CN116262803A - Maleic anhydride-isobutene copolymer microsphere and preparation method and application thereof - Google Patents
Maleic anhydride-isobutene copolymer microsphere and preparation method and application thereof Download PDFInfo
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- CN116262803A CN116262803A CN202111522526.2A CN202111522526A CN116262803A CN 116262803 A CN116262803 A CN 116262803A CN 202111522526 A CN202111522526 A CN 202111522526A CN 116262803 A CN116262803 A CN 116262803A
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 124
- 239000004005 microsphere Substances 0.000 title claims abstract description 89
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 71
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000012429 reaction media Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 239000002270 dispersing agent Substances 0.000 claims abstract description 15
- -1 polyethylene Polymers 0.000 claims abstract description 15
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 14
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 239000004698 Polyethylene Substances 0.000 claims abstract description 10
- 239000000839 emulsion Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 229920000573 polyethylene Polymers 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 57
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical group 0.000 claims description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 229920000642 polymer Polymers 0.000 abstract description 31
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 230000009965 odorless effect Effects 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 21
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- JDPQWHLMBJZURR-UHFFFAOYSA-N decan-5-one Chemical group CCCCCC(=O)CCCC JDPQWHLMBJZURR-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- RPOCFUQMSVZQLH-UHFFFAOYSA-N furan-2,5-dione;2-methylprop-1-ene Chemical group CC(C)=C.O=C1OC(=O)C=C1 RPOCFUQMSVZQLH-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229940117955 isoamyl acetate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- ZAJNGDIORYACQU-UHFFFAOYSA-N methyl n-octyl ketone Natural products CCCCCCCCC(C)=O ZAJNGDIORYACQU-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical group CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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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
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the field of polymers, and discloses a maleic anhydride-isobutene copolymer microsphere, and a preparation method and application thereof. The method comprises the steps of dissolving a polymerization monomer and an initiator in a medium in a protective atmosphere to obtain a mixed solution, carrying out polymerization reaction on the mixed solution to obtain a copolymer emulsion suspension, and separating the copolymer emulsion suspension to obtain maleic anhydride-isobutene copolymer microspheres; the polymerized monomers are maleic anhydride and isobutene; 50-90wt% of maleic anhydride and 10-50wt% of isobutene, based on the total weight of the polymerized monomers; the reaction medium is a mixture of a compound shown in the formula (1) and alkane;
wherein R is 1 And R is 2 Each independently is an alkyl group having 1 to 6 carbon atoms. The copolymer microsphere prepared by the specific reaction medium and the specific dosage of monomer has uniform particle size, and is clean and odorless. The polymer microsphere has the effect of no migration and no precipitation in polyethylene as a dispersing agent.
Description
Technical Field
The invention relates to the field of high molecular polymers, in particular to a maleic anhydride-isobutene copolymer microsphere, and a preparation method and application thereof.
Background
The copolymer of isobutene and maleic anhydride is an amphiphilic polymer with good heat stability and hydrophilicity and lipophilicity, and is commonly used as a dispersing agent. Conventional polymers of maleic anhydride isobutylene are typically prepared in aliphatic hydrocarbon, dimethylformamide or ester solvents.
In the prior art, the traditional maleic anhydride copolymer uses some reaction solvents and post-treatment solvents, the preparation process is complex, many solvents are environment-friendly and poor, and generally, microsphere materials are difficult to obtain. The maleic anhydride microsphere material can be prepared by adopting an ester solvent such as isoamyl acetate, but the material has smell even if the material contains a small amount of residual ester solvent due to the special interaction of the polymer and the ester solvent and the special smell of the ester solvent, so that the application occasion of the material is limited by the existence of smell, and the traditional organic micromolecular dispersing agent is easy to migrate, so that the dispersion stability is poor.
Therefore, developing a reasonably simple preparation process of the maleic anhydride copolymer is beneficial to popularization and application of the polymer.
