JP2018154715A - Polar olefin copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polar olefin copolymer having improved physical properties such as adhesiveness, close adhesion, and filler compatibility.SOLUTION: A polar olefin copolymer has ethylene and a polar monomer unit selected from compounds represented by formulas (1) and/or (2).SELECTED DRAWING: None

Description

  The present invention relates to a novel polar olefin copolymer, and more specifically, at least one nonpolar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, and various organic compounds and polymer compounds. It is a novel polar olefin copolymer composed of a polar monomer unit containing a tetrahydrofuran ring and / or a furan ring as a polar group, which is compatible with.

Generally, polyolefin-based materials represented by polyethylene and polypropylene are inexpensive, have high mechanical strength, excellent impact resistance, chemical resistance, corrosion resistance, etc., and excellent moldability. For example, injection molding, extrusion molding, It is formed into a film, a laminate, a container, a blow bottle or the like by blow molding or the like and used in various applications. However, since polyolefin-based materials are usually non-polar, adhesion / adhesion with other materials, printability, compatibility with fillers, etc. are not sufficient, and there is a drawback that application fields are limited. . For example, if a polyolefin-based material is used as a laminated material with a different material such as a metal or a high-polarity resin, the adhesive strength is very weak or the desired laminated material cannot be formed without bonding at all. .
For the purpose of overcoming the drawbacks of the polyolefin-based material, which is such a nonpolar material, the addition of polarity to the polyolefin-based material has been studied. For example, ethylene-vinyl acetate copolymer or ethylene- (meth) acrylic acid copolymer can be obtained by radical polymerization of vinyl acetate or (meth) acrylic olefin as polar comonomer with ethylene under high temperature and high pressure conditions. It is widely known that Furthermore, research is also underway to obtain a copolymer of an olefin such as ethylene or propylene and a polar comonomer under mild conditions using a late transition metal complex catalyst called so-called postmetallocene. As polar comonomers, those using acrylonitrile (Non-Patent Document 1), vinyl ether (Non-Patent Document 2), etc. have been reported. On the other hand, a vinyl polymer using biomass-derived 5-hydroxymethylfurfural (HMF) as a raw material has also been reported (Patent Document 1).

K. Nozaki et al. , J .; Am. Chem. Soc. 2007, 129, 8948-8949. R. Jordan et al. , J .; Am. Chem. Soc. , 2007, 129, 8946-8947.

JP 2010-43203 A

  As described above, improvement of polyolefin-based materials by imparting polarity to polyolefin-based materials using various polar comonomers has been studied. However, when using polar comonomers proposed so far, hydrolysis resistance, heat resistance In some cases, problems such as property and coloring may occur. In addition, there are cases where sufficient effects are not exhibited in improving physical properties such as adhesion to other materials, adhesion, and compatibility with fillers. Therefore, there is no problem of hydrolysis resistance or heat resistance even when copolymerized with a polyolefin-based material for imparting polarity to the polyolefin-based material, and further, adhesion with other materials, adhesion, It has been desired to develop polar comonomers that can sufficiently improve the physical properties such as compatibility.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have expressed at least one nonpolar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, represented by the general formula (1). A polar olefin copolymer obtained by copolymerizing at least one polar monomer unit selected from the compound represented by formula (2) and / or at least one polar monomer unit selected from the compound represented by formula (2): For example, it has been found that problems such as hydrolysis resistance, heat resistance, coloring, etc. do not occur, and further physical properties improvement effects such as adhesion with other materials, adhesion, and compatibility with fillers can be sufficiently obtained, The present invention has been completed.

Hereinafter, the present invention will be described.
[1] At least one nonpolar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, at least one polar monomer unit selected from a compound represented by the following general formula (1), and / or A polar olefin copolymer comprising at least one polar monomer unit selected from the compound represented by formula (2).

(In the formula, R1 and R2 each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.)
[2] The polar olefin copolymer according to [1], wherein the total amount of the monomer units derived from the general formula (1) and / or the general formula (2) is 0.001 to 10 mol%. .
[3] The polar olefin copolymer according to [1] or [2], wherein the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 5000 to 1000000. .
[4] The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is in the range of 1.2 to 6.5, [1 ] The polar olefin copolymer of any one of [3].
[5] The polar olefin copolymer according to any one of [1] to [4], wherein the melting point is 50 to 140 ° C.

