WO2012124345A1 - Polyoléfine réactive, son procédé de production, et composition contenant une telle polyoléfine - Google Patents

Polyoléfine réactive, son procédé de production, et composition contenant une telle polyoléfine Download PDF

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WO2012124345A1
WO2012124345A1 PCT/JP2012/001838 JP2012001838W WO2012124345A1 WO 2012124345 A1 WO2012124345 A1 WO 2012124345A1 JP 2012001838 W JP2012001838 W JP 2012001838W WO 2012124345 A1 WO2012124345 A1 WO 2012124345A1
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polyolefin
weight
group
reactive
reactive polyolefin
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町田　修司
巽　富美男
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出光興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C09J123/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • 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
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators

Definitions

  • the present invention relates to a reactive polyolefin, a method for producing the same, and a composition containing the reactive polyolefin.
  • polyolefin especially polypropylene
  • the adhesive in the industrial field is required to have adhesion with metal, resin other than polyolefin or polyolefin resin, and paintability.
  • a pretreatment process such as surface modification of the polyolefin resin or plummer treatment is required.
  • urethane-based adhesives are mainly used.
  • urethane-based adhesives have a problem that they have poor adhesion to the polyolefin interface and have a large environmental load without pretreatment.
  • an adhesive that does not depend on an isocyanate compound is desired, and a polyolefin-based adhesive has been actively studied.
  • polyolefin adhesives have problems of poor workability due to poor low temperature coatability and short open time.
  • the coating property and the heat resistance after curing which is important as an adhesive, are in inverse proportion to each other, and it has been a problem to achieve both coating property and heat resistance.
  • Patent Document 1 discloses a composition based on a low stereoregular polyolefin, which contains polypropylene modified with alkoxysilicon and an acrylic monomer.
  • Patent Document 2 discloses a polypropylene obtained by modifying a low stereoregular polypropylene with maleic anhydride or the like.
  • Patent Document 1 has improved low-temperature coating properties, the heat resistance is low in a test assuming an actually used environment. Moreover, the polypropylene of patent document 2 is not disclosed about the heat resistant expression effect important as an adhesive, and moisture hardening.
  • An object of the present invention is to provide a reactive polyolefin having a long open time, a low melting temperature, which can be applied at a low temperature, and excellent in heat resistance after moisture curing. It is another object of the present invention to provide a reactive polyolefin and / or a method for producing a reactive polyolefin capable of controlling the curing rate and improving the low temperature characteristics.
  • [Vinylalkoxysilane] CH 2 CR 1 -Si (OR 2 ) 3-n R 3 n (I) (Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 and R 3 are each an alkyl group having 1 to 10 carbon atoms.
  • n is an integer of 0, 1 or 2.
  • X 1 -CR 3 CR 4 -X 2 formula (II) (Wherein X 1 and X 2 are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X 1 and X 2 are bonded to each other to form a ring. Provided that when one of X 1 and X 2 is a hydrogen atom, the other is a functional group containing an oxygen, nitrogen, or sulfur atom. R 3 and R 4 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ) 3. 3. 3.
  • Heat-resistant creep temperature after moisture curing is 65 to 130 ° C (6) Open time is 15 seconds to 5 minutes (7) Acetone dissolution amount at 25 ° C. is the following formulas (7-1) and (7-2), or the following formulas (7-3) and (7-4) Meet.
  • Mesopentad fraction [mmmm] is in the range of 20 to 80 mol%
  • weight average molecular weight (Mw) is in the range of 10,000 to 500,000
  • molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4.0.
  • CH 2 CR 1 -Si (OR 2 ) 3-n R 3 n (I) (Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
  • R 2 and R 3 are each an alkyl group having 1 to 10 carbon atoms. n is an integer of 0, 1 or 2. ) 8). 8. The process for producing a reactive polyolefin according to 7, wherein the polyolefin (1) is a polyolefin having 0.5 to 1.0 terminal unsaturated groups per molecule. 9. 9.
  • X 1 -CR 3 CR 4 -X 2 formula (II)
  • X 1 and X 2 are each a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom, or a hydrogen atom, and X 1 and X 2 are bonded to each other to form a ring.
  • X 1 and X 2 are bonded to each other to form a ring.
  • the other is a functional group containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom.
  • R 3 and R 4 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • 10. 10 The method for producing a reactive polyolefin according to any one of 7 to 9, further using 0.2 to 30 parts by weight of the crystalline polyolefin (2). 11. 11. The method for producing a reactive polyolefin according to 10, wherein the crystalline polyolefin (2) is an ethylene polymer or a crystalline polyolefin having a mesopentad fraction [mmmm] of more than 80%.
  • the reaction according to 10 wherein the crystalline polyolefin (2) is a homopolyethylene, an ethylene / ⁇ -olefin copolymer, an olefin copolymer containing a polar group, or a polypropylene having a mesopentad fraction [mmmm] of more than 80%.
  • the crystalline polyolefin (2) is a homopolyethylene, an ethylene / ⁇ -olefin copolymer, an olefin copolymer containing a polar group, or a polypropylene having a mesopentad fraction [mmmm] of more than 80%.
  • a composition comprising the reactive polyolefin according to any one of 1 to 6 and at least one of a curing agent and a curing accelerator.
  • An adhesive composition comprising 100 parts by weight of the reactive polyolefin according to any one of 1 to 6; 0 to 200 parts by weight of a thermoplastic resin; and 0 to 100 parts by
  • the adhesive composition according to 14 which is moisture curable under an atmosphere substantially containing moisture. 16.
  • a reactive polyolefin that has a long open time, has a low melting temperature, can be applied at a low temperature, and is excellent in heat resistance after moisture curing.
  • FIG. 2 is an electron micrograph of a reactive polyolefin of Example 24.
  • FIG. 4 is an electron micrograph of a silane-modified polypropylene of Comparative Example 6.
  • the reactive polyolefin of the present invention is a polyolefin that can be moisture-cured by having an alkoxysilicon group that forms a crosslinked structure by silanol condensation reaction, and is derived from a vinylalkoxysilane represented by the following formula (I) (A) And a structure (B) in which at least one selected from ethylene and an ⁇ -olefin having 3 to 20 carbon atoms is a polymerized chain (except that the structure (B) is a homopolyethylene chain).
  • CH 2 CR 1 -Si (OR 2 ) 3-n R 3 n (I) (Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 and R 3 are each an alkyl group having 1 to 10 carbon atoms.
  • n is an integer of 0, 1, or 2.
  • polyolefin includes a homopolymer and a copolymer
  • homopolyolefin means a homopolymer
  • the structure (A) is a group derived from a vinylalkoxysilane represented by the formula (I), and an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms) of R 1 , R 2 and R 3. Examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclohexyl group, and an octyl group.
  • vinylalkoxysilane represented by the formula (I) include OR 2 having a methoxy group, an ethoxy group, a 1-propoxy group, a 2-propoxy group, a 1-butoxy group, a 2-butoxy group, a tert-butyloxy group, Or the vinyl alkoxysilane which is an octoxy group is mentioned, From a viewpoint with easy acquisition as an industrial raw material, Preferably it is a trimethoxy vinyl silane and a triethoxy vinyl silane.
  • the structure (B) is a chain formed by polymerizing at least one selected from ethylene excluding the homopolyethylene chain and an ⁇ -olefin having 3 to 20 carbon atoms, and the chain having 3 to 20 carbon atoms constituting the chain.
  • olefins include propylene, 1-butene, 1-pentene, 4-methylpentene-1, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 -Pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and the like.
  • Examples of the chain form of the chain composed of ethylene and / or ⁇ -olefin include, for example, a chain composed of one homopolymer or two or more copolymers selected from ⁇ -olefins having 3 to 20 carbon atoms; And a chain composed of a copolymer of 90% by mass or more of one or more monomers selected from ⁇ -olefins of 20 to 10% by mass and 10% by mass or less of ethylene.
  • the homopolymer chain is preferably a propylene chain or a 1-butene chain, more preferably a propylene chain.
  • the chain formed by polymerizing at least one selected from ethylene having the structure (B) and an ⁇ -olefin having 3 to 20 carbon atoms is preferably 0.5 to 1.0 terminal unsaturated groups ( For example, a polyolefin chain having a terminal vinylidene group).