Disclosure of Invention
The invention aims to solve the problems of limited application range and poor dispersion stability caused by the difficulty in removing reaction solvents of microsphere polymers and the long process flow in the prior art, and provides a maleic anhydride-isobutene copolymer microsphere, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a method for preparing maleic anhydride-isobutylene copolymer microspheres, comprising: in a protective atmosphere, dissolving a polymerization monomer and an initiator in a reaction medium to obtain a mixed solution, carrying out polymerization reaction on the mixed solution, and separating an obtained copolymer emulsion suspension to obtain the maleic anhydride-isobutene copolymer microsphere;
wherein the polymerization monomers are maleic anhydride and isobutene; the amount of the maleic anhydride is 50-90wt% and the amount of the isobutene is 10-50wt% based on the total weight of the polymerized monomers;
the reaction medium is a mixture of a compound shown in the formula (1) and alkane;
wherein R is 1 And R is 2 Each independently is an alkyl group having 1 to 6 carbon atoms.
In a second aspect, the invention provides maleic anhydride-isobutylene copolymer microspheres, which are characterized in that the maleic anhydride-isobutylene copolymer microspheres are prepared by the above method.
In a third aspect, the invention provides a method for preparing the maleic anhydride-isobutylene copolymer microspheres and/or the use of the maleic anhydride-isobutylene copolymer microspheres as a dispersant in polyethylene.
Through the technical scheme, the maleic anhydride-isobutene copolymer microsphere provided by the invention has the beneficial effects that:
the maleic anhydride-isobutene copolymer microsphere provided by the invention can be matched with a specific dosage of monomers by selecting a specific reaction medium, so that stable and uniform polymer microspheres can be formed after polymerization, and the conventional ester solvent is not used due to improvement of the solvent, so that the obtained copolymer microsphere has no special odor, has a wide application range, and has the excellent characteristics of no migration and no precipitation compared with the conventional small organic molecule dispersing agent.
Drawings
FIG. 1 is a scanning electron microscope image of maleic anhydride-isobutylene copolymer microspheres of example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a method for preparing maleic anhydride-isobutylene copolymer microspheres, which is characterized by comprising the following steps: in a protective atmosphere, dissolving a polymerization monomer and an initiator in a reaction medium to obtain a mixed solution, carrying out polymerization reaction on the mixed solution, and separating an obtained copolymer emulsion suspension to obtain the maleic anhydride-isobutene copolymer microsphere;
wherein the polymerization monomers are maleic anhydride and isobutene; the amount of the maleic anhydride is 50-90wt% and the amount of the isobutene is 10-50wt% based on the total weight of the polymerized monomers;
the reaction medium is a mixture of a compound shown in the formula (1) and alkane;
wherein R is 1 And R is 2 Each independently is an alkyl group having 1 to 6 carbon atoms.
In the invention, a copolymerization mode is adopted to copolymerize maleic anhydride monomer and comonomer isobutene according to a specific proportion, so that the prepared maleic anhydride-isobutene copolymer is uniformly microspherical, and the copolymer microsphere particles are uniformly dispersed, and have more stable dispersion performance compared with a small-molecule dispersing agent.
According to the invention, the maleic anhydride is used in an amount of 50 to 60% by weight and the isobutene is used in an amount of 40 to 50% by weight, based on the total weight of the polymerized monomers.
In the invention, when the amount of the maleic anhydride and the isobutene satisfies the above range, the obtained maleic anhydride-isobutene copolymer microsphere has clean surface, uniform particle size, more stable dispersibility when used as a dispersing agent, and no migration and precipitation.
According to the invention, the total mass concentration of the polymerized monomers is 5-25wt% and the mass concentration of the initiator is 0.01-1wt%, based on the total weight of the mixed solution.
Further, the total mass concentration of the polymerization monomer is 5 to 20wt% and the mass concentration of the initiator is 0.1 to 0.5wt% based on the total weight of the mixed solution.
According to the invention, the initiator is an organic peroxide and/or an azo compound.
Further, the organic peroxide is at least one selected from dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
Still further, the azo compound is selected from azobisisobutyronitrile and/or azobisisoheptonitrile.
According to the invention, in formula (1), R 1 And R is 2 Each independently is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
According to the invention, the alkane is an alkane having 6 to 12 carbon atoms.
In the invention, the mixture of the compound shown in the formula (1) and alkane is selected as a reaction medium, and can be matched with the maleic anhydride and the comonomer with specific dosage, so that the surface of the obtained polymer microsphere is clean and odorless, and compared with an ester solvent, the application range of the prepared copolymer microsphere serving as a dispersing agent is wider.
Further, the alkane is selected from at least one of hexane, heptane and octane.
Still further, the alkane is hexane.
According to the invention, the alkane is used in an amount of 35 to 70% by volume, preferably 40 to 55% by volume, based on the total volume of the reaction medium.
