阅读说明：本技术 一种丙烯共聚物及其制备方法与应用 (Propylene copolymer and preparation method and application thereof ) 是由 牛慧 华哲 何宗科 刘姝慧 包卓 于 2019-09-25 设计创作，主要内容包括：本发明公开了一种丙烯共聚物及其制备方法与应用,该共聚物由含呋喃的丙烯共聚物与偶联剂小分子之间反应形成交联网络,从而在聚丙烯树脂相和乙丙共聚物弹性体相之间实现化学键连接,从根本上增强两相之间的作用力,提高材料力学性能。同时该共聚物熔融加工时可实现材料的解交联,使材料具有热塑性；其降温后可以再次交联产生网络结构。(The invention discloses a propylene copolymer and a preparation method and application thereof, wherein the copolymer is formed by the reaction between a furan-containing propylene copolymer and coupling agent micromolecules to form a cross-linked network, so that chemical bond connection is realized between a polypropylene resin phase and an ethylene-propylene copolymer elastomer phase, the acting force between the two phases is fundamentally enhanced, and the mechanical property of the material is improved. Meanwhile, the decrosslinking of the material can be realized during the melt processing of the copolymer, so that the material has thermoplasticity; which can be crosslinked again to produce a network structure after cooling.)

1. A propylene copolymer characterized by: in the propylene copolymer, the mass content of propylene is 49-95%, the mass content of ethylene is 3-49%, the mass content of a furan substituted olefin monomer is 1-30%, and the mass content of a coupling agent is 0.1-30%.

2. The propylene copolymer according to claim 1, characterized in that: the furan substituted olefin monomer has the following structure:

wherein R is¹、R²And R³Which may be the same or different, R¹、R²And R³Each independently selected from hydrogen, methyl, ethyl, isopropyl; m is an integer of 1-12.

3. The propylene copolymer according to claim 1, characterized in that: the coupling agent is aliphatic or aromatic hydrocarbon with maleimide substituent groups at two ends, and has the following structure:

wherein R is⁴Selected from alkyl groups having 1 to 20 carbon atoms.

4. Process for the preparation of propylene copolymers as claimed in any of claims 1 to 3, characterized in that: the method comprises the following steps:

1) mixing a Ziegler-Natta catalyst, a cocatalyst, propylene and a furan substituted olefin monomer for polymerization;

2) after the reaction in the step 1) is finished, emptying the residual propylene, and introducing a mixture consisting of ethylene, propylene and furan substituted olefin monomers into the reaction system in the step 1) for polymerization;

3) after the reaction in the step 2) is finished, mixing the polymerization product with a coupling agent to obtain a premixed raw material, adding the premixed raw material into an extrusion device, and carrying out melt extrusion to obtain the propylene copolymer.

5. The method of claim 4, wherein: the using amount of the Ziegler-Natta catalyst in the step 1) is 0.0005-0.1% of the mass of the propylene, and the using amount of the furan-substituted olefin monomer is 0.1-5% of the mass of the propylene; the reaction temperature of the polymerization reaction in the step 1) is-20-120 ℃; the reaction time is 0.1-10 hours; the reaction pressure is 0.01-6 MPa;

in the step 2), introducing a mixture consisting of ethylene, propylene and furan substituted olefin monomers into the reaction system in the step 1) to perform polymerization reaction, wherein the addition amount of ethylene is 1-100% of the addition amount of propylene in the step 1); the adding amount of the propylene in the step 2) is 1-100% of the adding amount of the propylene in the step 1); the adding amount of the furan-substituted olefin is 1-40% of the total mass of the ethylene and the propylene in the step 2); the reaction temperature in the step 2) is-20-120 ℃; the reaction time is 0.1-10 hours; the reaction pressure is 0.01-6 MPa;

the adding amount of the coupling agent in the step 3) is 0.1-40% of the mass of the product in the step 2); the temperature of the melt extrusion in the step 3) is 160-250 ℃.