  • a polyolefin chain having a terminal vinylidene group When the number of terminal unsaturated groups per molecule of the structure (B) is less than 0.5, heat resistance may not be sufficiently imparted by a reaction starting from the terminal unsaturated group.
  • the number of terminal unsaturated groups per molecule is more than 1.0, the structure (B) having unsaturated groups at both ends increases, and the melt fluidity changes due to high molecular weight due to crosslinking. The applicability may change.
  • the reactive polyolefin of the present invention satisfies the following (1) to (4).
  • Mesopentad fraction [mmmm] representing average stereoregularity is 25 to 85 mol%
  • Content of structure (A) is 0.1 to 20% by weight
  • Molecular weight distribution (Mw / Mn) 1.5-10 (4)
  • Melt viscosity measured at 190 ° C. is 2000 to 80000 mPas
  • the reactive polyolefin of the present invention has a mesopentad fraction [mmmm] of 25 to 85 mol%, preferably 30 to 75 mol%, more preferably 35 to 70 mol%, particularly preferably 35 to 60 mol%. .
  • a mesopentad fraction of 25 mol% or more means that the reactive polyolefin is crystalline, and the reactive polyolefin can exhibit excellent mechanical strength. Further, when the mesopentad fraction is 85 mol% or less, the reactive polyolefin becomes moderately soft and melts at a low temperature, so that excellent coating workability can be exhibited.
  • the average mesopentad fraction measured for the reactive polyolefin of the present invention is within the above range. Good.
  • stereoregularity can be evaluated by the following method.
  • the mesopentad fraction [mmmm] of the reactive polyolefin is based on the method proposed by A. Zambelli et al. In “Macromolecules, 6,925 (1973)”, and the methyl group signal of the 13 C-NMR spectrum. Is the meso fraction in pentad units in the polypropylene molecule as measured by As the mesopentad fraction [mmmm] increases, the stereoregularity increases.
  • the 13 C-NMR spectrum can be measured by the following apparatus and conditions according to the attribution of the peak proposed by A. Zambelli in “Macromolecules, 8, 687 (1975)”. it can.
  • Apparatus JNM-EX400 type 13 C-NMR apparatus manufactured by JEOL Ltd.
  • Method Proton complete decoupling method Concentration: 220 mg / ml
  • Solvent 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene Temperature: 130 ° C Pulse width: 45 ° Pulse repetition time: 4 seconds Integration: 10,000 times
  • stereoregularity can be evaluated by the following method.
  • Mesopentad fraction [mmmm] is reported in “Polymer Journal, 16, 717 (1984)”, J. Asakura et al. “Macromol. Chem. Phys., C29, 201 (1989)” reported by Randall et al. It can be measured according to the method proposed in “Macromol. Chem. Phys., 198, 1257 (1997)” reported by Busico et al. That is, the mesopentad fraction in the poly (1-butene) molecule can be determined by measuring the signals of methylene group and methine group using 13 C nuclear magnetic resonance spectrum. The 13 C nuclear magnetic resonance spectrum can be measured using the above apparatus and conditions.
  • stereoregularity can be evaluated by the following method.
  • the mesopentad fraction is determined by T.W. Asakura, M .; Demura, Y .; It can be determined in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama. That is, the mesopentad fraction is obtained by utilizing the fact that the CH 2 carbon at the ⁇ -position of the side chain derived from a higher ⁇ -olefin is split and observed in the 13 CNMR spectrum, reflecting the difference in stereoregularity. Can do.
  • the 13 C nuclear magnetic resonance spectrum measuring apparatus and conditions are the same as described above.
  • Content of structure (A) is 0.1 to 20% by weight
  • the content (configuration ratio) in the reactive polyolefin of the structure (A) is preferably 0.25 to 20% by weight, more preferably 0.25 to 18% by weight, and still more preferably 0.30 to It is 15% by weight, particularly preferably 0.50 to 10% by weight, more particularly preferably 0.50 to 6.0% by weight, and most preferably 0.50 to 5.0%.
  • the content of the structure (A) is less than 0.1% by weight, the heat resistance of the reactive polyolefin due to moisture curing may be insufficient.
  • the content of the structure (A) is more than 20% by weight, the heat resistance of the reactive polyolefin is improved, but the flexibility may be lowered.
  • the content of the structure (A) in the reactive polyolefin can be measured by a known method such as NMR, infrared absorption spectrum, or titration.
  • a known method such as NMR, infrared absorption spectrum, or titration.
  • the structure (B) of the reactive polyolefin is a polypropylene type
  • in the infrared absorption spectrum method a characteristic absorption based on Si—O bonds (1130.0 to 1054.0 cm ⁇ 1 ) is obtained using a sample with a clear composition in advance.
  • a calibration curve based on the thickness-corrected (standardized) numerical value of 4500.0-3850.0 cm ⁇ 1 which is a combined sound of CH stretching of polyolefin and various peaks in the fingerprint region.
  • the method of calculating by this is mentioned.
  • the content ratio of the structure (A) can be directly determined by NMR.
  • the content (configuration ratio) of the structure (B) is preferably 99.9 to 60% by weight, more preferably 99.5 to 70% by weight, and further preferably 99.0 to 75% by weight. It is.
  • the content of the structure (B) can be measured by a known method such as NMR, infrared absorption spectrum, or titration.
  • the reactive polyolefin of the present invention has a molecular weight distribution (Mw / Mn) of 1.5 to 10.0, preferably 1.5 to 4.5, more preferably 1.5 to 4.3, Particularly preferred is 1.7 to 4.3. If the Mw / Mn of the reactive polyolefin is less than 1.5, the melt fluidity may decrease when compared with the same molecular weight. On the other hand, when Mw / Mn is more than 10.0, low molecular weight substances increase, so that the adhesive strength, heat resistance, etc. may be reduced.
  • the molecular weight distribution (Mw / Mn) of the reactive polyolefin can be determined by measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) by the GPC method.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are determined by the Universal Calibration method using the constants K and a of the Mark-Houwink-Sakurada formula in order to convert the polystyrene equivalent molecular weight into the molecular weight of the corresponding polymer. Can do. Specifically, it can be determined by the method described in ““ Size Exclusion Chromatography ”” written by Sadao Mori, P67-69, 1992, Kyoritsu Shuppan. K and ⁇ are “Polymer Handbook” John Wiley & Sons, Inc. Is described in each. Moreover, it can also determine by a conventional method from the relationship of the intrinsic viscosity with respect to the newly calculated absolute molecular weight.
  • Detector RI detector for liquid chromatography Waters 150C Column: TOSO GMHHR-H (S) HT Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 ml / min Sample concentration: 0.3% by mass
  • the reactive polyolefin of the present invention has a melt viscosity (B viscosity) measured at 190 ° C. of 2000 to 80000 mPas, preferably 2000 to 50000 mPas, more preferably 2200 to 45000 mPas. And particularly preferably 2500 to 40000 mPas.
  • B viscosity measured at 190 ° C.
  • the B viscosity of the reactive polyolefin is less than 2000, dripping may occur when applying in a molten state, and workability may be reduced.
  • the B viscosity is more than 80000, the applicability may decrease due to the high viscosity.
  • the B viscosity of the reactive polyolefin can be measured by using a Brookfield viscometer based on JISK-6862 and a reactive polyolefin melted at 190 ° C. or a composition containing the reactive polyolefin.
  • a Brookfield viscometer based on JISK-6862
  • a reactive polyolefin melted at 190 ° C. or a composition containing the reactive polyolefin for example, TVB-10 type viscometer manufactured by Toki Sangyo Co., Ltd. and M2 rotor (No. 21) may be used, and an H-2 type small sample adapter may be used.
  • the reactive polyolefin of the present invention preferably satisfies any one or more of the following (5) to (7).
  • Heat-resistant creep temperature after moisture curing is 65 to 130 ° C
  • Open time is 15 seconds to 5 minutes
  • Acetone dissolution amount at 25 ° C. is the following formulas (7-1) and (7-2), or the following formulas (7-3) and (7-4) Meet.
  • the reactive polyolefin of the present invention preferably has a heat-resistant creep temperature after moisture curing of 65 to 130 ° C, more preferably 66 to 130 ° C, and even more preferably 67 to 130 ° C. 130 ° C.
  • the heat-resistant creep temperature after moisture curing of the reactive polyolefin is less than 65 ° C., the use environment of the reactive polyolefin may be limited. On the other hand, it is technically limited that the heat-resistant creep temperature after moisture curing of the reactive polyolefin exceeds 130 ° C.