According to the present invention, the polymerization reaction is carried out in an inert atmosphere, which is not particularly limited, and may be provided by inert gases conventional in the art, such as nitrogen.
According to the invention, the polymerization conditions include: the polymerization temperature is 61-100 ℃, preferably 70-90 ℃; the polymerization time is 1 to 24 hours, preferably 2 to 12 hours.
In the present invention, a water bath and/or an oil bath is used to provide the heat required for the polymerization of the present invention.
In the present invention, the separation may be a solid-liquid separation means conventional in the art, such as centrifugal separation.
In the invention, when centrifugal separation is adopted, the centrifugal rotating speed is 1500-5000rad/min, and the centrifugal time is 5-60min.
In a second aspect, the invention provides maleic anhydride-isobutylene copolymer microspheres, which are characterized in that the maleic anhydride-isobutylene copolymer microspheres are prepared by the above method.
According to the present invention, the copolymer in the maleic anhydride-isobutylene copolymer microspheres comprises a structural unit a derived from maleic anhydride and a structural unit B derived from isobutylene.
According to the invention, the molar content of the structural units A is 47 to 54mol% and the molar content of the structural units B is 46 to 53mol%, based on the total molar amount of the structural units in the copolymer.
In the invention, when the copolymer contains the structural units with the specific molar content in the maleic anhydride-isobutene copolymer microsphere, the maleic anhydride-isobutene copolymer microsphere with good uniformity can be enabled to have better dispersibility and higher comprehensive performance.
Further, the molar content of the structural unit A is 49 to 54mol%, and the molar content of the structural unit B is 46 to 51mol%.
In the present invention, the molar content of each structural unit in the copolymer is as follows 1 H NMR is carried out, in particular, by 1 The ratio of the characteristic hydrogen corresponding to the peak area in the corresponding structural unit in H NMR is calculated.
According to the present invention, the average particle diameter of the maleic anhydride-isobutylene copolymer microspheres is 500 to 1300nm, preferably 600 to 1200nm.
In the invention, the average particle diameter of the copolymer microsphere is measured by adopting a scanning electron microscope measurement method.
According to the present invention, the number average molecular weight of the copolymer in the maleic anhydride-isobutylene copolymer microspheres is 10,000 to 35,000, preferably 10,000 to 25,000.
In a third aspect, the invention provides a method for preparing the maleic anhydride-isobutylene copolymer microspheres and/or the use of the maleic anhydride-isobutylene copolymer microspheres as a dispersant in polyethylene.
In the invention, the maleic anhydride-isobutene copolymer microsphere prepared by the method has uniform particle size, and compared with an ester solvent, the prepared copolymer microsphere is cleaner and odorless by utilizing a specific solvent and a specific proportion, has wider application range as a dispersing agent, does not migrate or precipitate, and has stronger stability.
The present invention will be described in detail by examples. In the following examples, the polymerization yields (C) p ) Performing calculation
C p ＝Mp×100％/Mm
Wherein Mp is the mass of the resulting polymer; mm is the total mass of the monomers added;
the tensile strength of the polyethylene composite was tested by GB/T1040-2006;
the material migration amount is measured by liquid chromatography after the sample is washed by a solvent;
the morphology of the copolymer microsphere is observed and measured by adopting a scanning electron microscope SEM;
the average particle diameter of the copolymer microsphere is measured by adopting a Scanning Electron Microscope (SEM);
the content of each structural unit in the copolymer is adopted 1 H NMR was performed;
the molecular weight of the copolymer was measured by Gel Permeation Chromatography (GPC);
the raw materials used in the examples and comparative examples are all commercially available.
Example 1
100g of maleic anhydride, 2g of azodiisoheptonitrile, 75g of isobutene, 350ml of acetone and 650ml of hexane are added into a 3L reaction kettle, after the materials are uniformly mixed, the temperature is raised to 50 ℃, the reaction is carried out for 5 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and the maleic anhydride-isobutene copolymer microsphere 1A 1593 g is obtained, and the yield of the corresponding copolymer is 90.9%. The size of the maleic anhydride-isobutylene copolymer microsphere 1A was 1300nm. Wherein, the dosage of maleic anhydride is 57.1wt%; the amount of isobutene was 42.9% by weight; the amount of hexane in the reaction medium was 65vol%.