6. The method of claim 4, wherein: adding hydrogen to the reaction system before the polymerization reaction in step 1); the adding amount of the hydrogen is 0.01-0.5% of the weight of the propylene in the step 1);

adding hydrogen to the reaction system before the polymerization reaction in the step 2); the addition amount of the hydrogen is 0.001-5% of the total weight of the ethylene and the alpha-olefin monomer.

7. The method of claim 4, wherein: the Ziegler-Natta catalyst comprises the following components I to III;

a component I: ti chloride, wherein the weight percentage of Ti element in the Ziegler-Natta catalyst is 0.5-10%; wherein the chloride of Ti is selected from TiCl₃、TiCl₄、TiOCl₃At least one of;

and (2) component II: magnesium chloride, wherein the weight percentage of metal element Mg in the Ziegler-Natta catalyst is 5-25%;

and (3) component III: an internal electron donor, wherein the weight percentage of the internal electron donor in the Ziegler-Natta catalyst is 1-30%; wherein the internal electron donor comprises diethyl succinate, dibutyl adipate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, succinate or 2, 2-diisobutyl-1, 3-dimethoxypropane or 9, 9-bis (methoxymethyl) fluorene.

8. The method of claim 4, wherein: the cocatalyst in the step 1) is one of aluminum alkyl or alkyl aluminoxane;

the alkyl aluminum is trialkyl aluminum or a mixture of trialkyl aluminum and halogenated alkyl aluminum or polyhalogenated alkyl aluminum, wherein the trialkyl aluminum is at least one of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum and trialkyl aluminum; the alkyl aluminum halide comprises AlEt₂Cl; the polyhaloalkylaluminum includes Al₂Et₃Cl₃(ii) a The alkylaluminoxane is at least one of methylaluminoxane and isobutylaluminoxane;

the addition amount of the cocatalyst is that the molar ratio of Al in the cocatalyst to Ti in the Ziegler-Natta catalyst is Al: and Ti is 10-20000.

9. The method of claim 4, wherein: adding an external electron donor into a reaction system before the polymerization reaction in the step 1);

the external electron donor is the same as the internal electron donor of claim 8 or has a structure such as R₁R₂Si(OR)₂A compound of formula (I), wherein R₁And R₂All the alkyl groups have 1-18 carbon atoms, cycloalkyl groups have 3-18 carbon atoms or aryl groups have 6-18 carbon atoms, and R is alkyl groups having 1-5 carbon atoms;

the external electron donor is at least one of tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, dicyclopentanyloxydiethylsilane, diphenyldimethoxysilane and diphenyldiethoxysilane;

the molar dosage of the external electron donor is 0.01-100 times of the molar dosage of the metal Ti element in the Ziegler-Natta catalyst.

10. Use of a propylene copolymer as claimed in any one of claims 1 to 3 as an impact polymer resin material.

Technical Field

The invention relates to a propylene copolymer and a preparation method and application thereof, in particular to a preparation method of a propylene copolymer with a thermally reversible crosslinking structure and application thereof as an impact-resistant resin.