  • the heat-resistant creep temperature can be measured according to JIS K6833.
  • Reactive polyolefin is preferably an adhesive having a low melt viscosity and a high heat-resistant creep temperature after curing.
  • the heat-resistant creep is the same B viscosity.
  • An adhesive having a high temperature is preferred, and a lower B viscosity is preferred if the heat resistant creep temperature is the same.
  • the reactive polyolefin of the present invention preferably has a B viscosity and a heat resistant creep temperature satisfying a heat resistant creep temperature ⁇ 18.2 log [B] +1.4, and satisfying a heat resistant creep temperature ⁇ 18.2 log [B] +2.0. More preferably, the heat resistant creep temperature ⁇ 18.2 log [B] +2.5 is more preferably satisfied.
  • [B] is the B viscosity of the reactive polyolefin, and when the reactive polyolefin satisfies the above formula, it can exhibit excellent heat resistance and low temperature flow.
  • the adhesive is easy to apply and has high heat resistance after moisture curing.
  • the reactive polyolefin must have a low melt viscosity and a high heat-resistant creep temperature. Is required.
  • the melt viscosity and the heat resistant creep temperature are contradictory properties, and if the reactive polyolefin has a low melt viscosity, the heat resistant creep temperature is generally low. Since the melt viscosity depends on the molecular weight, a low melt viscosity means a low molecular weight product.
  • a high heat-resistant creep temperature means that the reactive polyolefin has a structure in which a structure (B) in which an alkoxysilicon group has a chain length of a certain level or more is sandwiched. It means having. Therefore, it is estimated that the fact that the reactive polyolefin satisfies the above formula means that the reactive polyolefin is a low molecular weight substance and the concentration of the structure in which the alkoxysilicon group sandwiches the structure (B) is high.
  • the reactive polyolefin of the present invention preferably has an open time of 15 seconds to 5 minutes, more preferably 20 seconds to 5 minutes, and even more preferably 25 seconds to 4 minutes.
  • the above-mentioned open time means the time from applying the adhesive containing the reactive polyolefin of the present invention to stretching the adherend, and means the time until the initial adhesive force is maintained.
  • a long open time is preferable because a fine adjustment of the position at the time of bonding and a time margin for large-area bonding are created.
  • the open time is less than 15 seconds, it is necessary to finish the bonding operation in a short time, and there is a possibility that a defect is likely to occur due to bonding of a large area. On the other hand, it is technically difficult to make the open time longer than 5 minutes.
  • the reactive polyolefin of the present invention preferably has an acetone solubility at 25 ° C. of the following formulas (7-1) and (7-2), or (7-3) and Satisfies (7-4).
  • the structure (C) will be described later.
  • the acetone soluble amount of the reactive polyolefin is an index indicating whether or not the structure (A) is uniformly added regardless of the molecular weight of the reactive polyolefin. .
  • the acetone-soluble amount tends to increase, and the heat-resistant creep performance may decrease as the amount increases.
  • the acetone soluble amount (% by weight) preferably ⁇ 1.0 ⁇ [structure (A) content (% by weight)], more preferably the acetone soluble amount (% by weight). ⁇ 0.95 ⁇ [structure (A) content (% by weight)].
  • the acetone soluble amount (wt%) of the reactive polyolefin ⁇ 5 wt%, the acetone soluble amount (wt%) ⁇ 4 wt%, and the acetone soluble amount (wt%) ⁇ 3. 5 wt%, acetone soluble amount (wt%) ⁇ 3 wt%, acetone soluble amount (wt%) ⁇ 2.5 wt%, acetone soluble amount (wt%) ⁇ 2 wt%, acetone soluble amount ( % By weight) ⁇ 2% by weight.
  • the amount of acetone soluble in the reactive polyolefin is determined whether the structures (A) and (C) are uniformly added regardless of the molecular weight of the reactive polyolefin. It is an index to represent. In particular, when the reactive polyolefin has a low molecular weight and a large amount of addition of the structures (A) and (C), the acetone-soluble amount tends to increase, and the heat-resistant creep performance decreases as this amount increases. There is a fear.
  • the acetone soluble amount (wt%) ⁇ 0.87 ⁇ [structure (A) and (B) content (wt%)], more preferably the acetone soluble amount ( % By weight) ⁇ 0.85 ⁇ [content of structures (A) and (B) (% by weight)].
  • the acetone soluble amount (% by weight) of the reactive polyolefin ⁇ 20% by weight, the acetone soluble amount (% by weight) ⁇ 19% by weight, the acetone soluble amount (% by weight) ⁇ 17% by weight. Acetone soluble amount (% by weight) ⁇ 15% by weight is preferable.
  • the acetone soluble amount of the reactive polyolefin can be measured as follows.
  • the reactive polyolefin obtained by the production method described later was dried under reduced pressure at 150 ° C. for 8 hours to be an evaluation sample (1).
  • the raw material of the structure (B) used for the production of the reactive polyolefin is also treated in the same manner as the evaluation sample (1) to obtain an evaluation sample (2).
  • Extraction processing is performed at 25 ° C. for 8 hours while dispersing 5 g (referred to as W 0 ) of the micronized sample (1) in 150 ml of acetone and stirring.
  • W 0 dispersing 5 g
  • the solid-liquid level becomes constant by standing or by a centrifuge, and then the solid is separated by filtration.
  • the separated solid is subjected to a second extraction process in the same manner, and the solid components separated for the first time and the second time are all dried under reduced pressure at 100 ° C. for 8 hours, and the weight thereof is measured.
  • the weight is defined as W 1 . .
  • the entire amount of the filtrate was recovered, the solid component was recovered by evaporation to dryness, dried under reduced pressure at 100 ° C.
  • Acetone soluble part (% by weight) 100 ⁇ W 2 / (W 1 + W 2 ) (However, (W 1 + W 2 ) / W 0 ⁇ 0.98.)
  • the same operation is performed for the evaluation sample (2), and the acetone-soluble amount is measured.
  • the acetone soluble amount of the normal evaluation sample (2) is in the range of 0.01 to 0.1% by weight.
  • a value obtained by subtracting the acetone soluble amount (% by weight) of the evaluation sample (2) from the acetone soluble amount (% by weight) of the evaluation sample (1) obtained from the above formula is defined as the acetone soluble amount of the reactive polyolefin. .
  • the reactive polyolefin of the present invention preferably satisfies the following (8) in addition to the above (1) to (4).
  • a vinylalkoxysilane residue is present in the “sea” component observed based on morphological observation with an electron microscope.
  • the presence of a vinylalkoxysilane residue in the “sea” component indicates that the structure (A) is uniformly added. Whether or not the structure (A) is uniformly added (hereinafter also referred to as “uniformity”) can be evaluated by measuring the acetone-soluble amount, but whether or not the requirement (8) is satisfied. It can also be evaluated by measuring. As described in the evaluation of the acetone-soluble amount, in order for the reactive polyolefin to be excellent in heat resistance, the reactive polyolefin is required to be uniformly crosslinked. For this purpose, it is preferable that an alkoxysilane group serving as a crosslinking point is present in the sea (matrix) of the reactive polyolefin.
  • the reactive polyolefin of the present invention is a uniform reactive polyolefin obtained by uniformly reacting vinyl alkoxysilane with the polyolefin (1) forming the structure (B). Since it is a uniform reactive polyolefin, it is estimated that heat resistance is exhibited.
  • Whether or not a vinylalkoxysilane residue is present in the “sea” component can be evaluated by the following measurement method.
  • the cross section of the reactive polyolefin is subjected to elemental analysis by an electron microscope to measure the dispersion state of silicon atoms derived from vinylalkoxysilane.
  • the uniformity is low, the sea (matrix) / island (domain) structure is formed, and the amount of silicon elements existing in the sea island is different, and a large amount of silicon atoms exist on the island.
  • the heat resistance improvement by the crosslinking reaction is limited to the island portion, and the sea portion of the main component has a small degree of crosslinking reaction and does not improve the heat resistance.