Maleic anhydride-isobutylene copolymer microsphere 1A 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 49mol% and the molar content of the structural unit B derived from isobutylene was 51mol% based on the total molar amount of the structural units in the copolymer. The molecular weight of the polymer was 35,000g/mol.
FIG. 1 is an SEM image of maleic anhydride-isobutylene copolymer microspheres 1A, and it can be seen from FIG. 1 that the maleic anhydride-isobutylene copolymer particles produced in example 1 are spherical polymer particles.
Example 2
50g of maleic anhydride, 2g of azodiisoheptonitrile, 39g of isobutene, 350ml of acetone and 650ml of hexane are added into a 3L reaction kettle, after the materials are uniformly mixed, the temperature is raised to 50 ℃, the reaction is carried out for 5 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and 67.3g of maleic anhydride-isobutene copolymer microsphere 2A is obtained, and the corresponding copolymer yield is 75.6%. The size of the maleic anhydride-isobutylene copolymer microspheres 2A was 900nm. Wherein, the dosage of maleic anhydride is 56.2wt percent; the amount of isobutene was 43.8% by weight; the amount of hexane in the reaction medium was 65vol%.
Maleic anhydride-isobutylene copolymer microspheres 2A 1 H NMR measurement, it was found that the molar content of the structural unit A derived from maleic anhydride was 50mol% and the molar content of the structural unit B derived from isobutylene was 50mol% based on the total molar amount of the structural units in the copolymer. The molecular weight of the polymer was 15,000g/mol.
Example 3
25g of maleic anhydride, 2g of azodiisoheptonitrile, 19g of isobutene, 350ml of acetone and 650ml of heptane are added into a 3L reaction kettle, after the materials are uniformly mixed, the temperature is raised to 50 ℃, the reaction is carried out for 5 hours, after the reaction is finished, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and the maleic anhydride-isobutene copolymer microsphere 3A 33g is obtained, and the corresponding copolymer yield is 75%. The size of the maleic anhydride-isobutylene copolymer microspheres 3A was 500nm. Wherein, the dosage of maleic anhydride is 56.8wt percent; the amount of isobutene was 43.2% by weight; the amount of hexane in the reaction medium was 65vol%.
Maleic anhydride-isobutylene copolymer microspheres 3A 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 52mol% and the molar content of the structural unit B derived from isobutylene was 48mol% based on the total molar amount of the structural units in the copolymer. The molecular weight of the polymer was 10,000g/mol.
Example 4
50g of maleic anhydride, 2g of azodiisoheptonitrile, 35g of isobutene, 500ml of acetone and 500ml of hexane are added into a 3L reaction kettle, after the materials are uniformly mixed, the temperature is raised to 50 ℃, the reaction is carried out for 5 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and 70.2g of maleic anhydride-isobutene copolymer microsphere 4A is obtained, and the corresponding polymer yield is 82.6%. The size of the maleic anhydride-isobutylene copolymer microspheres 4A was 1000nm. Wherein, the dosage of maleic anhydride is 58.8wt percent; the amount of isobutene was 41.2% by weight; the amount of hexane in the reaction medium was 50vol%.
Maleic anhydride-isobutylene copolymer microspheres 4A 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 54mol% and the molar content of the structural unit B derived from isobutylene was 46mol% based on the total molar amount of the structural units in the copolymer. The molecular weight of the polymer was 20,000g/mol.
Example 5
50g of maleic anhydride, 2g of azodiisoheptonitrile, 35g of isobutene, 700ml of acetone and 300ml of heptane are added into a 3L reaction kettle, after the materials are uniformly mixed, the temperature is raised to 50 ℃, the reaction is carried out for 5 hours, after the reaction is completed, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifugal machine at the rotating speed of 2000rad/min, and 68.8g of maleic anhydride-isobutene copolymer microsphere 5A is obtained, and the corresponding copolymer yield is 80.9%. The size of the maleic anhydride-isobutylene copolymer microspheres 5A was 960nm. Wherein, the dosage of maleic anhydride is 58.8wt percent; the amount of isobutene was 41.2% by weight; the amount of hexane in the reaction medium was 30vol%.
The maleic anhydride-isobutylene copolymer microspheres 5A were subjected to 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 53mol% and the molar content of the structural unit B derived from isobutylene was 47mol% based on the total molar amount of the structural units in the copolymer. The molecular weight of the polymer was 25,000g/mol.
