Maleic anhydride-isobutylene-styrene terpolymer microspheres, methods of making and applications thereof

Abstract

The application relates to the field of high-molecular polymers and discloses a maleic anhydride-isobutene-styrene ternary copolymer microsphere and a preparation method and application thereof. Based on the total mole amount of the copolymer, the mole content of a structural unit provided by maleic anhydride is 47-52%; the mole ratio of a structural unit provided by isobutene to a structural unit provided by styrene is 1:0.2-7.5. The copolymer microsphere is uniform in particle size and clean in surface. The structural unit provided by isobutene and the structural unit provided by styrene have a specific mole ratio, and are matched with the specific mole content of the structural unit provided by maleic anhydride, so that the ternary copolymer microsphere has good application as a polarity modifier in polyolefins, significantly reduces the water contact angle of polyolefin materials and does not cause the mechanical property of the materials to decrease.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high molecular polymers, in particular, to a maleic anhydride-isobutylene-styrene terpolymer microsphere and a preparation method and application thereof. BACKGROUND

[0002] Maleic anhydride copolymers have a wide range of applications due to their good processing performance, excellent reactivity, good hydrophilicity, and low price. Sun Dalili et al. in "Application Research of Styrene-maleic Anhydride Copolymer in Continuous Multistage Treatment of High Concentration Lead Ion Wastewater, New Chemical Materials, 2022, 50(01): 303-307+312" achieved the purification of high-concentration lead ion wastewater by using styrene-maleic anhydride copolymer.

[0003] Tang Longdong et al. in "Wear Resistance Modification of Nylon 6 / Glass Fiber Composites by Styrene-maleic Anhydride Copolymer, Plastics Industry, 2017, 45(04): 48-51." prepared polyamide 6 / glass fiber / styrene-maleic anhydride copolymer composite materials using styrene-maleic anhydride copolymer as a modifier, which effectively improved the wear resistance of polyamide 6 / glass fiber composite materials.

[0004] In the prior art, most of the copolymers containing maleic anhydride are prepared by solution or traditional precipitation polymerization. Ling Zhicheng et al. in "Esterification and Application of Star-shaped Styrene-maleic Anhydride Copolymer [J]. Coatings and Protection, 2019, 40(11): 20-25." prepared star-shaped maleic anhydride-styrene copolymer by precipitation polymerization, and through esterification modification, the glass transition temperature of the copolymer was reduced, and the dispersion effect on pigments was improved.

[0005] Shi Xuelong et al. in "Synthesis and Characterization of Styrene-maleic Anhydride Random Copolymer in Green Solvent, Plastics Science and Technology, 2019, 47(02): 24-28." prepared styrene-maleic anhydride random copolymer by solution polymerization using green solvent dimethyl carbonate as solvent.

[0006] Polypropylene is an important general-purpose thermoplastic material, which is widely used due to its good mechanical properties, processing performance, corrosion resistance, and electrical insulation. At the same time, polypropylene is a crystalline polymer with a regular structure, and the surface lacks active groups, so its water contact angle is large and the surface wettability is poor, which limits its application in water environment, surface coating, surface bonding, and composite materials. At present, the main methods to improve the hydrophilicity of polypropylene materials include flame treatment, isopropyl alcohol wiping, and adding polar modifiers such as grafted polypropylene. Among them, flame treatment and isopropyl alcohol wiping are the most commonly used, but they have the problems of high labor cost and high safety risk.

[0007] However, there is no report in the prior art that a copolymer containing maleic anhydride-isobutylene-styrene can be added to a polymer system such as polypropylene as a polar modifier to improve the hydrophilicity thereof. SUMMARY

[0008] The present application aims to overcome the problems in the prior art that the preparation process of styrene-maleic anhydride copolymer is complex, and no scheme for preparing a copolymer containing maleic anhydride-isobutylene-styrene is involved, and the grafting rate of the grafted polypropylene polar modifier currently used to improve the hydrophilicity of the polyolefin system is low, the improvement of the hydrophilicity is limited, and the aging resistance is poor. A maleic anhydride-isobutylene-styrene terpolymer microsphere, a preparation method and application thereof are provided. The surface of the maleic anhydride-isobutylene-styrene terpolymer microsphere is clean and free of pollution, and the microsphere particles are uniform. The structural units provided by isobutylene and the structural units provided by styrene have a specific molar ratio, and are matched with a specific molar content of the structural units provided by maleic anhydride. When the terpolymer is used as a polar modifier in a polyolefin, the water contact angle of the polyolefin material can be reduced without causing a decrease in the mechanical properties of the material.