  • the specific measurement method is as follows. Sea-island structure and elemental analysis method by transmission electron microscope (TEM) a) TEM observation: device, sample pretreatment, measurement conditions Device: JEM-2100 (HR) manufactured by JEOL Ltd. Sample pretreatment: Ultra-thin section (-100 ° C) with ultramicrotome ULTRACUT R manufactured by Leica Microsystems Co., Ltd. was used to prepare ultrathin slices, placed on Cu grid, and 0.5% RuO 4 Vapor stained. Measurement conditions: Observation was performed at an acceleration voltage of 200 kV (imaging magnification of 50,000 times (when elemental analysis was performed, the imaging magnification was 200,000 times in STEM mode). b) Elemental analysis: Equipment, sample pretreatment, measurement conditions Detector: EX-24063JGT manufactured by JEOL Ltd. Accelerating voltage: 200kV Sample: An ultrathin section (on a Cu grid) prepared for TEM observation was used.
  • the form is observed with a transmission electron microscope to confirm that the island component is not present, and the vinylalkoxysilane content is 0.1 to 20% by weight. It is in the range.
  • “the island component does not exist” is more specifically described as follows. As a result of observation with a transmission electron microscope, there is no island component of 50 nm or more in a field of view with a photographing magnification of 50,000 to 200,000 times. If there is a defect or the like on the observation surface, it may be recognized as an island component. In this case, the presence of silicon atoms and oxygen atoms derived from vinylalkoxysilane by elemental analysis Confirm that there is no difference. Moreover, as a preferable form when an island component exists, when the form is observed with a transmission electron microscope and it is confirmed that a sea island exists, at least a silicon element derived from vinylalkoxysilane can be detected in the sea component.
  • the reactive polyolefin of the present invention preferably has 1 to 35% by weight of a structure (C) derived from a vinyl monomer represented by the following formula (II).
  • R 3 and R 4 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • Examples of the vinyl monomer represented by the above formula (II) include the following compounds [i] to [vii].
  • Acrylic acid and its derivatives represented by the formula (II) include the following (1) to (6).
  • Acrylic acid (2) Acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, normal octyl acrylate, 2-ethylhexyl acrylate; polyethylene glycol monoacrylate, polyethylene glycol polypropylene glycol acrylate, poly ( Ethylene glycol-n-tetramethylene glycol) monoacrylate, propylene glycol polybutylene glycol monoacrylate, polypropylene glycol monoacrylate, etc., long-chain polyalkylene glycols having a molecular weight of 30,000 or less (3) sodium acrylate, potassium acrylate, acrylic acid Acrylic acid salt composed of acrylic acid and typical metallic elements such as magnesium and calcium acrylate (4) Ester residue, oxygen atom, Acrylic acid esters containing one or more atoms selected from elemental atoms, sulfur atoms and silicon atoms (
  • Vinyl esters and derivatives thereof, and alkoxy vinyl silanes Vinyl esters and derivatives thereof represented by formula (II) and alkoxy vinyl silanes include vinyl acetate, vinyl propionate, vinyl isolactate, vinyl pivalate, vinyl caproate, and capryl. Vinyl esters such as vinyl acrylate, vinyl octylate, vinyl caprate, vinyl undecanoate, vinyl myristate, vinyl palmitate, vinyl stearate, and vinyl cyclohexanecarboxylate; and alkoxy vinyl silanes such as trimethoxy vinyl silane and triethoxy vinyl silane Is mentioned.
  • Styrene and its derivatives include ⁇ -methyl styrene, p-methyl styrene, p-ethyl styrene, p-propyl styrene, p-isopropyl styrene, p-butyl styrene.
  • P-tert-butylstyrene P-tert-butylstyrene, p-phenylstyrene, o-methylstyrene, o-ethylstyrene, o-propylstyrene, o-isopropylstyrene, m-methylstyrene, m-ethylstyrene, m-isopropylstyrene, m- Alkyl styrenes such as butyl styrene, mesityl styrene, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 3,5-dimethyl styrene; alkoxy such as p-methoxy styrene, o-methoxy styrene, m-methoxy styrene Styrenes; p-chlorostyren
  • Maleic anhydride and its substitutes Maleic anhydride represented by formula (II) and its substitutes include maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, phenyl maleic anhydride, diphenyl maleic anhydride And maleic anhydride such as
  • Maleic acid and its ester Maleic acid represented by the formula (II) and its ester include maleic acid, methyl maleic acid, dimethyl maleate, diethyl maleate, dibutyl maleate, monomethyl maleate, maleic acid and the like These esters are mentioned.
  • Maleimide and its Substitutes Maleimides represented by formula (II) and their substitutes include maleimides such as maleimide, N-alkyl substituted maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and the like The substitution body of this is mentioned.
  • the vinyl monomer represented by the formula (II) is preferably a vinyl monomer having a glass transition temperature (Tg) of 20 ° C. or lower from the viewpoint of increasing the open time.
  • Tg glass transition temperature
  • acrylic acid and derivatives thereof are acrylic acid having a long-chain alkyl ester group and derivatives thereof. Specific examples include acrylate esters containing long-chain alkyls such as butyl acrylate, 2-ethylhexyl acrylate, and lauryl acrylate.
  • Methacrylic acid and ⁇ -alkyl substituted acrylic acid are ⁇ -alkyl substituted methacrylic acid having a long-chain alkyl ester group, specifically, acrylic acid having the long-chain alkyl ester group and A compound having a methyl group as an ⁇ -alkyl group of the derivative;
  • Vinyl esters and derivatives thereof include vinyl caprylate having a long-chain alkyl ester group, vinyl octylate, vinyl caprate, vinyl undecanoate, vinyl myristate, vinyl palmitate, and vinyl stearate,
  • Examples of styrene and its derivatives include p-propylstyrene and p-butylstyrene.
  • preferred vinyl monomers represented by the formula (II) are butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, etc. from the viewpoint that low temperature flexibility can be effectively imparted.
  • the content in the reactive polyolefin of the structure (C) derived from the vinyl monomer represented by the formula (II) is 1 to 35% by weight, preferably 1 to 30% by weight, more preferably 2 to 25% by weight.
  • the open time can be extended.
  • the mechanical strength of the reactive polyolefin is not lowered, which is preferable.
  • the content of the structure (C) in the reactive polyolefin can be measured by a known method such as NMR, infrared absorption spectrum, or titration.
  • a characteristic absorption based on, for example, C ⁇ O bond (1780.0 to 1700.0 cm ⁇ 1 )
  • the reactive polyolefin has a structure (C) derived from two or more kinds of vinyl monomers
  • a calibration curve may be prepared in advance based on the respective characteristic absorption bands.
  • the monomer (*) content is first determined from the different absorption bands derived from one monomer (*), and the monomer (*) is subtracted from the overlapping characteristic absorption. The remainder can also be determined as the content of other monomers.
  • the content ratio of the structure (C) can be directly determined by NMR.
  • the reactive polyolefin of the present invention can have a structure (D) derived from the crystalline polyolefin (2).
  • the crystalline polyolefin (2) will be described later.
  • the content of the reactive polyolefin of the structure (D) is 0.1 to 30% by weight, preferably 0.1 to 25% by weight, more preferably 0.1 to 20% by weight. Content of structure (D) can be measured similarly to structure (C).
  • the reactive polyolefin of the present invention may have the structures (A) and (B), and optionally the structures (C) and (D).
  • the structures (A) and (B) and the arbitrary structures (C) The total content of the structure (D) is, for example, 75% by weight, 80% by weight, 90% by weight, 92% by weight, 95% by weight, 96% by weight, 98% by weight, 99% by weight % Or more and 100% by weight.
  • the reactive polyolefin of the present invention may contain an antioxidant, an ultraviolet absorber, a pigment and the like.
  • the reactive polyolefin of the present invention has a mesopentad fraction [mmmm] in the range of 20 to 80 mol%, a weight average molecular weight (Mw) in the range of 10,000 to 500,000, and a molecular weight distribution (Mw / Mn) of 1.
  • polyolefin (1) obtained by polymerizing one or more selected from ethylene and ⁇ -olefin having 3 to 20 carbon atoms in the range of 5 to 4.0; vinyl alkoxysilane represented by the following formula (I) It can be produced by reacting 0.5 to 25 parts by weight; and 0.01 to 5 parts by weight of an organic peroxide in a temperature range of 120 to 260 ° C. in the molten state of the polyolefin (1).
  • polyolefin (1) is not homopolyethylene.
  • CH 2 CR 1 -Si (OR 2 ) 3-n R 3 n (I) (Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R 2 and R 3 are each an alkyl group having 1 to 10 carbon atoms.