Background

The polypropylene multiphase copolymer is one of the main varieties of polypropylene resin, and ethylene/alpha-olefin copolymer with elastomer property is dispersed in polypropylene matrix, so that the defect of toughness (especially low-temperature toughness) of homopolymerized polypropylene resin is overcome, and the application range of the polypropylene resin is greatly widened. The continuous multistage propylene polymerization and ethylene/alpha-olefin copolymerization in a reactor has become a current trend for the preparation of polypropylene heterophasic copolymers: firstly, an isotactic polypropylene resin matrix is synthesized in a first-stage reaction kettle, then the generated polypropylene is transferred to a second-stage reaction kettle to continue the copolymerization reaction of ethylene and propylene (or ethylene and other alpha-olefin), a copolymer with rubber property is synthesized, the in-situ dispersion of the copolymer in the polypropylene resin matrix is realized, and the toughness is provided for the polypropylene resin. The toughening mechanism is as follows: the rubber phase in the propylene copolymer can absorb or partially absorb the impact energy at the fracture part, thereby improving the overall impact strength of the material. The main factors influencing the toughening effect comprise three aspects: (1) rubber phase content: it is mentioned in patent US 3,627,852 that this rubber phase only achieves a certain content to achieve a significant toughening effect. (2) Dispersed size and uniformity of rubber phase: the rubber phase is generally distributed in the matrix of the polypropylene resin as a dispersed phase, and when the size of the dispersed phase is about 1 μm, the rubber phase can play a role of toughening the polypropylene well (Journal of Applied Polymer Science,1996,60,1391-1403), and the dispersed phase with too large or too small size is not beneficial to improving the material performance. However, the non-polar nature of the polyolefin itself makes the forces between the two phases weak and, in addition, there is no chemical bonding between the two phases, and as the heat treatment time or number of times increases, the phase separation will gradually progress and the dispersed phase (elastomeric copolymer) tends to aggregate to a large scale. The problem that the phase separation gradually develops and the rubber phase aggregates in the processing process is solved by crosslinking (Polymer,2016,85,10-18) the rubber phase during polymerization by Dong jin Yong et al of the institute of chemistry of the Chinese academy of sciences. (3) The magnitude of the interaction force (i.e., compatibility) of the rubber phase with the resin matrix phase: the enhancement of the interaction between the two phases is very critical to the inhibition of phase separation and the improvement of material properties, and at present, people introduce an ethylene/propylene copolymer with a block structure in the polymerization process to improve the compatibility between the two phases, but the improvement effect is very limited because no chemical bond exists between the two phases.

The Diels-Alder (D-A) reaction between furan and maleimide (4 +2 cyclization reaction) has the characteristics of easily available raw materials and easy reverse D-A reaction (rD-A), the D-A reaction occurs between furan and maleimide at normal temperature or under heating condition (about 60 ℃), the rD-A reaction occurs at about 120 ℃, and the method is an effective way for preparing high-performance materials. If the reaction is utilized to realize the chemical bonding of the resin phase and the rubber phase, the problem of poor compatibility between the two phases can be fundamentally solved, and the impact-resistant polymer material with excellent performance is obtained; meanwhile, the chemical bond can be broken at 120 ℃, so that the requirement of material melting processing is met, and the chemical bond can be realized during cooling after processing and forming, so that a new functional material is obtained.

Disclosure of Invention

The present invention provides a novel propylene copolymer in which: 49-95% of propylene, 3-49% of ethylene, 1-30% of furan substituted olefin monomer and 0.1-30% of coupling agent.

Wherein the furan-substituted olefin monomer has the following structure:

wherein R is¹、R²And R³Can be the same or different and are each independently selected from hydrogen, methyl, ethyl, isopropyl; m is an integer of 1-12.

The coupling agent is aliphatic or aromatic hydrocarbon with maleimide substituent groups at two ends, and has the following structure:

wherein R is⁴Selected from alkyl groups having 1 to 20 carbon atoms.

Another object of the present invention is to provide a process for preparing the above propylene copolymer, which comprises the following steps:

1) preparation of polypropylene resin: mixing a Ziegler-Natta catalyst, a cocatalyst, propylene and a furan substituted olefin monomer for polymerization;

2) preparation of ethylene-propylene copolymer elastomer: after the reaction in the step 1) is finished, emptying the residual propylene, and introducing a mixture consisting of ethylene, propylene and furan substituted olefin monomers into the reaction system in the step 1) for polymerization;