[0009] To achieve the above-mentioned purpose, the first aspect of the present application provides a maleic anhydride-isobutylene-styrene terpolymer microsphere, wherein the molar content of the structural units provided by maleic anhydride is 47-52% based on the total molar amount of the terpolymer; and the molar ratio of the structural units provided by isobutylene to the structural units provided by styrene is 1:0.2-7.5.

[0010] The second aspect of the present application provides a preparation method of a maleic anhydride-isobutylene-styrene terpolymer microsphere, wherein the method comprises the following steps:

[0011] S1. Dissolving polymer monomers and an initiator in a reaction medium to form a homogeneous solution in an inert atmosphere;

[0012] S2. After the homogeneous solution is subjected to a polymerization reaction to obtain a copolymer emulsion, the terpolymer microspheres are separated;

[0013] The polymer monomers are maleic anhydride, styrene and isobutylene;

[0014] The molar content of the maleic anhydride is 47-52% based on the total mass of the polymer monomers;

[0015] The molar ratio of the isobutylene to the styrene is 1:0.2-7.5.

[0016] The third aspect of the present application provides a maleic anhydride-isobutylene-styrene terpolymer microsphere prepared by the preparation method of the second aspect.

[0017] The fourth aspect of this invention provides the application of maleic anhydride-isobutylene-styrene terpolymer microspheres as described in the first or third aspect as a polar modifier in polyolefins.

[0018] Through the above technical solution, the maleic anhydride-isobutylene-styrene terpolymer microspheres, their preparation method, and applications provided by this invention achieve the following beneficial effects: the maleic anhydride-isobutylene-styrene terpolymer microspheres have uniform particle size and clean, uncontaminated surfaces. The structural units provided by isobutylene and styrene have a specific molar ratio, combined with a specific molar content of structural units provided by maleic anhydride, enabling the terpolymer microspheres to function effectively as polar modifiers in polyolefins, significantly reducing the water contact angle of polyolefin materials without causing a decrease in their mechanical properties. Attached Figure Description

[0019] Figure 1 This is the infrared spectrum of the copolymer microspheres prepared in Example 1;

[0020] Figure 2 This is a scanning electron microscope image of the copolymer microspheres prepared in Example 1. Detailed Implementation

[0021] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0022] The first aspect of the present invention provides maleic anhydride-isobutylene-styrene terpolymer microspheres, wherein, based on the total molar amount of the terpolymer, the molar content of the structural units provided by maleic anhydride is 47-52%; and the molar ratio of the structural units provided by isobutylene to the structural units provided by styrene is 1:0.2-7.5.

[0023] In this invention, the structural units provided by isobutylene and the structural units provided by styrene in the terpolymer microspheres satisfy the above-mentioned molar ratio range. Combined with a specific molar content of the structural units provided by maleic anhydride, the terpolymer microspheres, when used as a polar modifier in polyolefins, can significantly reduce the water contact angle of the polyolefin material without causing a decrease in the mechanical properties of the material.

[0024] According to the application, the mole content of the structural unit provided by maleic anhydride is 48-51% based on the total mole amount of the terpolymer; the mole ratio of the structural unit provided by isobutylene to the structural unit provided by styrene is 1:1-5.

[0025] According to the application, the particle size of the terpolymer microspheres is 500-920m.

[0026] In the application, the particle size of the terpolymer microspheres meets the above range, which can further improve the water contact angle of polyolefin when applied.

[0027] Further, the particle size of the terpolymer microspheres is 530-800nm.

[0028] The second aspect of the application provides a preparation method of maleic anhydride-isobutylene-styrene terpolymer microspheres, wherein the method comprises the following steps:

[0029] S1, dissolving polymer monomers and initiators in a reaction medium to form a homogeneous solution in an inert atmosphere;

[0030] S2, after the homogeneous solution is subjected to a polymerization reaction to obtain a copolymer emulsion suspension, the terpolymer microspheres are separated;

[0031] The polymer monomers are maleic anhydride, styrene and isobutylene;

[0032] The mole content of the maleic anhydride is 47-52% based on the total mass of the polymer monomers;

[0033] The mole ratio of the isobutylene to the styrene is 1:0.2-7.5.