Example 6
The procedure of example 1 was followed except that acetone was replaced with pentanone. 70.5g of maleic anhydride-isobutylene copolymer microspheres 6A was obtained, corresponding to a copolymer yield of 82.4%. The size of the maleic anhydride-isobutylene copolymer microspheres 6A was 1050nm.
The resulting maleic anhydride-isobutylene copolymer microspheres 6A were subjected to 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 48mol% and the molar content of the structural unit B derived from isobutylene was 52mol% based on the total molar amount of the structural units in the copolymer. The polymer molecular weight was 22,000g/mol.
Example 7
The procedure of example 1 was followed except that maleic anhydride was used in an amount of 70g and isobutylene was used in an amount of 30g, to obtain 66g of maleic anhydride-isobutylene copolymer microspheres 7A, corresponding to a copolymer yield of 77.4%. The size of the maleic anhydride-isobutylene copolymer microspheres 7A was 900nm.
The resulting maleic anhydride-isobutylene copolymer microspheres 7A were subjected to 1 H NMR measurement gave a molar content of 49mol% of structural unit A derived from maleic anhydride and a molar content of 51mol% of structural unit B derived from isobutylene based on the total molar amount of the copolymerized structural units. The polymer molecular weight was 20,000g/mol.
Example 8
The procedure of example 1 was followed except that 750mL of acetone was used and 250mL of heptane was used. 64g of maleic anhydride-isobutylene copolymer microspheres 8A was obtained, corresponding to a copolymer yield of 75.3%. The size of the maleic anhydride-isobutylene copolymer microspheres 8A was 880nm. The polymer molecular weight was 18,000g/mol.
The obtained maleic anhydride-isobutylene copolymer microspheres 8A were subjected to 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 46mol% and the molar content of the structural unit B derived from isobutylene was 54mol% based on the total molar amount of the structural units in the copolymer.
Comparative example 1
The procedure of example 1 was followed, except that: the reaction medium contained no hexane and 1000mL of acetone. After the completion of the reaction, a transparent solution was obtained, and no microsphere-like copolymer material was obtained.
Comparative example 2
The procedure of example 1 was followed, except that: the reaction medium contained no acetone and 1000mL of hexane. After the reaction, a 2D block material was obtained instead of a suspension, and a microspherical copolymer material could not be obtained. Wherein, the dosage of maleic anhydride is 57.1wt%; the amount of isobutene was 42.9% by weight; the amount of hexane in the reaction medium was 100vol%.
2D subjecting the obtained maleic anhydride-isobutylene copolymer microspheres to 1 H NMR measurement revealed that the molar content of the structural unit A derived from maleic anhydride was 51mol% and the molar content of the structural unit B derived from isobutylene was 49mol% based on the total molar amount of the structural units in the copolymer.
Comparative example 3
The procedure of example 1 was followed, except that: maleic anhydride in an amount of 200g, azobisisoheptonitrile 2g, isobutylene 300g, acetone 500ml and heptane 500ml were charged into a 3L reaction vessel to carry out the reaction. After the reaction is completed, a solidified solid material 3D is obtained. Wherein, the dosage of maleic anhydride is 40wt%; the amount of isobutene was 60% by weight; the amount of hexane in the reaction medium was 50vol%.
3D carrying out the obtained maleic anhydride-isobutene copolymer microsphere 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 49mol% and the molar content of the structural unit B derived from isobutylene was 51mol% based on the total molar amount of the structural units in the copolymer.
Comparative example 4
The procedure of example 1 was followed except that acetone was replaced with decanone. A coagulated maleic anhydride-isobutylene copolymer 4D was obtained. Wherein, the dosage of maleic anhydride is 58.8wt percent; the amount of isobutene was 41.2% by weight; the amount of hexane in the reaction medium was 30vol%.
The obtained maleic anhydride-isobutylene copolymer microsphere 4D was subjected to 1 H NMR measurement, it was found that the molar content of the structural unit A derived from maleic anhydride was 50mol% and the molar content of the structural unit B derived from isobutylene was 50mol% based on the total molar amount of the structural units in the copolymer.
Comparative example 5
The procedure of example 1 was followed except that maleic anhydride was used in an amount of 84g and isobutylene was used in an amount of 91g. The maleic anhydride-isobutylene copolymer 5D 130g was obtained in a polymer yield of 74.3%. Wherein, the dosage of maleic anhydride is 48wt%; the amount of isobutylene was 52wt%; the amount of hexane in the reaction medium was 30vol%.