3) coupling reaction of the polymer: after the reaction in the step 2) is finished, mixing the polymerization product with a coupling agent to obtain a premixed raw material, adding the premixed raw material into extrusion equipment, and carrying out melt extrusion to obtain the propylene copolymer;

further, in the above technical solution, the amount of the Ziegler-Natta catalyst used in step 1) is 0.0005 to 0.1%, preferably 0.001 to 0.01% of the mass of the propylene; the using amount of the furan-substituted olefin monomer is 0.1-5% of the mass of the propylene, and preferably 0.5-2%;

further, in the technical scheme, the reaction temperature in the step 1) is-20-120 ℃, preferably 50-90 ℃; the reaction time is 0.1-10 hours, preferably 0.5-3 hours; the reaction pressure is 0.01-6 MPa, preferably 0.1-4 MPa;

further, in the above technical scheme, before the polymerization reaction in the step 1), hydrogen is added into the reaction system; the adding amount of the hydrogen is 0.01-0.5% of the weight of the propylene, and preferably 0.01-0.2%;

further, in the above technical scheme, the Ziegler-Natta catalyst in step 1) comprises the following components I to iii;

a component I: ti chloride, wherein the weight percentage of Ti element in the Ziegler-Natta catalyst is 0.5-10%; wherein the chloride of Ti is selected from TiCl₃、TiCl₄、TiOCl₃At least one of;

and (2) component II: magnesium chloride, wherein the weight percentage of the metal element Mg in the Ziegler-Natta catalyst is 5-25%;

and (3) component III: an internal electron donor, wherein the weight percentage of the internal electron donor in the Ziegler-Natta catalyst is 1-30%; wherein the internal electron donor comprises diethyl succinate, dibutyl adipate, diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, succinate, 2-diisobutyl-1, 3-dimethoxypropane or 9, 9-bis (methoxymethyl) fluorene.

Further, in the above technical scheme, before the polymerization reaction in step 1), a cocatalyst is added into the reaction system; the cocatalyst is one of alkyl aluminum or alkyl aluminoxane;

wherein the alkyl aluminum is trialkyl aluminum or a mixture of trialkyl aluminum and halogenated alkyl aluminum or polyhalogenated alkyl aluminum, wherein the trialkyl aluminum is preferably at least one of triethyl aluminum, triisobutyl aluminum, tri-n-butyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum and trialkyl aluminum, and the halogenated alkyl aluminum is preferably AlEt₂Cl; the polyhaloalkylaluminum is preferably Al₂Et₃Cl₃(ii) a The alkylaluminoxane is preferably at least one of methylaluminoxane and isobutylaluminoxane;

the addition amount of the cocatalyst is respectively Al: ti is 10 to 20000, preferably 100 to 10000.

Further, in the above technical scheme, before the polymerization reaction in step 1), an external electron donor is added to the reaction system;

the external electron donor is the same as or different from the internal electron donor; when the external electron donor is different from the internal electron donor, the external electron donor has a structure as R₁R₂Si(OR)₂A compound of formula (I), wherein R₁And R₂All the alkyl groups have 1-18 carbon atoms, cycloalkyl groups have 3-18 carbon atoms or aryl groups have 6-18 carbon atoms, and R is alkyl groups having 1-5 carbon atoms;

furthermore, in the above technical solution, the external electron donor is preferably at least one of tetramethoxysilane, dimethyldimethoxysilane, tetraethoxysilane, triethoxyethylsilane, dicyclopentanyloxydiethylsilane, diphenyldimethoxysilane and diphenyldiethoxysilane;

further, in the above technical scheme, the amount of the external electron donor is 0.01 to 100 times, preferably 1 to 50 times, the molar amount of the metal Ti element in the Ziegler-Natta catalyst.