[0034] In the application, the maleic anhydride monomers, isobutylene monomers and styrene monomers are polymerized in a specific ratio by copolymerization, so that the prepared maleic anhydride-isobutylene-styrene copolymer presents excellent microspheres in uniformity, and the terpolymer has the characteristics of clean surface and uniform particle size, and the obtained terpolymer microspheres have polarity, which can significantly reduce the water contact angle and improve the hydrophilicity.

[0035] According to the application, the mole content of the maleic anhydride is 48-51% based on the total mass of the polymer monomers; the mole ratio of the isobutylene to the styrene is 1:1-5.

[0036] According to the application, the mass concentration of the polymer monomers is 4-23wt%, preferably 6-21wt% based on the total weight of the homogeneous solution.

[0037] According to the application, the initiator is an organic peroxide and / or an azo compound.

[0038] According to the present invention, the organic peroxide is selected from at least one of benzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, dodecyl peroxide, tert-butyl peroxide, diisopropyl peroxide, and dicyclohexyl peroxide.

[0039] According to the present invention, the azo compound is selected from azobisisobutyronitrile and / or azobisisoheptanenitrile.

[0040] According to one embodiment of the present invention, the reaction medium is an organic acid alkyl ester.

[0041] According to one embodiment of the present invention, the reaction medium is a mixed solvent of ketone compounds and alkane compounds.

[0042] According to one embodiment of the present invention, the reaction medium is a mixed solvent of organic acid alkyl esters, ketone compounds and alkane compounds.

[0043] In this invention, compounds selected from the above-mentioned types are used as reaction media, which can cooperate with the specific amount of polymerizable monomers described in this invention. Without the need for additional stabilizers and precipitants, etc., the self-stabilizing precipitation polymerization reaction of maleic anhydride, isobutylene, and styrene can be achieved. No stabilizers or co-stabilizers are needed in the polymerization reaction system, which has a self-stabilizing dispersion effect. The obtained copolymer microspheres have clean surfaces and uniform particle sizes. The copolymer microspheres obtained thereby can be used as polar modifiers in polyolefins to reduce the water contact angle of polyolefin materials.

[0044] Furthermore, when using a mixed solvent of ketone compounds and alkane compounds, or a mixed solvent of organic acid alkyl esters, ketone compounds and alkane compounds, the problem of the material having a special odor caused by using ester solvents alone can be improved.

[0045] According to the present invention, the general formula of the organic acid alkyl ester is R1COOR2, wherein R1 is selected from H and C. 1-5 alkyl or C 6-10 Aryl group, R2 is C 1-10 Alkyl groups.

[0046] In this invention, C 1-5 The alkyl groups include straight-chain alkyl groups of C1-C5 and branched alkyl groups of C3-C5, and specific examples may include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl and isopentyl, etc.

[0047] In this invention, the term "aryl group" can be represented as Ar. x-N-, wherein x Ar's are the same or different, each independently an aryl group, N is an alkyl group, and x is an integer from 1 to 3. In the present application, the aryl group of the aralkyl group has 6 to 10 carbon atoms. 10 Specific examples of the aralkyl group of the formula -C6-C10 aryl-C1-C4 alkyl- can include, but are not limited to, phenylmethyl, phenylethyl, phenyl-n-propyl, phenyl-n-butyl, phenyl-t-butyl, phenyl-i-propyl, and phenyl-n-butyl, etc.

[0048] Further, R1 is a C1-C4 alkyl group or a C6-C10 aralkyl group, R2 is a C1-C4 alkyl group, and R3 and R4 are each independently a C1-C3 alkyl group. 1-5 Further, R1 is a C1-C4 alkyl group or a C6-C10 aralkyl group, R2 is a C1-C4 alkyl group, and R3 and R4 are each independently a C1-C3 alkyl group. 6-9 Further, R1 is a C1-C4 alkyl group or a C6-C10 aralkyl group, R2 is a C1-C4 alkyl group, and R3 and R4 are each independently a C1-C3 alkyl group. 1-7 Further, R1 is a C1-C4 alkyl group or a C6-C10 aralkyl group, R2 is a C1-C4 alkyl group, and R3 and R4 are each independently a C1-C3 alkyl group.

[0049] According to a particularly preferred embodiment of the present application, the organic acid alkyl ester is selected from at least one of ethyl formate, propyl formate, i-butyl formate, pentyl formate, ethyl acetate, butyl acetate, i-butyl acetate, sec-butyl acetate, pentyl acetate, i-amyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, i-amyl butyrate, ethyl i-amylate, i-amyl i-amylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, i-amyl benzoate, methyl phenylacetate, and ethyl phenylacetate.