The obtained maleic anhydride-isobutylene copolymer microsphere 5D was subjected to 1 H NMR measurement was conducted to determine that the molar content of the structural unit A derived from maleic anhydride was 49mol% and the molar content of the structural unit B derived from isobutylene was 51mol% based on the total molar amount of the structural units in the copolymer.
TABLE 1
TABLE 2
| Comparative example | 1 | 2 | 3 | 4 | 5 |
| Maleic anhydride amount/wt% | 57.1 | 57.1 | 40 | 58.8 | 47.9 |
| Isobutene content/wt% | 42.9 | 42.9 | 60 | 41.2 | 52.1 |
| Initiator/wt% | 0.18 | 0.18 | 0.13 | 0.18 | 0.13 |
| Hexane content/vol% > | 0 | 100 | 50 | 30 | 30 |
| Ketone species | Acetone (acetone) | Acetone (acetone) | Acetone (acetone) | Decyl ketone | Acetone (acetone) |
| Mole content of A/mole% | 48 | 51 | 49 | 50 | 49 |
| Molar content of B/mol% | 52 | 49 | 51 | 50 | 51 |
| Copolymer yield/% | 50 | 40 | 60 | 45 | 74.3 |
| Particle size/nm | - | - | - | - | 800 |
| Number average molecular weight | 60000 | 10000 | 20000 | 21000 | 12000 |
Test case
The copolymer microspheres of examples and comparative examples, ethylene bis-stearamide and zinc stearate were divided into compositions for talc filled polyethylene as dispersants, wherein the polyethylene was added in an amount of 2000g and the talc was filled in an amount of 5wt% based on the weight of the polyethylene. Blending and granulating the components by a double-screw extruder, wherein the blending and granulating process parameters are as follows: the temperature of each section is 180 ℃,190 ℃,200 ℃,210 ℃,220 ℃,210 ℃,200 ℃ and 190 ℃. The polymer blend obtained after pelletization was injection molded into a sheet and subjected to a performance test, the test results of which are shown in Table 3.
TABLE 3 Table 3
Note that: t is t 0 T is the initial tensile strength 1 For tensile strength, m is the dispersant which migrates out of the polyethylene surface after half a year of storage
As can be seen from the above examples and comparative examples, the preparation method provided by the invention can realize self-stabilizing precipitation polymerization reaction to obtain stable polymer microsphere suspension, so that the prepared microsphere has uniform particle size and clean and pollution-free surface, and as can be seen from Table 3, the copolymer microsphere prepared by the examples has stable performance, the tensile strength reduction rate is not more than 3.55% after half a year of storage, and the detection amount of the migrating polymer is not more than 0.12mg/g.
However, the method of comparative examples 1 to 4 was not able to obtain a stable suspension and thus a polymer microsphere was not obtained, and the solid mass was not suitable for use as a dispersant, and even if it was added to a polyethylene composite, the initial tensile strength was low and did not exceed 9MPa. Comparative example 5 can produce copolymer microspheres, but it can be seen from Table 3 that the tensile strength decrease rate after half a year of storage was 3.89% and the amount of the migrating polymer was examined to be 0.15mg/g when applied as a dispersant.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (13)
1. A method for preparing maleic anhydride-isobutylene copolymer microspheres, the method comprising: in a protective atmosphere, dissolving a polymerization monomer and an initiator in a reaction medium to obtain a mixed solution, carrying out polymerization reaction on the mixed solution, and separating an obtained copolymer emulsion suspension to obtain the maleic anhydride-isobutene copolymer microsphere;
wherein the polymerization monomers are maleic anhydride and isobutene; the amount of the maleic anhydride is 50-90wt% and the amount of the isobutene is 10-50wt% based on the total weight of the polymerized monomers;
the reaction medium is a mixture of a compound shown in the formula (1) and alkane;
wherein R is 1 And R is 2 Each independently is an alkyl group having 1 to 6 carbon atoms.
2. The process according to claim 1, wherein the maleic anhydride is used in an amount of 50 to 60wt% and the isobutylene is used in an amount of 40 to 50wt% based on the total weight of the polymerized monomers.
3. The preparation method according to claim 1 or 2, wherein the total mass concentration of the polymerized monomers is 5 to 25wt%, preferably 5 to 20wt%, and the mass concentration of the initiator is 0.01 to 1wt%, preferably 0.1 to 0.5wt%, based on the total weight of the mixed solution.