  According to the present invention, a polar monomer containing a tetrahydrofuran ring and / or furan ring having compatibility with various organic compounds and polymer compounds as a polar group is used as a polar comonomer in a copolymer with a polyolefin-based material. As a result, polar olefin copolymers that do not cause problems such as hydrolysis resistance, heat resistance, and coloration, and that can sufficiently improve physical properties such as adhesion to other materials, adhesion, and compatibility with fillers. A polymer can be obtained.

Hereinafter, the polar olefin copolymer according to the present invention will be described.
The scope of the present invention is not restricted by these explanations, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.

(Copolymer)
The copolymer in the present invention includes at least one nonpolar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, and at least one polar monomer unit selected from a compound represented by the general formula (1). And / or a polar olefin copolymer comprising at least one polar monomer unit selected from the compound represented by formula (2).

  The at least one nonpolar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms is an α-olefin having 3 to 10 carbon atoms represented by the following structural formula (3).

(R ₃ is a hydrocarbon group having 1 to 8 carbon atoms, and may be a straight chain structure or branched).
From the viewpoint of industrial availability, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1- Butene, 4-methyl-1-pentene, butadiene, isoprene, styrene, allylbenzene, vinylcyclohexane, and cyclohexene are preferable, and ethylene, propylene, butadiene, and styrene are more preferable.

  Examples of the compound represented by the general formula (1) include 2-allylfuran, 5-methyl-2-allylfuran, 5-ethyl-2-allylfuran, 5-propyl-2-allylfuran, and 5-butyl-2. -Allylfuran, 5-pentyl-2-allylfuran, 5-isopropyl-2-allylfuran, 5-tertbutyl-2-allylfuran, 5-secbutyl-2-allylfuran and the like can be exemplified. Of these, 2-allylfuran, 5-methyl-2-allylfuran, 5-ethyl-2-allylfuran, and 5-propyl-2-allylfuran are preferred from the viewpoint of functional expression as a polar group of the furan ring. 2-allylfuran and 5-methyl-2-allylfuran are more preferable.

  Examples of the compound represented by the general formula (2) include 2-allyltetrahydrofuran, 5-methyl-2-allyltetrahydrofuran, 5-ethyl-2-allyltetrahydrofuran, 5-propyl-2-allyltetrahydrofuran, and 5-butyl-2. -Allyltetrahydrofuran, 5-pentyl-2-allyltetrahydrofuran, 5-isopropyl-2-allyltetrahydrofuran, 5-tertbutyl-2-allyltetrahydrofuran, 5-secbutyl-2-allyltetrahydrofuran and the like can be exemplified. Among these, 2-allyltetrahydrofuran furan, 5-methyl-2-allyltetrahydrofuran furan, 5-ethyl-2-allyltetrahydrofuran furan, 5-propyl-2-allyltetrahydrofuran furan from the viewpoint of functional expression as a polar group of the tetrahydrofuran ring. 2-allyltetrahydrofuran furan and 5-methyl-2-allyltetrahydrofuran are more preferred.

In addition, the copolymer of the present invention may include any one of the general formula (1) and / or the general formula (2) as a monomer unit, and may include both.
Moreover, as a copolymer of this invention, it is preferable that the total amount of the monomer unit derived from General formula (1) and / or General formula (2) is 0.001-10 mol%. When the content of the monomer unit derived from the general formula (1) and / or the general formula (2) is less than 0.001 mol%, the absolute amount of the tetrahydrofuran ring and / or the furan ring contained in the copolymer There is a possibility that performance such as adhesiveness may not be exhibited. On the other hand, even when the monomer unit derived from the general formula (1) and / or the general formula (2) is contained in an amount exceeding 10 mol%, it is often impossible to expect an improvement in function corresponding to the content. Preferably, it is 0.01-10 mol%, More preferably, it is 0.01-5 mol%.

The weight average molecular weight (Mw) calculated | required by the gel permeation chromatography (GPC) of the copolymer of this invention has the preferable range of 5000-1 million. When the weight average molecular weight (Mw) exceeds 1,000,000, the melt viscosity becomes very high, and the molding process may be difficult. In addition, when the weight average molecular weight (Mw) is less than 5000, characteristics as a copolymer may not be obtained.
Preferably, it is 10,000 to 500,000, More preferably, it is 10,000 to 300,000.

  The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably in the range of 1.2 to 6.5. If it is less than 1.2, various workability tends to be insufficient, and if it exceeds 6.5, performance such as adhesion tends to be insufficient. Preferably, it is 1.2 to 5.0, more preferably 1.2 to 4.5.

