benzene, toluene, ethylbenzene, and xylene.

[0030] Preferably, the organic alkanoate solvent has a general structure of wherein R1 is any one of H, a C1-C20 alkyl group, or a C6-C10 aromatic group, and R2 is any one of a C1-C20 alkyl group or a C6-C10 aromatic group.

[0031] In the general structure of the organic alkanoate solvent, the C1-C20 alkyl group includes a C1 alkyl group, a C2 alkyl group, a C3 alkyl group, a C4 alkyl group, a C5 alkyl group, a C6 alkyl group, a C7 alkyl group, a C8 alkyl group, a C9 alkyl group, a C10 alkyl group, a C11 alkyl group, a C12 alkyl group, a C13 alkyl group, a C14 alkyl group, a C15 alkyl group, a C16 alkyl group, a C17 alkyl group, a C18 alkyl group, a C19 alkyl group, or a C20 alkyl group.

[0032] In the general structure of the organic alkanoate solvent, the C6-C10 aromatic group includes a C6 aromatic group, a C7 aromatic group, a C8 aromatic group, a C9 aromatic group, or a C10 aromatic group.

[0033] Preferably, the organic alkanoate solvent includes any one of ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, or isoamyl phenylacetate, or a combination of at least two.

[0034] Preferably, the mass ratio of the functional monomer to the solvent in step (1) is 1:(2-50), such as 1:2, 1:5, 1:10, 1:15, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45, or 1:50, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0035] Preferably, the olefin of step (2) comprises any one or a combination of at least two of ethylene, propylene or an α-olefin, typical but non-limiting combinations include a combination of ethylene and propylene, a combination of ethylene and an α-olefin, a combination of propylene and an α-olefin, or a combination of ethylene, propylene and an α-olefin.

[0036] Preferably, the α-olefin comprises any one or a combination of at least two of 1-butene, 1-hexene or 1-octene, typical but non-limiting combinations include a combination of 1-butene and 1-hexene, a combination of 1-hexene and 1-octene, or a combination of 1-butene, 1-hexene and 1-octene.

[0037] Preferably, the pressure of the polymerization reaction of step (2) is 0.1-10 MPa, for example, it can be 0.1 MPa, 0.5 MPa, 1 MPa, 2 MPa, 3 MPa, 4 MPa, 5 MPa, 6 MPa, 7 MPa, 8 MPa, 9 MPa or 10 MPa, but is not limited to the listed values, other values not listed within the range of values are also applicable.

[0038] Preferably, the temperature of the polymerization reaction of step (2) is 50-150℃, for example, it can be 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃, 120℃, 130℃, 140℃ or 150℃, but is not limited to the listed values, other values not listed within the range of values are also applicable.

[0039] Preferably, the total time of the polymerization reaction of step (2) is 0.01-10 h, for example, it can be 0.01 h, 0.05 h, 0.1 h, 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, but is not limited to the listed values, other values not listed within the range of values are also applicable.

[0040] Further preferably, the form of the reactor used in the polymerization reaction of the present application comprises any one or a combination of at least two of a tank reactor, a pipe reactor, a micro-channel reactor, a horizontal reactor or a column reactor.

[0041] For the micro-channel reactor, the total time of the polymerization reaction refers to the residence time of the raw material liquid; for the tank reactor, the pipe reactor, the horizontal reactor or the column reactor, the total time of the polymerization reaction refers to the feeding time of the raw material liquid and the reaction time (holding time) after feeding.

[0042] Preferably, the reaction product of step (2) is subjected to pressure relief to obtain unreacted olefin and a remaining material.

[0043] The obtained unreacted olefin is recycled to the polymerization reaction of step (2); the obtained remaining material is subjected to step (3).

[0044] Preferably, the filtrate obtained from the solid-liquid separation in step (3) is subjected to solvent recovery, and the recovered solvent is reused in step (1).

[0045] Preferably, the method for recovering the solvent comprises any one or a combination of at least two of rectification, distillation or membrane separation, preferably rectification.