[0050] According to the present application, the ketone compound has a structure shown in the formula I:

[0051]

[0052] wherein R3 and R4 are each independently a C1-C6 alkyl group.

[0053] Further, R3 and R4 are each independently a C1-C3 alkyl group.

[0054] According to the present application, the alkane compound is an alkane having 6 to 12 carbon atoms, preferably an alkane having 6 to 10 carbon atoms.

[0055] According to an embodiment of the present application, the reaction medium is a mixed solvent of the ketone compound and the alkane compound, wherein the amount of the alkane compound is 50 to 90 vol% of the mixed solvent of the ketone compound and the alkane compound.

[0056] In the present application, the amount of the alkane compound satisfies the above range, and the copolymer microspheres prepared thereby can further reduce the water contact angle of the polyolefin when applied to the polyolefin.

[0057] Further, the amount of the alkane compound is 50 to 80 vol% of the mixed solvent of the ketone compound and the alkane compound.

[0058] According to one embodiment of the present application, the reaction medium is a mixed solvent of organic acid alkyl ester, ketone compound and alkane compound, wherein the amount of alkane compound is 0-50 vol% of the mixed solvent, preferably 1-30 vol%; the amount of ketone compound is 1-10 vol% of the mixed solvent of organic acid alkyl ester, ketone compound and alkane compound, preferably 1-5 vol%.

[0059] In the present application, it is to be noted that when the reaction medium is a mixed solvent of organic acid alkyl ester, ketone compound and alkane compound, the amounts of ketone compound and alkane compound are not both 0.

[0060] In the present application, the polymerization reaction is carried out in a protective atmosphere, which can be provided by conventional inert gas or nitrogen gas in the prior art.

[0061] According to the present application, the conditions of the polymerization reaction include: the polymerization temperature is 40-95℃, preferably 50-80℃; the polymerization time is 1-24h, preferably 3-10h.

[0062] In the present application, in order to realize self-stabilization of the polymerization system and further obtain copolymer microspheres with uniform particle size and clean surface without pollution, the inventors have studied the conditions of the polymerization reaction. It has been found that when the polymerization temperature is 40-95℃ and the polymerization time is 1-24h, the polymerization system forms a stable self-stabilization system, in which maleic anhydride, isobutene and styrene are polymerized to form microspheres, and the microspheres do not aggregate and have good dispersibility.

[0063] In the present application, the separation can be a conventional solid-liquid separation method in the art, such as centrifugal separation.

[0064] In the present application, when centrifugal separation is used, the rotation speed of centrifugation is 1500-5000 rad / min, and the centrifugation time is 5-60 min.

[0065] The third aspect of the present application provides a maleic anhydride-isobutene-styrene terpolymer microsphere prepared by the preparation method of the second aspect.

[0066] According to the present application, the mole content of structural units provided by maleic anhydride is 47-52%, preferably 48-51%, based on the total mole amount of the terpolymer; and the mole ratio of structural units provided by isobutene to structural units provided by styrene is 1:0.2-7.5, preferably 1:1-5.

[0067] According to the present application, the particle size of the terpolymer microsphere is 500-920 nm, preferably 530-800 nm.

[0068] The fourth aspect of the present application provides the use of the maleic anhydride-isobutylene-styrene terpolymer microspheres of the first aspect or the third aspect as a polar modifier in polyolefins.

[0069] According to the present application, the amount of the terpolymer microspheres is 1-10 wt% based on the total weight of the polyolefin.

[0070] In the present application, the amount of the terpolymer microspheres meets the above range, which can reduce the water contact angle of the polyolefin material without reducing the mechanical property of the polyolefin material.

[0071] Further, the amount of the terpolymer microspheres is 2-6 wt% based on the total weight of the polyolefin.

[0072] According to the present application, the polyolefin is polypropylene.

[0073] According to the present application, the melt index of the polypropylene is 3-12 g / 10 min under a load of 2.16 kg at 190℃.

[0074] In the present application, the melt index of the polypropylene meets the above range, which can better blend with the microsphere material.

[0075] Further, the melt index of the polypropylene is 4-10 g / 10 min under a load of 2.16 kg at 190℃.