Furthermore, the melting point of the copolymer of the present invention is preferably 50 to 140 ° C. Among these, Preferably it is 60 to 138 degreeC, More preferably, it is the range of 70 to 135 degreeC. When this range is satisfied, heat resistance and adhesiveness are excellent.
Hereinafter, a method for obtaining the copolymer of the present invention will be described.
(Method for producing copolymer)
As a method for obtaining the copolymer of the present invention, methods such as radical polymerization and coordination anion polymerization can be employed. However, radical polymerization generally requires high-temperature and high-pressure conditions. Preference is given to coordination anionic polymerization which allows the reaction below.

  Coordinated anionic polymerization is a polymerization in the presence of a transition metal catalyst. As transition metal catalysts, organometallic complexes having organic ligands in their structures have been widely developed, and these can be used. Moreover, the outstanding catalyst activity can be acquired by making an alkylalumoxane, a boron containing compound, etc. coexist in a reaction system as a co-catalyst.

  The copolymerization reaction in the present invention is generally performed in an inert gas atmosphere. For example, a nitrogen or argon atmosphere can be used, and a nitrogen atmosphere is preferable.

  In a state where ethylene and / or an α-olefin having 3 to 10 carbon atoms does not coexist in the copolymerization reactor, a solvent, a polar monomer containing a tetrahydrofuran ring and / or a furan ring as a polar group, a promoter component are added, and then A catalyst solution in which a transition metal catalyst is dissolved in a solvent is added to the copolymerization reactor, and then at least one nonpolar monomer selected from ethylene and an α-olefin having 3 to 10 carbon atoms is introduced to start the copolymerization reaction. To do.

  The copolymerization reaction temperature is not particularly limited. Usually, it is performed in the range of -30 to 400 ° C, preferably 0 to 180 ° C, more preferably 20 to 150 ° C. The internal pressure of the copolymerization reaction is carried out within the range of normal pressure to 100 MPa, preferably from normal pressure to 20 MPa, more preferably within the range of normal pressure to 10 MPa.

  The solvent is not particularly limited as long as it does not affect the copolymerization reaction, and examples thereof include aliphatic hydrocarbons such as isobutane, pentane, hexane, heptane, and cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and xylene. .

  Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples, and may be implemented with appropriate modifications within a range that can meet the gist of the present invention. These are all included in the technical scope of the present invention.

[Method of analyzing polymer structure]
1. Content of olefin having polar group The structure of the (co) polymer obtained in the Examples was determined by analyzing various NMR measurement results using 300 MHz NMR (model number: AVANCE300M) manufactured by Bruker BRUKER. The content of the monomer unit derived from the olefin having a polar group is determined based on the peak derived from the olefin having a polar group by 1H-NMR measurement at 80 ° C. using 1,1,2,2-tetrachloroethane-d 2 as a solvent. Calculation was based on the integration ratio of the main chain (0.8 to 1.8 ppm).
2. Molecular Weight The number average molecular weight (Mn) and the weight average molecular weight (Mw) are determined by gel permeation chromatography (GPC). The molecular weight distribution parameter (Mw / Mn) was calculated as Mw / Mn from the ratio of Mw and Mn determined by gel permeation chromatography (GPC).
(Measurement condition)
Model used: HLC-8121GPC / HT manufactured by Tosoh Corporation
Measurement temperature: 140 ° C
Solvent: orthodichlorobenzene (including 2,6-di-t-butyl-4-methylphenol)
Column: manufactured by Tosoh Corporation, 018420, TSK-gel (registered trademark) GMHHR-HHT, filler particle diameter 5 μm, inner diameter 7.8 mm, length 300 mm
(Sample preparation)
A sample was prepared by preparing a solution using orthodichlorobenzene (including 2,6-di-t-butyl-4-methylphenol) and dissolving it at 140 ° C.
(Calculation of molecular weight)
The standard polystyrene method was used, and the conversion from the retention capacity to the molecular weight was performed using a standard curve prepared in advance by standard polystyrene.
3. Melting point The melting point is about 3 mg of sample packed in an aluminum pan using a DSC7020 differential scanning calorimeter manufactured by Hitachi High-Tech Science Co., Ltd., heated from 30 ° C. to 250 ° C. at a heating rate of 20 ° C./min, and held for 5 minutes. Then, the temperature was lowered to −30 ° C. at 10 ° C./min and held for 5 minutes for crystallization, then heated to 250 ° C. at 10 ° C./min, held for 5 minutes, and then up to 30 ° C. at 20 ° C./min. A melting curve was obtained by lowering the temperature. The peak top temperature of the main endothermic peak in the final temperature increase step performed to obtain the melting curve was determined as the melting point Tm.