[0046] Preferably, the pressure of the rectification is 0.1-101 kPa, for example, it can be 0.1 kPa, 1 kPa, 10 kPa, 30 kPa, 50 kPa, 80 kPa or 101 kPa, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0047] Preferably, the rectification has a top temperature of 40-150℃ and a bottom temperature of 100-250℃.

[0048] The rectification has a top temperature of 40-150℃, for example, it can be 40℃, 50℃, 60℃, 80℃, 100℃, 120℃ or 150℃, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0049] The rectification has a bottom temperature of 100-250℃, for example, it can be 100℃, 120℃, 150℃, 160℃, 180℃, 200℃, 240℃ or 250℃, but is not limited to the listed values, and other values not listed in the range are also applicable.

[0050] As a preferred technical solution of the preparation method, the preparation method comprises the following steps:

[0051] (1) mixing a functional monomer, an ethylene ester comonomer, an initiator and a solvent to obtain a raw material solution; the molar ratio of the functional monomer, the ethylene ester comonomer and the initiator is 1:(0.1-5):(0.001-0.2); and the mass ratio of the functional monomer to the solvent is 1:(2-50);

[0052] (2) mixing an olefin and the raw material solution obtained in step (1) under an oxygen-free condition to perform a polymerization reaction, thereby obtaining a reaction product; the reaction product is subjected to pressure relief to obtain unreacted olefin and a remaining material; the unreacted olefin is reused in the polymerization reaction; the polymerization reaction has a pressure of 0.1-10 MPa, a temperature of 50-150℃ and a total time of 0.01-10 h;

[0053] (3) the remaining material is subjected to solid-liquid separation and drying to obtain the olefin functional polymer; the filtrate obtained from the solid-liquid separation is subjected to solvent recovery, and the recovered solvent is reused in step (1);

[0054] The anhydride value of the olefin functional polymer is 5-75%.

[0055] In a second aspect, the present application provides an application of the olefin functional polymer obtained by the method of the first aspect, and the olefin functional polymer is used for modifying a polyester substrate, a polyamide substrate, a polyolefin substrate or a glass fiber material.

[0056] The olefin functional polymer obtained by the present application can be used for modifying various substrates due to the multiple functional groups thereof, including but not limited to a polyester substrate, a polyamide substrate, a polyolefin substrate and / or a glass fiber material, etc.

[0057] Compared with the prior art, the present application has the following beneficial effects:

[0058] The present application provides a preparation method with mild reaction conditions. By introducing the ethylene ester comonomer, the anhydride value of the olefin functional polymer can be controlled in the range of 5-75% by adjusting the feeding amount of the ethylene ester comonomer, thereby expanding the application range and scenarios of the polymer modification. Meanwhile, by introducing the ethylene ester comonomer, the content of ester groups in the olefin functional polymer is increased, and the compatibility with the polyester material matrix is improved, so that the obtained olefin functional polymer is suitable for modifying the polyester material. Meanwhile, potential hydroxyl groups can be obtained by hydrolysis, which can further enrich the application range of the olefin functional polymer. DETAILED DESCRIPTION

[0059] The technical solutions of the present application are further illustrated by specific embodiments. Those skilled in the art should understand that the embodiments are only used to help understand the present application, and should not be regarded as specific limitations on the present application.

[0060] Example 1

[0061] The present embodiment provides a preparation method of an olefin functional polymer, which comprises the following steps:

[0062] (1) mixing a functional monomer (maleic anhydride), an ethylene ester comonomer (vinyl acetate), an initiator (benzoyl peroxide) and a solvent (butyl acetate) to obtain a raw material solution; the molar ratio of the functional monomer, the ethylene ester comonomer and the initiator is 1:0.1:0.01; the mass ratio of the functional monomer to the solvent is 1:4;

[0063] (2) after nitrogen replacement of a microchannel reactor, ethylene is introduced and the temperature is increased to 100℃ for polymerization reaction, the ethylene pressure is controlled to make the polymerization reaction pressure 5MPa, then the raw material solution obtained in step (1) is introduced for polymerization reaction to obtain a reaction material, and the residence time of the raw material solution is 0.2h;

[0064] (3) The reaction mixture is subjected to solid-liquid separation and drying to obtain the olefin functional polymer; the filtrate obtained by solid-liquid separation is subjected to rectification to recover the solvent for use in step (1); the rectification is carried out at a pressure of 50 kPa, a top temperature of 100°C, and a bottom temperature of 200°C.