[0076] The present application will be described in detail by way of examples below. In the following examples,

[0077] The polymerization yield (Cp) is calculated according to the following formula p ) is calculated according to the following formula

[0078] Cp=Mp×100% / Mm

[0079] wherein Mp is the mass of the obtained polymer; Mm is the total mass of the added monomers;

[0080] The morphology and particle size of the copolymer microspheres are observed and measured by scanning electron microscopy (SEM);

[0081] The infrared spectrum of the copolymer is tested by FI-IR;

[0082] The content of each structural unit in the copolymer is tested by H NMR, and the testing method is to calculate the content of each structural unit by the ratio of the peak area of the characteristic hydrogen in the corresponding structural unit in H NMR; 1 1

[0083] ​​The water contact angle of the modified polypropylene material was tested according to GB-T-30693-2014, using a sample size of 20mm*20mm*2mm, and a dynamic contact angle measuring instrument was used for testing.

[0084] The room temperature cantilever beam notched impact strength of the modified polypropylene material was tested according to GB-T-1843-2008.

[0085] All other raw materials used in the examples and comparative examples are commercially available products.

[0086] Example 1

[0087] 49g of maleic anhydride, 1g of azobisisobutyronitrile (AIBN), 8.4g of isobutylene, 36.4g of styrene, and 500mL of isoamyl acetate (R1 is a C1 alkyl group, R2 is a C5 alkyl group) were added to a 2L reactor. After the materials were mixed evenly, the temperature was raised to 70℃ and the reaction was carried out for 4 hours. After the reaction was completed, the resulting polymer emulsion suspension was centrifuged at 2000 rad / min for 20 minutes to obtain 85.43g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 90.12%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A1 was 650nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutylene to styrene was 1:2.3.

[0088] like Figure 1 The FI-IR image of copolymer microspheres A1 shown is at 1785 cm⁻¹. -1 1850cm -1 The characteristic absorption peak of the anhydride group is shown.

[0089] like Figure 2 The SEM image of copolymer microsphere A1 shown shows that the copolymer microspheres are uniform in size and the particle surface is clean and uncontaminated.

[0090] Example 2

[0091] 49g of maleic anhydride, 1g of azobisisobutyronitrile (AIBN), 4.66g of isobutylene, 43.43g of styrene, and 500mL of isoamyl acetate (R1 is a C1 alkyl group, R2 is a C5 alkyl group) were added to a 2L reactor. After the materials were mixed evenly, the temperature was raised to 70℃ and the reaction was carried out for 6 hours. After the reaction was completed, the resulting polymer emulsion suspension was centrifuged at 2000 rad / min for 20 minutes to obtain 88.08g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 89.79%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A2 was 750nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutylene to styrene was 1:5.

[0092] Example 3

[0093] 51 g of maleic anhydride, 1 g of azobisisobutyronitrile, 14 g of isobutene, 26 g of styrene, 500 mL of butyl acetate (R1 is C1 alkyl, R2 is C4 alkyl) were added to a 2 L reaction kettle, after the material was uniformly mixed, the temperature was raised to 65°C, and the reaction was carried out for 6 h. After the reaction was completed, the obtained polymer emulsion suspension was separated by centrifuge at a speed of 2000 rad / min for 20 min, and maleic anhydride-isobutene-styrene terpolymer microspheres 78.38 g were obtained, corresponding to the yield of copolymer 85.2%. The particle size of maleic anhydride-isobutene-styrene terpolymer microspheres A3 was 590 nm. Among them, the molar content of maleic anhydride was 51%; the molar ratio of isobutene to styrene was 1:1.

[0094] Example 4

[0095] 47.08 g of maleic anhydride, 1 g of azobisisobutyronitrile, 3.51 g of isobutene, 45.57 g of styrene, 500 mL of butyl acetate (R1 is C1 alkyl, R2 is C4 alkyl) were added to a 2 L reaction kettle, after the material was uniformly mixed, the temperature was raised to 65°C, and the reaction was carried out for 8 h. After the reaction was completed, the obtained polymer emulsion suspension was separated by centrifuge at a speed of 2000 rad / min for 20 min, and maleic anhydride-isobutene-styrene terpolymer microspheres 91.18 g were obtained, corresponding to the yield of copolymer 93.85%. The particle size of maleic anhydride-isobutene-styrene terpolymer microspheres A4 was 770 nm. Among them, the molar content of maleic anhydride was 49%; the molar ratio of isobutene to styrene was 1:7.3.