Further, in the above technical scheme, the addition amount of the ethylene in the step 2) is 1-100%, preferably 10-40% of the addition amount of the propylene in the step 1); the adding amount of the propylene in the step 2) is 1-100%, preferably 10-40% of the adding amount of the propylene in the step 1); the adding amount of the furan-substituted olefin in the step 2) is 1-40%, preferably 5-20% of the total mass of the ethylene and the propylene in the step 2);

further, in the technical scheme, the reaction temperature in the step 2) is-20-120 ℃, and preferably 45-95 ℃; the reaction time is 0.1-10 hours, preferably 0.5-4 hours; the reaction pressure is 0.01-6 MPa, preferably 0.1-4 MPa;

further, in the above technical scheme, before the polymerization reaction of step 2), hydrogen is added into the reaction system; the amount of the hydrogen added is 0.001-5%, preferably 0.005-1%, more preferably 0.02-0.15% of the total weight of the ethylene and the alpha-olefin monomer.

Further, in the technical scheme, the adding amount of the coupling agent in the step 3) is 0.1-40% of the mass of the product in the step 2), and is preferably 1-10%;

further, in the above technical scheme, the temperature of melt extrusion of the mixture of the polymerization product and the coupling agent in the step 3) is 160-250 ℃, preferably 180-230 ℃.

The propylene copolymer of the invention is a material with a reversible cross-linked network structure: the coupling agent is used for realizing chemical bond connection between the polypropylene resin prepared in the step 1) and the ethylene-propylene copolymer elastomer prepared in the step 2) to form a cross-linked network structure, so that the acting force between the two phases is enhanced fundamentally; by utilizing the thermal reversibility of the D-A reaction, the decrosslinking of the material can be realized when the copolymer is heated to more than 120 ℃, so that the material has thermoplasticity; when the temperature is reduced to below 60 ℃, the material can be crosslinked again to generate a network structure, so that the mechanical property of the material is enhanced.

The invention also provides the application of the propylene copolymer as an impact-resistant polymer resin material.

Drawings

FIG. 1 shows nuclear magnetic hydrogen spectrograms of the products of comparative example 3 and example 7.

FIG. 2 is a comparison of the IR spectra of the products of comparative example 3 and example 7.

FIG. 3 is a comparison of scanning electron micrographs of the cross-section of the products of comparative example 4 and example 3 before and after hexane etching.

Detailed Description

The following examples are presented as further illustrations and are not intended to limit the scope of the claims. The olefin monomer A containing a furan substituent, the olefin monomer B containing a furan substituent, the coupling agent C and the coupling agent D used in the comparative examples and examples of the present invention were obtained by the following routes or manners.

Furan substituent-containing olefin monomer:

the olefin monomers containing furan substituents can be purchased from commercial products or synthesized directly. For synthetic furan substituent-containing olefin monomers, the present application provides a general synthetic method, and does not limit the furan substituent-containing olefin monomers.

(1) Furan substituent-containing olefin monomer a:

adding n-butyllithium solution (90mmol) into 50mL of anhydrous tetrahydrofuran dissolved with 147mmol of furan at-78 ℃, heating to room temperature for reaction for 4 hours, cooling to-78 ℃, dissolving 126mmol of 5-bromo-1-pentene into 20mL of anhydrous tetrahydrofuran, dropwise adding into the reaction system, and stirring at room temperature overnight. The reaction solution was poured into ice water, extracted with ethyl acetate, anhydrous MgSO₄Drying, distilling under reduced pressure to remove the solvent and unreacted 5-Bromo-1-pentene to give the product furan pentene a. The structural formula is as follows:

(2) furan substituent-containing olefin monomer B:

adding an n-butyllithium solution (44mmol) into 20mL of anhydrous tetrahydrofuran dissolved with 73.5mmol of furan at-78 ℃, heating to room temperature for reaction for 4 hours, cooling to-78 ℃, dissolving 68mmol of 8-bromo-1-octene in 10mL of anhydrous tetrahydrofuran, dropwise adding into the reaction system, and stirring at room temperature overnight. The reaction solution was poured into ice water, extracted with ethyl acetate, anhydrous MgSO₄Drying, and distilling under reduced pressure to remove the solvent and unreacted 8-bromo-1-octene to obtain furan octene B. The structural formula is as follows:

coupling agent:

the coupling agent can be purchased from commercial products or directly synthesized. For synthesizing the coupling agent containing maleimide at two ends, the application provides a conventional synthesis method, and the structure of the coupling agent is not limited.