  • n is an integer of 0, 1 or 2.
  • the polyolefin (1) corresponds to the structure (B) of the reactive polyolefin, and specific examples, combinations and the like are the same as those of the structure (B).
  • Mesopentad fraction [mmmm] is in the range of 20 to 80 mol%
  • weight average molecular weight (Mw) is in the range of 10,000 to 500,000
  • molecular weight distribution (Mw / Mn) is in the range of 1.5 to 4.0.
  • a certain polyolefin (1) is obtained by polymerizing one or more selected from ethylene and an ⁇ -olefin having 3 to 20 carbon atoms using hydrogen as a molecular weight regulator in the presence of a main catalyst, a co-catalyst and organoaluminum described later. Can be manufactured.
  • a metallocene catalyst can be used as the main catalyst used for the production of the polyolefin (1).
  • the metallocene catalyst is preferably a double bridged metallocene catalyst or a C 1 symmetric ansa metallocene compound, more preferably a double bridged metallocene catalyst.
  • Examples of the double bridged metallocene catalyst include bibridged complexes represented by the following formula (I ′).
  • M represents a metal element of Groups 3 to 10 of the periodic table, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium, and lanthanoid series. Metal etc. are mentioned. Among these, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity and the like, and zirconium is most preferable from the viewpoint of yield of terminal vinylidene group and catalytic activity.
  • E 1 and E 2 are substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N ⁇ ), phosphine group (—P ⁇ ), Hydrocarbon group [>CR-,> C ⁇ ] and silicon-containing group [>SiR-,> Si ⁇ ] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group)
  • a ligand selected from among (A) is shown, and a crosslinked structure is formed through A 1 and A 2 .
  • E 1 and E 2 may be the same as or different from each other.
  • a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable, and at least one of E 1 and E 2 is a cyclopentadienyl group, A substituted cyclopentadienyl group, an indenyl group or a substituted indenyl group;
  • X represents a ⁇ -bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E 1 , E 2 or Y.
  • X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include silicon-containing groups having 1 to 20 carbon atoms, phosphide groups having 1 to 20 carbon atoms, sulfide groups having 1 to 20 carbon atoms, acyl groups having 1 to 20 carbon atoms, and the like.
  • Y represents a Lewis base, and when there are a plurality of Ys, the plurality of Ys may be the same or different, and may be cross-linked with other Y, E 1 , E 2 or X.
  • Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
  • a 1 and A 2 are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group.
  • R 1 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and they may be the same as each other May be different.
  • q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.
  • At least one is preferably a crosslinking group composed of a hydrocarbon group having 1 or more carbon atoms.
  • an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable.
  • R 2 and R 3 are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they are the same as each other. However, they may be different from each other and may be bonded to each other to form a ring structure, and e represents an integer of 1 to 4.
  • transition metal compound represented by the formula (I ′) include specific examples described in WO2008 / 066168 and WO2008 / 047860.
  • a transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.
  • the compounds represented by the formula (II ′) are preferable.
  • M represents a metal element of Groups 3 to 10 of the periodic table
  • a 1a and A 2a each represent a bridging group represented by the formula (a) in the above formula (I ′). shows, CH 2, CH 2 CH 2 , (CH 3) 2 C, (CH 3) 2 C (CH 3) 2 C, the (CH 3) 2 Si, and (C 6 H 5) 2 Si preferred.
  • a 1a and A 2a may be the same as or different from each other.
  • R 4 to R 13 each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group.
  • R 4 and R 5 a group containing a hetero atom such as halogen, oxygen, or silicon is preferable because of high polymerization activity.
  • R 6 to R 13 are preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • X and Y are the same as those in formula (I ′).
  • q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3.
  • transition metal compounds represented by the above formula (II ′) when both indenyl groups are the same, examples of the transition metal compounds in Group 4 of the periodic table include those described in WO2008 / 066168 and WO2008 / 047860. An example is given. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.
  • transition metal compounds represented by the above formula (II ′) when R 5 is a hydrogen atom and R 4 is not a hydrogen atom, examples of the transition metal compound belonging to Group 4 of the periodic table include WO2008 / 066168 and Specific examples described in WO2008 / 047860 can be given. Further, it may be a compound similar to a metal element other than Group 4. A transition metal compound belonging to Group 4 of the periodic table is preferred, and a zirconium compound is particularly preferred.
  • the C 1 symmetric ansa metallocene compound is a transition metal compound represented by the following formula (I ′′).
  • a 1 and A 2 are each a conjugated 5-membered ring ligand, and at least one of A 1 and A 2 is an adjacent substituent on the conjugated 5-membered ring ligand.
  • M represents a transition metal atom selected from Group 4 of the periodic table
  • X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group, an alkylamide group, or a halogenated carbon atom bonded to M.
  • a hydrogen group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, a silicon-containing hydrocarbon group, and a sulfur-containing group are shown.
  • the conjugated 5-membered ring ligand include a cyclopentadienyl group which may have a substituent.
  • substituent include hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms.
  • Examples include butenyl, butadienyl, and triphenylcarbyl groups.
  • substituent other than the hydrocarbon group examples include hydrocarbon residues containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur. Specific examples thereof include methoxy group, ethoxy group, phenoxy group, furyl group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, carbazolyl group, dimethylphosphino group, diphenylphosphino group, diphenylboron group. , Dimethoxyboron group, thienyl group and the like.
  • substituents include a halogen atom or a halogen-containing hydrocarbon group.
  • At least one of A 1 and A 2 is bonded to an adjacent substituent on the conjugated 5-membered ring ligand to form a 7-10 membered condensed ring including 2 atoms of the 5-membered ring.
  • Specific examples thereof include compounds such as azulene and derivatives thereof.
  • hydroazurenyl group methylhydroazurenyl group, ethylhydroazurenyl group, dimethylhydroazurenyl group, methylethylhydroazurenyl group, methylisopropylhydroazurenyl group, methylphenylisopropylhydroazurenyl group, various types Hydrogenated azulenyl group, bicyclo- [6.3.0] -undecanyl group, methyl-bicyclo- [6.3.0] -undecanyl group, ethyl-bicyclo- [6.3.0] -undecanyl group, Phenyl-bicyclo- [6.3.0] -undecanyl group, methylphenyl-bicyclo- [6.3.0] -undecanyl group, ethylphenyl-bicyclo- [6.3.0] -undecanyl group, methyldiphenyl-
  • substituent for each group examples include the hydrocarbon groups described above, hydrocarbon groups containing atoms such as silicon, oxygen, nitrogen, phosphorus, boron, and sulfur, halogen atoms, or halogen-containing hydrocarbon groups.
  • Q represents a binding group that bridges two conjugated 5-membered ring ligands at an arbitrary position. That is, Q is a divalent linking group and crosslinks A 1 and A 2 .
  • the type of Q is not particularly limited.
  • Examples thereof include a germylene group as a substituent.
  • the silylene group or germylene group which has an alkylene group, a cycloalkylene group, an arylene group, and a hydrocarbon group as a substituent is preferable.
  • M represents a transition metal atom selected from Group 4 of the periodic table, and is preferably zirconium or hafnium.
  • X and Y are each independently a hydrogen atom bonded to M, a halogen atom, a hydrocarbon group, an alkylamide group, a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, or a phosphorus-containing hydrocarbon.
  • the number of carbon atoms in each of the hydrocarbon groups is usually 1-20, preferably 1-12.
  • a hydrogen atom, a chlorine atom, a methyl group, an isobutyl group, a phenyl group, a dimethylamide group, a diethylamide group, and a sulfinato group are preferable.
  • C 1 symmetric ansa metallocene compound examples include specific examples described in JP-A-2003-231714.
  • the co-catalyst for the polyolefin (1) is a compound that can react with the transition metal compound as the main catalyst to form an ionic complex, and examples thereof include aluminoxane, borate compounds and clay minerals, and preferably borate compounds.
  • R 15 is a hydrocarbon group such as an alkyl group, an alkenyl group, an aryl group, an arylalkyl group or the like having 1 to 20 (preferably 1 to 12) carbon atoms, or a halogen atom.
  • w represents an average degree of polymerization and is usually an integer of 2 to 50, preferably 2 to 40.
  • R 15 may be the same or different from each other.
  • aluminoxanes may be used alone or in combination of two or more.