[0096] Example 5

[0097] 51 g of maleic anhydride, 1 g of azobisisobutyronitrile, 19.64 g of isobutene, 15.62 g of styrene, 500 mL of isoamyl acetate (R1 is C1 alkyl, R2 is C5 alkyl) were added to a 2 L reaction kettle, after the material was uniformly mixed, the temperature was raised to 70°C, and the reaction was carried out for 4 h. After the reaction was completed, the obtained polymer emulsion suspension was separated by centrifuge at a speed of 2000 rad / min for 20 min, and maleic anhydride-isobutene-styrene terpolymer microspheres 74.92 g were obtained, corresponding to the yield of copolymer 85.86%. The particle size of maleic anhydride-isobutene-styrene terpolymer microspheres A5 was 548 nm. Among them, the molar content of maleic anhydride was 51%; the molar ratio of isobutene to styrene was 1:0.4.

[0098] Example 6

[0099] 49g of maleic anhydride, 1g of azobisisobutyronitrile (AIBN), 22.44g of isobutylene, 10.42g of styrene, and 500mL of ethyl acetate (R1 is a C1 alkyl group, and R2 is a C2 alkyl group) were added to a 2L reactor. After the materials were mixed evenly, the temperature was raised to 70℃ and the reaction was carried out for 4 hours. After the reaction was completed, the resulting polymer emulsion suspension was centrifuged at 2000 rad / min for 20 minutes to obtain 56.86g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 86.11%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A6 was 532nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutylene to styrene was 1:0.25.

[0100] Example 7

[0101] 49g of maleic anhydride, 1g of azobisisobutyronitrile, 8.4g of isobutylene, 36.4g of styrene, 250mL of acetone (50 vol%), and 250mL of hexane (50 vol%) were added to a 2L reactor. After the materials were mixed evenly, the temperature was raised to 50℃ and the reaction was carried out for 6 hours. After the reaction was completed, the resulting polymer emulsion suspension was centrifuged at 2000 rad / min for 20 minutes to obtain 84.92g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 89.58%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A7 was 676nm. The molar content of maleic anhydride was 51%, and the molar ratio of isobutylene to styrene was 1:2.3.

[0102] Example 8

[0103] The polymerization was carried out according to the method of Example 1, except that the polymerization temperature was 85°C and the reaction time was 6 hours. 74.21 g of maleic anhydride-isobutylene-styrene terpolymer microspheres were obtained, corresponding to a copolymer yield of 78.28%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A8 was 643 nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutylene to styrene was 1:2.3.

[0104] Example 9

[0105] The method of Example 7 was followed, except that 50 mL of acetone (10 vol%) and 450 mL of hexane (90 vol%) were used to prepare 65.73 g of maleic anhydride-isobutylene-styrene terpolymer microspheres, corresponding to a copolymer yield of 69.34%. The particle size of the maleic anhydride-isobutylene-styrene terpolymer microspheres A9 was 918 nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutylene to styrene was 1:2.3.

[0106] Example 10

[0107] 49 g of maleic anhydride, 1 g of azobisisobutyronitrile, 8.4 g of isobutene, 36.4 g of styrene, 300 mL (60 vol%) of ethyl acetate, 20 mL (4 vol%) of acetone, and 180 mL (36 vol%) of hexane were used to prepare 80.16 g of maleic anhydride-isobutene-styrene terpolymer microspheres, with a yield of 84.56% of copolymer. The particle size of the maleic anhydride-isobutene-styrene terpolymer microspheres A10 was 665 nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutene to styrene was 1:2.3.

[0108] Comparative Example 1

[0109] The method of Example 1 was followed, except that 49 g of maleic anhydride, 1 g of azobisisobutyronitrile, 25.2 g of isobutene, and 5.2 g of styrene were used to obtain 70.52 g of maleic anhydride-isobutene-styrene terpolymer microspheres, with a yield of 88.71% of copolymer. The particle size of the maleic anhydride-isobutene-styrene terpolymer microspheres D1 was 492 nm. The molar content of maleic anhydride was 50%, and the molar ratio of isobutene to styrene was 1:0.11.

[0110] Comparative Example 2

[0111] The method of Example 1 was followed, except that 49 g of maleic anhydride, 1 g of azobisisobutyronitrile, and 52 g of styrene were used without isobutene to obtain 96.67 g of maleic anhydride-styrene binary copolymer microspheres, with a yield of 94.77% of copolymer. The particle size of the maleic anhydride-styrene binary copolymer microspheres D2 was 947 nm. The molar content of maleic anhydride was 50%, and the molar content of styrene was 50%.