Ligand 1: Synthesis of bis [N, N ′-(2,6-diisopropylphenyl) imino] acenaphthene 500 mL capacity equipped with stirrer, thermometer, temperature controller, dripping device, nitrogen inlet tube and condenser tube A necked flask was charged with acenaphthenequinone (4.5 g, 25 mmol) and acetonitrile (125 mL), and heated under reflux conditions for 1 hour under a nitrogen stream. Acetic acid (45 g, 750 mmol) was added and heated under reflux conditions for 1 hour under a nitrogen stream. 2,6-Diisopropylaniline (10 g, 57 mmol) was added dropwise over 30 minutes, and the mixture was further heated under reflux conditions for 5 hours under a nitrogen stream. After cooling to room temperature, the yellow-orange solid was filtered off and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 11.7 g of ligand 1 with a yield of 95%.

Metal complex catalyst 1: Synthesis of bis [N, N ′-(2,6-diisopropylphenyl) imino] acenaphthene-nickel bromide In a 100 mL three-necked flask equipped with a stirrer and a nitrogen inlet tube, nickel (II) bromide was added. An ethylene glycol dimethyl ether complex (1.0 g, 3.2 mmol) and dichloromethane (31 mL) were charged. Under a nitrogen stream, ligand 1 (1.7 g, 3.4 mmol) and dichloromethane (15 mL) were added, and the mixture was stirred at room temperature for 15 hours. The solvent was distilled off under reduced pressure and washed with n-hexane. The obtained solid was dried under reduced pressure to obtain 2.3 g of metal complex catalyst 1 with a yield of 99%.

[Example 1] Copolymerization of allylfuran and ethylene (Preparation of copolymer 1)
Toluene (7 mL), allyl furan (3 mL, 0.39 mmol), and methylaluminoxane (5 mmol) were added in a 50 mL autoclave under a nitrogen atmosphere. Separately, a toluene (5 mL) solution containing metal complex catalyst 1 (100 μmol) was prepared in a nitrogen atmosphere, added to the autoclave using a syringe, then filled with ethylene (0.8 MPa), and the autoclave was kept at 25 ° C. After stirring for 4 hours with a stirrer, the ethylene supply was stopped, and methanol was added to terminate the reaction. The content solution was added to a hydrochloric acid methanol solution (about 100 mL) to precipitate a copolymer. The resulting copolymer was recovered by filtration, washed with methanol, and then dried under reduced pressure to obtain copolymer 1. The yield was 144 mg.
In 1H-NMR measurement, a new peak was detected in the vicinity of 2.5 ppm by introduction of allyl furan. The peak is identified as a peak derived from a hydrogen atom present in the furan ring α-position methylene of allyl furan incorporated into the polyethylene chain. The allylfuran introduction rate into polyethylene calculated from the 1H-NMR measurement result was 1.5 mol% (5.7 mass%). The number average molecular weight was calculated to be 7000 and the weight average molecular weight was 15000 by size exclusion chromatography, and Mw / Mn was 2.1. The melting point measured by a differential scanning calorimeter was 107 ° C.

  According to the present invention, a polar olefin copolymer comprising at least one nonpolar monomer selected from ethylene and an α-olefin having 3 to 10 carbon atoms and a polar monomer containing a tetrahydrofuran ring and / or a furan ring as a polar group is obtained. It became possible.

  Thus, it becomes possible to provide a novel polar olefin copolymer, which is very useful in the industrial field of polyolefin copolymers. Specifically, it is suitable for uses such as a thermoplastic resin composition, a compatibilizing agent, an adhesive, an adhesive resin, a resin modifier, and a filler dispersant.

Claims (5)

At least one non-polar monomer unit selected from ethylene and an α-olefin having 3 to 10 carbon atoms, at least one polar monomer unit selected from a compound represented by the following general formula (1), and / or the following general formula ( 2) A polar olefin copolymer comprising at least one polar monomer unit selected from the compounds represented by 2).

(In the formula, R1 and R2 each represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms.) The polar olefin copolymer according to claim 1, wherein the total amount of the monomer units derived from the general formula (1) and / or the general formula (2) is 0.001 to 10 mol%. The polar olefin copolymer according to claim 1 or 2, wherein the weight average molecular weight (Mw) determined by gel permeation chromatography (GPC) is in the range of 5000 to 1000000. The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) determined by gel permeation chromatography (GPC) is in the range of 1.2 to 6.5. The polar olefin copolymer of any one of these. Melting | fusing point is 50-140 degreeC, The polar olefin copolymer of any one of Claims 1-4 characterized by the above-mentioned.