[0065] Example 2

[0066] This example provides a method for preparing an olefin functional polymer, wherein the molar ratio of the functional monomer, the ethylene ester comonomer, and the initiator in step (1) is 1:0.3:0.01, and the other steps are the same as in Example 1.

[0067] Example 3

[0068] This example provides a method for preparing an olefin functional polymer, wherein the molar ratio of the functional monomer, the ethylene ester comonomer, and the initiator in step (1) is 1:0.5:0.01, and the other steps are the same as in Example 1.

[0069] Example 4

[0070] This example provides a method for preparing an olefin functional polymer, wherein the molar ratio of the functional monomer, the ethylene ester comonomer, and the initiator in step (1) is 1:1:0.01, and the other steps are the same as in Example 1.

[0071] Example 5

[0072] This example provides a method for preparing an olefin functional polymer, wherein the molar ratio of the functional monomer, the ethylene ester comonomer, and the initiator in step (1) is 1:2:0.01, and the other steps are the same as in Example 1.

[0073] Example 6

[0074] This example provides a method for preparing an olefin functional polymer, wherein the molar ratio of the functional monomer, the ethylene ester comonomer, and the initiator in step (1) is 1:5:0.01, and the other steps are the same as in Example 1.

[0075] Example 7

[0076] This example provides a method for preparing an olefin functional polymer, wherein the molar ratio of the functional monomer, the ethylene ester comonomer, and the initiator in step (1) is 1:10:0.01, and the other steps are the same as in Example 1.

[0077] Example 8

[0078] The embodiment provides a preparation method of an olefin functional polymer, wherein, in addition to the molar ratio of the functional monomer, the vinyl acetate comonomer and the initiator being 1:20:0.01 in step (1), the rest is the same as in embodiment 1.

[0079] Embodiment 9

[0080] The embodiment provides a preparation method of an olefin functional polymer, and the preparation method comprises the following steps:

[0081] (1) mixing a functional monomer (maleic anhydride), a vinyl acetate comonomer (vinyl acetate), an initiator (azobisisobutyronitrile) and a solvent (xylene) to obtain a raw material solution; the molar ratio of the functional monomer, the vinyl acetate comonomer and the initiator is 1:5:0.2; and the mass ratio of the functional monomer to the solvent is 1:50;

[0082] (2) after nitrogen replacement is performed on a reaction kettle, 1-butene is introduced and the temperature is increased to 50 DEG C, the polymerization reaction temperature, the 1-butene pressure is controlled to make the polymerization reaction pressure be 10 MPa, then the raw material solution obtained in step (1) is introduced to perform a polymerization reaction, the feeding time is 6 h, and after the reaction is completed, a reaction material is obtained, and the total residence time of the raw material solution is 10 h (namely, the reaction time is 10 h);

[0083] (3) the reaction material is subjected to solid-liquid separation and drying to obtain the olefin functional polymer; the filtrate obtained through the solid-liquid separation is subjected to rectification, and the solvent is recycled to step (1); the rectification pressure is 0.1 kPa, the top temperature is 40 DEG C, and the bottom temperature is 100 DEG C.