  • the aluminoxane may be insoluble in toluene.
  • the aluminoxane can be produced by a known method, for example, a method in which an alkylaluminum is brought into contact with a condensing agent such as water. Specifically, a method of dissolving an organoaluminum compound in an organic solvent and bringing it into contact with water; a method of initially adding an organoaluminum compound at the time of polymerization and a method of adding water later; For example, a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound; a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum and further reacting with water.
  • borate compound that is a co-catalyst are described in WO2008 / 047860. These can be used individually by 1 type or in combination of 2 or more types.
  • the molar ratio of hydrogen to transition metal compound (hydrogen / transition metal compound) is 0, dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) borate and tetrakis (per Fluorophenyl) methylanilinium borate and the like are preferred.
  • clay minerals as promoters include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite, anorcite, halloysites such as metahalloysite, halloysite, serpentine such as chrysotile, risardite, and antigolite. Tribes, montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, etc. , Gyrome clay, hysingelite, pyrophyllite, ryokdee stone group and the like. These may form a mixed layer.
  • organoaluminum compound used for manufacture of polyolefin (1) As an organoaluminum compound used for manufacture of polyolefin (1), the specific example as described in WO2008 / 047860 is mentioned. These organoaluminum compounds may be used alone or in combination of two or more. Of these, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum is preferred, and triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum are more preferred. preferable.
  • trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trinormalhexylaluminum and trinormaloctylaluminum is preferred, and triis
  • the amount of the main catalyst used is usually 0.1 ⁇ 10 ⁇ 6 to 1.5 ⁇ 10 ⁇ 5 mol / L, preferably 0.15 ⁇ 10 ⁇ 6 to 1.3 ⁇ . 10 ⁇ 5 mol / L, more preferably 0.2 ⁇ 10 ⁇ 6 to 1.2 ⁇ 10 ⁇ 5 mol / L, particularly preferably 0.3 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 5 mol / L It is.
  • the amount of the main catalyst used is 0.1 ⁇ 10 ⁇ 6 mol / L or more, the catalyst activity is sufficiently expressed, and when it is 1.5 ⁇ 10 ⁇ 5 mol / L or less, the heat of polymerization is easily removed. can do.
  • the main catalyst / promoter which is the ratio of the main catalyst to the cocatalyst, is preferably 10/1 to 1/100, more preferably 2/1 to 1/10 in molar ratio.
  • the main catalyst / co-catalyst is in the range of 10/1 to 1/100, an effect as a catalyst can be obtained and the catalyst cost per unit mass polymer can be suppressed. Further, there is no fear that a large amount of boron is present in the polyolefin (1).
  • the main catalyst / organoaluminum compound which is the ratio of the main catalyst to the organoaluminum compound used, is preferably in a molar ratio of 1/1 to 1/10000, more preferably 1/5 to 1/2000, and even more preferably 1/10.
  • the polymerization activity per transition metal can be improved.
  • the main catalyst / organoaluminum compound is in the range of 1/1 to 1/10000, the balance between the addition effect of the organoaluminum compound and the economic efficiency is good, and a large amount of aluminum is present in the polyolefin (1). There is no fear.
  • preliminary contact can be carried out using the main catalyst and promoter described above, or the main catalyst, promoter and organoaluminum compound.
  • the preliminary contact can be performed by bringing the main catalyst into contact with, for example, a cocatalyst, but the method is not particularly limited, and a known method can be used.
  • Such preliminary contact is effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the cocatalyst used.
  • the polymerization temperature is usually ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C.
  • the polymerization pressure is 0.1 MPa to 100 MPa, preferably 0.3 MPa to 10 MPa, more preferably 0.5 MPa to 4 MPa, polymerization time.
  • the polyolefin (1) is preferably a polyolefin having 0.5 to 1.0 terminal unsaturated groups (for example, terminal vinylidene groups) per molecule, and when the polyolefin is produced, the main catalyst is preferably double It is a bridged metallocene compound, and the polymerization reaction may be carried out in the presence of a trace amount of hydrogen (hydrogen / main catalyst molar ratio is 10,000 or less). By carrying out the polymerization reaction in the presence of a small amount of hydrogen, a significant improvement in terminal vinylidene group selectivity can be obtained.
  • solvents used for solution polymerization include saturated hydrocarbon solutions such as hexane, heptane, butane, octane and isobutane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. A solvent is mentioned.
  • the terminal of the polyolefin (1) has an unsaturated group (for example, vinylidene group), because the unsaturated group is easily subjected to radical attack, so that the reaction with vinylalkoxysilane proceeds easily. Moreover, since copolymerization with a vinyl monomer (C) and a vinylidene unsaturated group advances and a uniformity improves, it is preferable.
  • unsaturated group for example, vinylidene group
  • the number of terminal vinylidene groups can also be determined using 13 C-NMR.
  • all end group species are determined, and their abundance is measured.
  • the number of terminal vinylidene groups per molecule can be determined from the proportion of terminal vinylidene groups relative to the total amount of terminal groups, and the selectivity of terminal vinylidene groups can be determined from the proportion of terminal vinylidene groups relative to all unsaturated groups.
  • the measurement of the number of terminal vinylidene groups using 1 H-NMR and 13 C-NMR will be described below using a propylene polymer as an example.
  • the peak intensity of the amount of terminal vinyl groups in 13 C-NMR is calculated as follows using (A) and (B) obtained by 1 H-NMR spectrum.
  • 13 C-NMR terminal vinyl group content peak intensity (B) / (A) ⁇ ⁇ 7>
  • T the total concentration (T) of the end groups is expressed as follows.
  • T (B) / (A) ⁇ ⁇ 7> + ⁇ 4> + ⁇ 5> + ⁇ 6> + ⁇ 7> Therefore, the ratio of each terminal is as follows.
  • Terminal vinylidene group ⁇ 7> / T ⁇ 100 Unit: mol%
  • Terminal vinyl group (B) / (A) ⁇ ⁇ 7> ⁇ 100
  • E) n-propyl terminal ⁇ 5> / T ⁇ 100
  • F) n-butyl group terminal ⁇ 6> / T ⁇ 100
  • G) iso-butyl end ⁇ 4> / T ⁇ 100
  • the number of terminal vinylidene groups per molecule is 2 ⁇ (C) / 100 units: pieces / molecule.
  • the vinyl alkoxysilane represented by the formula (I) used for the production of the reactive polyolefin of the present invention corresponds to the structure (A) of the reactive polyolefin, and specific examples thereof are the same as those of the structure (A).
  • the addition amount of the vinylalkoxysilane represented by the formula (I) is 0.5 to 25 parts by weight, preferably 1 to 20 parts by weight, more preferably 1.50 parts by weight with respect to 100 parts by weight of the polyolefin (1). 5 to 15 parts by weight.
  • the addition amount of vinyl alkoxysilane is less than 0.5 part by weight, the effect of developing the heat resistance of the reactive polyolefin may be reduced.
  • the amount of vinyl alkoxysilane added exceeds 25 parts by weight, the heat resistance is improved, but the reactive polyolefin becomes hard and the elasticity may be lowered.
  • the vinyl alkoxysilane has poor homopolymerization. More preferably, the vinyl alkoxysilane has low homopolymerization and high radical addition reactivity.
  • the homopolymerizability of vinyl alkoxysilane is high, a long chain of alkoxysilane may be locally formed in any part of the polyolefin (1) chain.
  • a polymer consisting only of vinylalkoxysilane without being added to the polyolefin (1) is by-produced to provide a highly uniform polymer reaction product.
  • trialkoxysilanes such as trimethoxyvinylsilane are suitable, and polar vinyl monomer types, such as methacryloxypropyltrimethoxysilane, have high homopolymerizability and are presumed to cause the above problems.
  • the organic peroxide used for the production of the reactive polyolefin is not particularly limited, but is preferably an organic peroxide that decomposes at a temperature at which the polyolefin (1) and the crystalline polyolefin (2) to be described later melt, more preferably 1 Organic peroxide having a minute half-life temperature of 140 to 270 ° C.
  • organic peroxide examples include diisobutyryl peroxide, cumyl peroxyneodecanoate, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, and di-sec-butyl peroxydicarbonate.