[0112] Test Example

[0113] Extrusion granulation: The copolymer microspheres prepared in the examples and comparative examples were added to polypropylene in the amounts shown in Table 1, and extrusion granulation was performed to obtain polypropylene materials. The experimental conditions for granulation were as follows: 180°C for the feeding section; 190°C for the plasticizing section; 195°C for the homogenizing section; 180°C for the die, and a rotation speed of 150 rad / min.

[0114] And the existing isopropyl alcohol wiping treatment to improve the hydrophilicity of polypropylene material test as a comparative example, the specific processing method is as follows:

[0115] (1) The surface of the polypropylene sample (20 mm*20 mm*2 mm) was cleaned with deionized water and dried with nitrogen blowing;

[0116] (2) The wiping cloth was soaked with isopropyl alcohol reagent, wrung out, and then uniformly wiped on the surface of the polypropylene sample, and naturally air-dried;

[0117] (3) Repeat step (2) for 3 times to obtain the modified polypropylene material.

[0118] The results of the performance of the polypropylene material after adding the copolymer microspheres to the polypropylene and the isopropanol wiping treatment are shown in Table 1.

[0119] Table 1

[0120]

[0121]

[0122] As can be seen from the results in Table 1, the terpolymer microspheres prepared by the embodiments 1-9 of the present application can effectively reduce the water contact angle of the polypropylene when applied to the polypropylene, and the water contact angle is not greater than 70°, while not reducing the mechanical properties.

[0123] Among them, the preferred embodiments 1-3, 10 can further reduce the water contact angle to achieve the effect of the water contact angle not greater than 63°.

[0124] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A maleic anhydride-isobutylene-styrene terpolymer microsphere, wherein, The mole content of the structural unit provided by maleic anhydride is 47-52% based on the total mole amount of the terpolymer; the mole ratio of the structural unit provided by isobutylene to the structural unit provided by styrene is 1:0.2-7.5; The reaction medium for preparing the terpolymer microspheres is an organic acid alkyl ester, or a mixed solvent of a ketone compound and an alkane compound, or a mixed solvent of an organic acid alkyl ester, a ketone compound and an alkane compound. The amount of the alkane compound in the mixed solvent of the ketone compound and the alkane compound is 50-80 vol% of the mixed solvent.

2. The terpolymer microspheres according to claim 1, wherein, The mole content of the structural unit provided by maleic anhydride is 48-51% based on the total mole amount of the terpolymer; The mole ratio of the structural unit provided by isobutylene to the structural unit provided by styrene is 1:1-5.

3. The terpolymer microspheres according to claim 1 or 2, wherein, The particle size of the terpolymer microspheres is 500-800 nm.

4. The terpolymer microspheres according to claim 1 or 2, wherein, The particle size of the terpolymer microspheres is 530-800 nm.

5. A process for the preparation of maleic anhydride-isobutylene-styrene terpolymer microspheres, wherein, The method comprises the following steps: S1. Dissolving polymer monomers and an initiator in a reaction medium in an inert atmosphere to form a homogeneous solution; S2. After the homogeneous solution is subjected to a polymerization reaction to obtain a copolymer emulsion suspension, the terpolymer microspheres are separated; The polymer monomers are maleic anhydride, styrene and isobutylene; The mole content of the maleic anhydride is 47-52% based on the total mass amount of the polymer monomers; The mole ratio of the isobutylene to the styrene is 1:0.2-7.5; The reaction medium is an organic acid alkyl ester, or a mixed solvent of a ketone compound and an alkane compound, or a mixed solvent of an organic acid alkyl ester, a ketone compound and an alkane compound. The amount of the alkane compound in the mixed solvent of the ketone compound and the alkane compound is 50-80 vol% of the mixed solvent.

6. The production method according to claim 5, wherein The mole content of the maleic anhydride is 48-51% based on the total mass amount of the polymer monomers; the mole ratio of the isobutylene to the styrene is 1:1-5.

7. The production method according to claim 5, wherein The mass concentration of the polymer monomers is 4-23 wt% based on the total weight of the homogeneous solution.

8. The production method according to claim 5, wherein The mass concentration of the polymer monomers is 6-21 wt% based on the total weight of the homogeneous solution.