[0084] Embodiment 10

[0085] The embodiment provides a preparation method of an olefin functional polymer, and the preparation method comprises the following steps:

[0086] (1) mixing a functional monomer (maleic anhydride), a vinyl acetate comonomer (vinyl acetate), an initiator (benzoyl peroxide) and a solvent (n-heptane) to obtain a raw material solution; the molar ratio of the functional monomer, the vinyl acetate comonomer and the initiator is 1:5:0.005; and the mass ratio of the functional monomer to the solvent is 1:10;

[0087] (2) after nitrogen replacement is performed on a tubular reactor, 1-octene is introduced and the temperature is increased to 110 DEG C, the polymerization reaction temperature, the 1-octene pressure is controlled to make the polymerization reaction pressure be 2 MPa, then the raw material solution obtained in step (1) is introduced to perform a polymerization reaction, the feeding time is 3 h, and after the reaction is completed, a reaction material is obtained, and the total residence time of the raw material solution is 5 h (namely, the reaction time is 5 h);

[0088] (3) The reaction mixture is subjected to solid-liquid separation and drying to obtain the olefin functional polymer; the filtrate obtained by solid-liquid separation is subjected to rectification to recover the solvent for use in step (1); the rectification is carried out at a pressure of 101 kPa, a top temperature of 150°C, and a bottom temperature of 250°C.

[0089] Comparative Example 1

[0090] This comparative example provides a preparation method suitable for the preparation of an olefin functional polymer, which is identical to Example 1 except that the raw material liquid in step (1) does not contain an ethylene ester comonomer.

[0091] Performance Test

[0092] The anhydride value, particle size D50, and particle size D90 of the olefin functional polymers obtained in Examples 1-10 and Comparative Example 1 were tested, and the functional monomer conversion, ethylene ester comonomer conversion, and polymer yield in each example and comparative example were calculated, and the results are shown in Table 1.

[0093] The anhydride value was determined according to ISO 1390-4:1977 (Maleic Anhydride for Industrial Use - Test Methods - Part 4: Determination of Maleic Anhydride Content - Titration Method).

[0094] The particle sizes D50 and D90 were determined using a laser particle size analyzer.

[0095] Table 1

[0096]

[0097]

[0098] The performance of the olefin functional polymers provided in Examples 1-10 and Comparative Example 1 was tested: dry HDPE, PA66, and the olefin functional polymer were weighed in a mass ratio of 70:20:10, mixed uniformly, and then added to a twin-screw extrusion device for extrusion granulation, and then injected into a standard sample bar by an injection molding machine. The melt index was measured according to ISO 1133 method; the tensile strength was measured according to ISO 527 method, and the elongation at break was calculated; the bending strength was tested according to ISO 180 method; and the impact strength was tested according to ISO 179-1982 method, and the results are shown in Table 2.

[0099] Among them, comparative example 2 as a blank contrast: the dry HDPE and PA66 are weighed according to the mass ratio of 78:22, mixed and then added to the twin-screw extrusion device for extrusion granulation, and then injected into a standard sample bar by an injection molding machine. The melt index is measured according to the ISO 1133 method; the tensile strength is measured according to the ISO 527 method, and the elongation at break is calculated; the bending strength is tested according to the ISO 180 method; and the impact strength is tested according to the ISO 179-1982 method.

[0100] Table 2

[0101]

[0102] The higher the anhydride value, the worse the flowability of the composite material in the molten state, and the lower the melt index; as a compatibilizer, the higher the anhydride value, the better the interfacial compatibility of the composite material, the toughness is enhanced, and the results embodied are that the tensile strength, notched impact strength and elongation at break are higher. The introduction of vinyl acetate monomer greatly improves the toughness and impact resistance of the composite material on the basis of the original, and therefore it is suitable for applications such as packaging heat sealing layer, shoe material, etc.

[0103] In summary, the reaction conditions of the preparation method provided by the present application are mild, the anhydride value of the olefin functional polymer is regulated in the range of 5-75% by adjusting the amount of ethylene ester comonomer, which expands the application range and scene of polymer modification; moreover, the content of ester groups in the olefin functional polymer is increased by introducing ethylene ester comonomer, which increases the compatibility with the polyester material matrix, so that the obtained olefin functional polymer is suitable for modification of polyester materials. In addition, the introduction of ethylene ester comonomer releases the hydroxyl groups in the polymerizable main chain through hydrolysis, so that the polymer has more excellent modification performance.