4. A production method according to any one of claims 1 to 3, wherein the initiator is selected from organic peroxides and/or azo compounds;
preferably, the organic peroxide is selected from at least one of dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate;
preferably, the azo compound is selected from azobisisobutyronitrile and/or azobisisoheptonitrile.
5. The process according to any one of claims 1 to 4, wherein R in formula (1) 1 And R is 2 Each independently is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group.
6. The production method according to any one of claims 1 to 5, wherein the alkane is an alkane having 6 to 12 carbon atoms;
preferably, the alkane is selected from at least one of hexane, heptane and octane, more preferably hexane.
7. The process according to any one of claims 1 to 6, wherein the alkane is used in an amount of 30 to 70 vol.%, preferably 40 to 55 vol.%, based on the total volume of the reaction medium.
8. The production method according to any one of claims 1 to 7, wherein the conditions of the polymerization reaction include: the polymerization temperature is 61-100 ℃, preferably 70-90 ℃; the polymerization time is 1 to 24 hours, preferably 2 to 12 hours.
9. Maleic anhydride-isobutylene copolymer microspheres, characterized in that the maleic anhydride-isobutylene copolymer microspheres are produced by the method of any one of claims 1-8.
10. The maleic anhydride-isobutylene copolymer microspheres according to claim 9, wherein the copolymer in the maleic anhydride-isobutylene copolymer microspheres comprises structural units a from maleic anhydride and structural units B from isobutylene;
the molar content of the structural unit A is 47-54mol% and the molar content of the structural unit B is 46-53mol% based on the total molar amount of the structural units in the copolymer.
11. The maleic anhydride-isobutylene copolymer microspheres according to claim 9 or 10, wherein the molar content of the structural unit a is 49 to 54mol% and the molar content of the structural unit B is 46 to 51mol%, based on the total molar amount of the respective structural units in the copolymer.
12. The maleic anhydride-isobutylene copolymer microspheres according to any one of claims 9-11, wherein the average particle size of the maleic anhydride-isobutylene copolymer microspheres is 500-1300nm, preferably 600-1200nm;
the number average molecular weight of the copolymer in the maleic anhydride-isobutylene copolymer microspheres is 10,000 to 35,000, preferably 10,000 to 25,000.
13. The method for the preparation of maleic anhydride-isobutylene copolymer microspheres according to any one of claims 1 to 8 and/or the use of maleic anhydride-isobutylene copolymer microspheres according to any one of claims 9 to 12 as a dispersant in polyethylene.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0292797A2 (en) * | 1987-05-25 | 1988-11-30 | Kao Corporation | Process for preparing particles of olefin-maleic anhydride copolymer |
| JPH051121A (en) * | 1990-07-13 | 1993-01-08 | Tosoh Corp | Maleic anhydride copolymer and scale inhibitor using the same copolymer |
| CN103304736A (en) * | 2013-06-13 | 2013-09-18 | 中国海洋石油总公司 | Preparation method of water soluble dispersant |
| CN104356295A (en) * | 2014-11-13 | 2015-02-18 | 中国海洋石油总公司 | Method for preparing high polymer bonding substrate from mixed C4 fraction |
| CN105916901A (en) * | 2013-12-03 | 2016-08-31 | 德莎欧洲公司 | Multi-phase polymer composition |
-
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0292797A2 (en) * | 1987-05-25 | 1988-11-30 | Kao Corporation | Process for preparing particles of olefin-maleic anhydride copolymer |
| US4795792A (en) * | 1987-05-25 | 1989-01-03 | Kao Corporation | Process for preparing particles of olefin-maleic anhydride copolyer |
| JPH051121A (en) * | 1990-07-13 | 1993-01-08 | Tosoh Corp | Maleic anhydride copolymer and scale inhibitor using the same copolymer |
| CN103304736A (en) * | 2013-06-13 | 2013-09-18 | 中国海洋石油总公司 | Preparation method of water soluble dispersant |
| CN105916901A (en) * | 2013-12-03 | 2016-08-31 | 德莎欧洲公司 | Multi-phase polymer composition |
| CN104356295A (en) * | 2014-11-13 | 2015-02-18 | 中国海洋石油总公司 | Method for preparing high polymer bonding substrate from mixed C4 fraction |
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