9. The production method according to claim 5, wherein The initiator is an organic peroxide and / or an azo compound.

10. The production method according to claim 9, wherein The organic peroxide is at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, dilauryl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.

11. The production method according to claim 9, wherein The azo compound is at least one selected from the group consisting of azobisisobutyronitrile and / or azobisisoheptyl nitrile.

12. The method of making according to claim 5, wherein, The general formula of the organic acid alkyl ester is R1COOR2, R1 is selected from H, C 1-5 alkyl or C 6-10 aralkyl, R2 is C 1-10 alkyl.

13. The method of making according to claim 12, wherein, R1in the general formula of the organic acid alkyl ester is C 1-5 alkyl or C 6-9 aralkyl, R2is C 1-7 alkyl.

14. The method of producing according to claim 5, wherein, The organic acid alkyl ester is at least one selected from the group consisting of methyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isoamylate, isoamyl isoamylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate.

15. The method of producing according to claim 5, wherein, The ketone compound has a structure shown in Formula I: Formula I; wherein R3and R4are each independently a C 1-6 alkyl group.

16. The method of making according to claim 15, wherein, R3and R4in said formula I are each independently C 1-3 alkyl.

17. The method of making according to claim 5, wherein, The alkane compound is a C 6-12 alkane.

18. The method of making according to claim 5, wherein, The alkane compound is a C 6-10 alkane.

19. The method of producing according to claim 5, wherein, The amount of the alkane compound in the mixed solvent of the organic acid alkyl ester, the ketone compound and the alkane compound is 0-50 vol% of the mixed solvent.

20. The method of manufacturing according to claim 5, wherein, The amount of the alkane compound in the mixed solvent of the organic acid alkyl ester, the ketone compound and the alkane compound is 1-30 vol% of the mixed solvent.

21. The method of manufacturing according to claim 5, wherein, The amount of the ketone compound in the mixed solvent of the organic acid alkyl ester, the ketone compound and the alkane compound is 0-10 vol% of the mixed solvent.

22. The method of manufacturing according to claim 5, wherein, The amount of the ketone compound in the mixed solvent of the organic acid alkyl ester, the ketone compound and the alkane compound is 1-5 vol% of the mixed solvent.

23. The method of making according to any one of claims 5-22, wherein, The conditions of the polymerization reaction include: the polymerization temperature is 40-95℃; and the polymerization time is 1-24h.

24. The method of making according to any one of claims 5-22, wherein, The conditions of the polymerization reaction include: the polymerization temperature is 50-80℃; and the polymerization time is 3-10h.

25. The maleic anhydride-isobutylene-styrene terpolymer microspheres prepared by the preparation method of any one of claims 5-24.

26. The maleic anhydride-isobutylene-styrene terpolymer microspheres of claim 25, wherein, The mole content of the structural units provided by the maleic anhydride is 47-52% based on the total mole amount of the terpolymer; and the mole ratio of the structural units provided by the isobutylene to the structural units provided by the styrene is 1:0.2-7.

5.

27. The maleic anhydride-isobutylene-styrene terpolymer microspheres of claim 25, wherein, The mole content of the structural units provided by the maleic anhydride is 48-51% based on the total mole amount of the terpolymer; and the mole ratio of the structural units provided by the isobutylene to the structural units provided by the styrene is 1:1-5.

28. The maleic anhydride-isobutylene-styrene terpolymer microspheres of claim 25, wherein, The particle size of the terpolymer microspheres is 500-800nm.

29. The maleic anhydride-isobutylene-styrene terpolymer microspheres of claim 25, wherein, The particle size of the terpolymer microspheres is 530-800nm.

30. The maleic anhydride-isobutylene-styrene terpolymer microspheres of any one of claims 1-4 and 25-29 as a polar modifier in a polyolefin.

31. The use according to claim 30, wherein, The amount of the terpolymer microspheres is 1-10 wt% based on the total weight of the polyolefin.

32. The use of claim 30, wherein, The amount of the terpolymer microspheres is 2-6 wt% based on the total weight of the polyolefin.

33. The use according to any one of claims 30-32, wherein, The polyolefin is polypropylene.

34. The use of claim 33, wherein, The melt index of the polypropylene at 190℃ under a load of 2.16kg is 3-12g / 10min.

35. The use of claim 33, wherein, The melt index of the polypropylene at 190℃ under a load of 2.16kg is 4-10g / 10min.

Images