(1) Coupling agent C:

commercial products: from Annaiji chemical company, CAS number: 13676-54-5.

(2) Coupling agent D:

the synthesis method comprises the following steps: 10g of furan-protected maleic anhydride and 7mL of triethylamine were dissolved in 60mL of methanol, and 2.92g of hexamethylenediamine dissolved in 40mL of methanol was added dropwise in an ice-water bath. Heating and refluxing for 48 hours at 70-80 ℃ under the protection of nitrogen. The product is filtered and dried, and a small amount of toluene (30-50 mL) is added and heated under reflux at 120 ℃ for 48 hours. The solvent was distilled off under reduced pressure to obtain product D. The structure is as follows:

comparative example 1

2kg of liquid propylene and 0.1MPa of hydrogen are added into a 10L polymerization reaction kettle, 0.076g of diphenyldimethoxysilane, 0.36g of triethylaluminum and 60mg of Ziegler-Natta catalyst are sequentially added at 30 ℃, the temperature is raised to 75 ℃, and the reaction is carried out for 120min, so that 1524g of polypropylene product is obtained. The product structure and properties are shown in table 1.

Comparative example 2

2kg of liquid propylene and 0.1MPa of hydrogen were put into a 10L polymerization reactor, and 0.076g of diphenyldimethoxysilane, 0.36g of triethylaluminum and 60mg of Ziegler-Natta catalyst were added in this order at 30 ℃ and the temperature was raised to 75 ℃ for 60 minutes. 850g of polypropylene was obtained.

And (3) emptying the residual propylene in the reaction kettle, introducing a mixed gas of 300g of ethylene and 300g of propylene and 0.1MPa of hydrogen, heating to 80 ℃, and reacting for 40min to finally obtain 1040g of a product.

The obtained product had an ethylene content of 11.5% by mass and a propylene content of 88.5% by mass. The product structure and properties are shown in table 1.

The nuclear magnetic hydrogen spectrum diagram is shown in figure 1.

Comparative example 3

2kg of liquid propylene and 0.25MPa of hydrogen are added into a 10L polymerization reaction kettle, 0.076g of diphenyldimethoxysilane, 0.36g of triethylaluminum and 60mg of Ziegler-Natta catalyst are added at 30 ℃, the temperature is raised to 75 ℃ and the reaction is carried out for 60 min. 990g of polypropylene was obtained.

And (3) emptying the residual propylene in the reaction kettle, introducing a mixed gas of 300g of ethylene and 300g of propylene and 0.15MPa of hydrogen, heating to 80 ℃, and reacting for 40min to finally obtain 1370g of a polymerization product.

The obtained product had an ethylene content of 18.0% by mass and a propylene content of 82.0% by mass. The product structure and properties are shown in table 1. The product structure and properties are shown in table 1.

Comparative example 4

2kg of liquid propylene, 10g of an olefin monomer A containing a furan substituent and 0.1MPa of hydrogen were added to a 10L polymerization reactor, 0.076g of diphenyldimethoxysilane, 0.36g of triethylaluminum and 60mg of a Ziegler-Natta catalyst were added in this order at 30 ℃, and the temperature was raised to 75 ℃ for 60 minutes. 780g of polypropylene was obtained.

Emptying the residual propylene in the reaction kettle, adding 20g of olefin monomer A containing furan substituent, introducing a mixed gas of 300g of ethylene and 300g of propylene and hydrogen at 0.1MPa, heating to 80 ℃, and reacting for 40min to finally obtain 950g of a product.

The obtained product had an ethylene content of 11.8% by mass, a propylene content of 86.1% by mass and a monomer A content of 2.1% by mass. The product structure and properties are shown in table 1.

The nuclear magnetic hydrogen spectrum diagram is shown in figure 2.