  • 1,1,3,3-tetramethylbutylperoxyneodecanoate di (4-tert-butylcyclohexyl) peroxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxy Neodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxypivalate, t-butylperoxypivalate, di (3,5,5-trimethylhexanoyl) peroxide, dilaurylper Oxide, 1,1,3,3-tetramethylbutyl Oxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methyl) Benzoyl) peroxide, t-butylperoxy-2-e
  • the addition amount of the organic peroxide is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, based on 100 parts by weight of the polyolefin (1).
  • the amount of the organic peroxide added is less than 0.01 parts by weight, the radical reaction may not proceed sufficiently.
  • the added amount of the organic peroxide exceeds 5 parts by weight, the odor of the decomposition product or the like may become strong, and yellowing may easily occur.
  • the organic peroxide is water, an inert solvent, in order to improve its quantitative supply, reduce the risk, improve the adhesion to the polyolefin (1) and / or the crystalline polyolefin (2), and improve the impregnation. Or you may use in combination with an inorganic compound. Also, a master batch of polyolefin (1) containing organic peroxide (1), crystalline polyolefin (2) containing organic peroxide, or polyolefin (1) and (2) containing organic peroxide was prepared. It may be used.
  • a vinyl monomer represented by the following formula (II) is preferably further used.
  • R 3 and R 4 are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
  • the vinyl monomer represented by the formula (II) used for the production of the reactive polyolefin of the present invention corresponds to the structure (C) of the reactive polyolefin, and specific examples thereof are the same as the structure (C).
  • the addition amount of the vinyl monomer represented by the formula (II) is preferably 1 to 40 parts by weight, more preferably 2 to 35 parts by weight, still more preferably 100 parts by weight of the polyolefin (1). 4 to 30 parts by weight.
  • the added amount of the vinyl monomer represented by the formula (II) is less than 1 part by weight, the effect of improving the open time may be lowered.
  • the addition amount of the vinyl monomer represented by the formula (II) exceeds 40 parts by weight, the mechanical strength of the reactive polyolefin may be lowered.
  • the crystalline polyolefin (2) include: high-density polyethylene; polypropylene-based resin and polybutene-based homopolypropylene, random polypropylene, block polypropylene, homopolybutene-1; linear low-density polyethylene, ethylene / 1- Butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene / decene copolymer, ethylene / ⁇ -olefin copolymer such as ethylene / eicosene copolymer, ethylene vinyl acetate copolymer Saponified polymer, ethylene acrylic acid copolymer, ethylene methyl acrylate copolymer, ethylene copolymer in which (meth) acrylic acid methyl ester
  • An olefin copolymer containing a polar group such as Low-density polyethylene made of ethylene alone, which is a low-density polyethylene produced by the pressure radical method, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer and its metal neutralized product (so-called ionomer), ethylene / methyl methacrylate And copolymers such as copolymers and ethylene / ethyl acrylate copolymers.
  • the “crystallinity” of the crystalline polyolefin (2) indicates that a melting point exists between 20 and 170 ° C. in DSC measurement.
  • the crystalline polyolefin (2) is preferably an ethylene polymer such as high density polyethylene or polyethylene having an ethylene content of 90% by weight or more, or a crystalline polyolefin having a mesopentad fraction [mmmm] of more than 80 mol%.
  • the crystalline polyolefin having a mesopentad fraction [mmmm] of more than 80 mol% is preferably a polypropylene-based resin or a polybutene-based resin, more preferably a homopolypropylene, a random polypropylene, or a block polypropylene.
  • the crystalline polyolefin (2) preferably has a polypropylene-converted weight average molecular weight (Mw) measured by GPC in the range of 3000 to 400,000.
  • the crystalline polyolefin (2) preferably has a crystal melting peak temperature measured by DSC in the range of 80 to 168 ° C.
  • the addition amount of the crystalline polyolefin (2) is 0.2 to 30 parts by weight, preferably 0.2 to 25 parts by weight, more preferably 0.2 to 30 parts by weight with respect to 100 parts by weight of the polyolefin (1). 20 parts by weight.
  • the addition of the crystalline polyolefin (2) is aimed at imparting heat resistance, but when the addition amount exceeds 30 parts by weight, the open time may be lowered and the low-temperature coating property may be lowered.
  • crystalline polyolefin (2) satisfy
  • ⁇ Glass transition temperature (Tg) is ⁇ 20 ° C. or less
  • Mw Weight average molecular weight (Mw) is 3000 to 400000
  • crystalline polyolefin (2) capable of imparting low-temperature flexibility include high-density polyethylene, low-density polyethylene by high pressure method, polybutene, polyhexene, polyoctene, polydecene, polyecene, and other ⁇ -olefin polymers such as ethylene.
  • Butene copolymer ethylene hexene copolymer, ethylene octene copolymer, ethylene / decene copolymer, ethylene / ⁇ -olefin copolymer such as ethylene / eicosene copolymer, ethylene vinyl acetate copolymer, ethylene acetate Saponified vinyl copolymer, ethylene (meth) acrylic acid copolymer, ethylene (meth) methyl acrylate copolymer, (meth) acrylic acid methyl ester moiety ethyl, butyl.
  • Examples thereof include olefinic copolymers containing polar groups such as hexyl, octyl, 2-ethylhexyl, ethylene copolymers changed to decyl groups, and the like.
  • olefinic copolymers containing polar groups such as hexyl, octyl, 2-ethylhexyl, ethylene copolymers changed to decyl groups, and the like.
  • an ethylene / ⁇ olefin copolymer, a low density polyethylene, an ethylene vinyl acetate copolymer, and the like are used.
  • a preferred composition ratio is 0.2 to 30 parts by weight, more preferably 1 to 30 parts by weight, 2 to 30 parts by weight, and 2.5 to 25 parts by weight with respect to 100 parts by weight of the polyolefin (1). is there. If the amount is less than 0.2 parts by weight, the low-temperature flexibility may not be sufficiently imparted. If the amount exceeds 30 parts by weight, the compatibility is deteriorated and separated, so that the heat resistance performance may not be exhibited.
  • crystalline polyolefin (2) satisfy
  • -Weight average molecular weight (Mw) is 3000-200000 ⁇
  • Glass transition temperature (Tg) is ⁇ 10 ° C. or lower ⁇
  • Tg Glass transition temperature
  • the content of polar groups is 1 to 50%
  • Specific examples of the crystalline polyolefin (2) capable of controlling the curing rate are the same as the specific examples of the crystalline polyolefin (2) capable of imparting the low-temperature flexibility.
  • ethylene alpha olefin copolymer, low density polyethylene, etc. are mentioned.
  • the blending amount is determined and used so as to achieve a desired curing rate between 0.2 and 30 parts by weight with respect to 100 parts by weight of the polyolefin (1). If it is less than 0.2 parts by weight, the curing rate is small, and it may take a long time to reach the desired heat-resistant adhesive strength. When it exceeds 30 parts by weight, the stability is lowered, and thus the viscosity increases during long-term storage and storage, and the storage stability may be lowered.
  • the polyolefin (1) is melted and the polyolefin (1), the vinylalkoxysilane represented by the formula (I) and the organic peroxide are melt-reacted at a temperature of 120 to 260 ° C. .
  • the melt reaction can be performed by, for example, a melt batch method, a melt extrusion method, or the like.
  • At least one of the vinyl monomer represented by the formula (II) and the crystalline polyolefin (2) is used, at least one of the vinyl monomer and the crystalline polyolefin (2) is used in the melt reaction stage.
  • Polyolefin (1), vinyl alkoxysilane represented by the formula (I), and organic peroxide may be present together.
  • polyolefin (1) 100 parts by weight of polyolefin (1), 0.5 to 25 parts by weight of vinylalkoxysilane represented by formula (I), 0.2 to 30 parts by weight of crystalline polyolefin (2), and organic peroxide
  • a process for producing a reactive polyolefin in which 0.01 to 5 parts by weight of an oxide are reacted in a temperature range of 120 to 260 ° C. in the molten state of the polyolefin (1), or 100 parts by weight of polyolefin (1), 0.5 to 25 parts by weight of vinylalkoxysilane represented by formula (I), 1 to 40 parts by weight of vinyl monomer represented by formula (II), and 0.
  • the polyolefin (1) and crystalline polyolefin (2) are melt-reacted in the coexistence of the organic peroxide and vinylalkoxysilane, so that the crystalline polyolefin is added to the reactive polyolefin.
  • the dispersibility is high, and the mechanical properties, heat resistance performance, and adhesion performance are excellent.