[0104] The above is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and those skilled in the art should understand that any changes or replacements within the technical scope disclosed by the present application can be easily thought of by those skilled in the art, which falls within the protection scope and disclosure scope of the present application.

Claims

1. A process for the preparation of an olefin-functional polymer, characterized by, The preparation method comprises the following steps: (1) mixing a functional monomer, an ethylene ester comonomer, an initiator and a solvent to obtain a raw material solution; (2) mixing an olefin and the raw material solution obtained in step (1) under an oxygen-free condition to perform a polymerization reaction, thereby obtaining a reaction material; (3) performing solid-liquid separation and drying on the reaction material to obtain the olefin functional polymer; The molar ratio of the functional monomer to the ethylene ester comonomer in step (1) is 1:(1-5); The anhydride value of the olefin functional polymer is 9.9-46.8%, The ethylene ester comonomer in step (1) comprises any one or a combination of at least two of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate or vinyl decanoate, The functional monomer in step (1) is maleic anhydride, The reactor used in the polymerization reaction is a kettle reactor, The olefin in step (2) comprises any one or a combination of at least two of ethylene, propylene or an α-olefin, The α-olefin comprises any one or a combination of at least two of 1-butene, 1-hexene or 1-octene, The solvent in step (1) comprises any one or a combination of at least two of an organic alkanoate solvent or an aromatic compound.

2. The production method according to claim 1, characterized by, The initiator in step (1) comprises any one or a combination of at least two of an azo initiator, a peroxide initiator or a photoinitiator.

3. The preparation method according to claim 2, characterized in that, The azo initiator comprises azobisisobutyronitrile and / or azobisisoheptyl nitrile.

4. The production method according to claim 2, characterized by, The peroxide initiator comprises any one or a combination of at least two of benzoyl peroxide, dodecanoyl peroxide, dicumyl peroxide or diisopropyl peroxydicarbonate.

5. The preparation method according to claim 1, characterized in that, The molar ratio of the functional monomer to the initiator in step (1) is 1:(0.001-0.2).

6. The method of claim 1, wherein, The aromatic compound comprises any one or a combination of at least two of benzene, toluene, ethylbenzene or xylene.

7. The preparation method according to claim 1, characterized in that, The structural general formula of the organic alkanoate solvent is wherein R1 is any one of H, a C1-C20 alkyl group or a C6-C10 aryl group, and R2 is any one of a C1-C20 alkyl group or a C6-C10 aryl group.

8. The preparation method according to claim 7, characterized in that, The organic alkanoate solvent comprises any one or a combination of at least two of ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate or isoamyl phenylacetate.

9. The method of claim 1, wherein, The mass ratio of the functional monomer to the solvent in step (1) is 1:(2-50).

10. The method of claim 1, wherein, The pressure of the polymerization reaction in step (2) is 0.1-10 MPa.

11. The method of claim 1, wherein, The temperature of the polymerization reaction in step (2) is 50-150℃.

12. The method of claim 1, wherein, The total time of the polymerization reaction in step (2) is 0.01-10 h.

13. The method of claim 1, wherein, The reaction product obtained in step (2) is subjected to pressure relief to obtain unreacted olefin and residual material; The unreacted olefin is reused in the polymerization reaction in step (2); and the residual material is subjected to step (3).

14. The method of claim 1, wherein, The filtrate obtained through the solid-liquid separation in step (3) is subjected to solvent recovery, and the recovered solvent is reused in step (1).

15. The method of claim 14, wherein, The method for recovering the solvent includes any one or a combination of at least two of rectification, distillation or membrane separation.

16. The method of claim 15, wherein, The pressure of the rectification is 0.1-101 kPa.

17. The preparation method according to claim 15, characterized in that, The overhead temperature of the rectification is 40-150℃, and the bottom temperature is 100-250℃.

18. The application of an olefin functional polymer obtained by the preparation method according to any one of claims 1-17, characterized in that, The olefin functional polymer is used for modification of a polyester base material, a polyamide base material, a polyolefin base material or a glass fiber material.

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