  • the polyolefin (1) and the crystalline polyolefin (2) are melt-reacted in the coexistence of the organic peroxide and the vinylalkoxysilane, thereby improving the uniformity of the reactive polyolefin and improving the performance such as low-temperature characteristics. Can be preferable.
  • the vinyl monomer when a vinyl monomer is used, it is considered that the vinyl monomer is copolymerized with a part or all of the terminal unsaturated groups generated by the decomposition of the polyolefin (1).
  • the copolymer of decomposed polyolefin (1) and vinyl monomer contained in the reactive polyolefin increases the uniformity of the reactive polyolefin.
  • the vinyl monomer is a long-chain alkyl ester such as 2-ethylhexyl acrylate, the glass transition temperature can be lowered to improve the low temperature characteristics.
  • Factors that can control the primary structure of the reactive polyolefin of the present invention include the following (a) to (g), and the conditions are as described above or below. a) Stereoregularity of polyolefin (1), b) Structure and amount of vinylalkoxysilane c) Organic peroxide species and amount used, d) melting reaction temperature, e) Residence time or reaction time, f) Agitation strength g) Terminal structure of polyolefin (1)
  • the most effective method is a method of changing the organic peroxide concentration in the presence of a certain amount of vinylalkoxysilane, and then a method of controlling by changing the temperature.
  • the organic peroxide is added in an amount of 0.01 to 5 parts by weight in a temperature range where polyolefin radicals are sufficiently generated at a temperature of 120 ° C. or higher, preferably 130 ° C. or higher, more preferably 140 ° C. or higher.
  • it is based on a method of changing the temperature while keeping the organic peroxide constant.
  • the vinylalkoxysilane content can be controlled by changing the vinylalkoxysilane in the range of 0.5 to 25 parts by weight as described above.
  • a reactive polyolefin having a desired viscosity and alkoxysilane content can be produced by first setting conditions for controlling the viscosity to a desired value and then changing the amount of vinylalkoxysilane charged.
  • the amount of vinylalkoxysilane added is somewhat affected by the organic peroxide concentration, but its fluctuation is slight, so that the production conditions can be determined by repeating the above operation once or twice.
  • the uniformity of the reactive polyolefin can be controlled by performing the melting reaction in a homogeneous reaction field.
  • the polyolefin (1) since the polyolefin (1) has low stereoregularity and a low melting point, it does not require a high temperature to be in a molten state, and further, a vinyl alkoxysilane such as trimethoxyvinylsilane is uniformly dissolved in the molten state, The melting reaction can be performed in a uniform reaction field.
  • polar vinyl monomer types such as methacryloxypropyltrimethoxysilane are separated in the molten state and the reaction field becomes non-uniform.
  • polyolefin (1) absorbs vinylalkoxysilane in a solid state like a pellet, has no wetness on the surface, and becomes a highly fluid pellet, so that it is very easy to handle as an impregnated pellet.
  • the main component is polyolefin (1) that does not contain homopolyethylene, for example, propylene base or 1-butene base, cross-linking between polyolefins that normally occurs in homopolyethylene is suppressed. Therefore, it is easy to reduce the viscosity, and it is possible to produce a reactive polyolefin excellent in coatability.
  • homopolyethylene for example, propylene base or 1-butene base
  • the melt reaction When the melt reaction is carried out by a melt batch method, it is preferably carried out in an inert gas atmosphere such as nitrogen, argon, helium, etc.
  • an inert gas atmosphere such as nitrogen, argon, helium, etc.
  • polyolefin (1) or polyolefin (1) and crystalline polyolefin (2) are stirred
  • the melting reaction by continuously or intermittently adding the organic peroxide and the vinylalkoxysilane after heating and melting in a batch reactor.
  • the molten batch method when at least one of the vinyl monomer represented by the formula (II) and the crystalline polyolefin (2) is used, it may be added together with the organic peroxide and the vinyl alkoxysilane. Each addition may be performed independently. Moreover, you may mix arbitrary 2 or more types of components, and may add from one or more insertion ports.
  • the addition time of the above components is usually in the range of 1 minute to 10 hours, and the reaction may be continued for 1 minute to 5 hours after
  • the stirring state affects the molecular weight of the reactive polyolefin and the amount of vinylalkoxysilane added.
  • the rotational speed is in the range of 50 to 800 rpm, preferably 100 to 800 rpm, more preferably 120 to 700 rpm.
  • the polyolefin (1), the vinyl alkoxysilane represented by the formula (I), and the organic peroxide are brought into contact in a molten state, and only the vinyl monomer and the organic peroxide are in the reaction temperature range.
  • a method that excludes the case of contact can be adopted.
  • the reaction time in the above case is, for example, 20 seconds to 10 minutes as an average residence time.
  • the melt reaction is carried out by a melt extrusion method in which the polyolefin (1) or the polyolefin (1) and the crystalline polyolefin (2) are preliminarily represented by the formula (I), a vinyl alkoxysilane, an organic peroxide.
  • the vinyl monomer represented by the arbitrary formula (II) may be impregnated in whole or in part and used as impregnated pellets that have no wetness or adhesion on the polyolefin pellet surface or have reduced adhesion.
  • all the raw materials may be supplied all at once from the upstream hopper and melt extrusion may be carried out.
  • polyolefin (1) or polyolefin (1) and crystalline polyolefin (2 ) From the upstream hopper, polyolefin (1) or polyolefin (1) and crystalline polyolefin (2 ) And by supplying vinylalkoxysilane, vinyl monomer, and organic peroxide downstream, the melt extrusion can be carried out.
  • polyolefin (1) or polyolefin (1) and crystalline polyolefin (2) and vinylalkoxysilane may be introduced from an upstream hopper, and an organic peroxide may be supplied downstream.
  • the melting reaction is carried out under conditions that can maintain uniformity in the molten state.
  • the decomposition of the polyolefin (1) is accompanied, and the molecular weight of the resulting reactive polyolefin is reduced.
  • the ratio of the molecular weight reduction is the weight average molecular weight of the polyolefin (1). (Mw) or 90 to 20% of the average weight average molecular weight (Mw) of the polyolefin (1) and the crystalline polyolefin (2).
  • the reaction temperature of the melt reaction is 120 to 260 ° C., preferably 130 to 250 ° C., more preferably 140 to 240 ° C.
  • the reaction temperature is less than 120 ° C., the reaction does not proceed sufficiently, and the heat resistance performance of the resulting reactive polyolefin may not be exhibited.
  • the reaction temperature exceeds 260 ° C., the decomposition of vinylalkoxysilane may be accelerated.
  • the polyolefin (1) supply port is at the uppermost stream side
  • the vinylalkoxysilane and organic peroxide supply port is downstream
  • the downstream portion is the reaction zone.
  • a vent for removing volatile components exists on the downstream side of the reaction zone, and a discharge port such as a die is provided on the most downstream side.
  • the reaction temperature refers to the temperature of the reaction zone.
  • the lab plast mill made by Toyo Seiki Co., Ltd. shown in the examples corresponds to the C2 to C5 zones.
  • the temperature in the other region can be appropriately set so as to be normally performed from the viewpoint of setting the supply stability of the polyolefin (1) pellets and the temperature of the discharged resin.
  • the primary structure of the reactive polyolefin can be controlled by reacting at a temperature and peroxide conditions at which polyolefin radicals are sufficiently generated.
  • the reaction proceeds by a mechanism in which vinylsilane is added under the condition that the polyolefin (1) has a low molecular weight. That is, a radical is generated in the polyolefin (1) chain, which becomes a reaction point, and alkoxysilane is added.
  • radicals generated in the polyolefin (1) chain are cleaved into an unsaturated terminal polyolefin and a radical terminal polyolefin with a certain probability.
  • the radical-terminated polyolefin undergoes an addition reaction with vinylalkoxysilane, and the unsaturated-terminated polyolefin is easily radical-reactive and therefore easily reacts with alkoxysilane. From this, it is important for the addition reaction of alkoxysilane to generate radicals of polyolefin chain, and it reacts while lowering the molecular weight.
  • the reaction proceeds according to the above reaction mechanism, and the molecular weight of the produced reactive polyolefin is lower than that of the raw material polyolefin (1). Radicals that cleave at low temperatures are not active enough to produce the tertiary carbon radical of polyolefin (1), and in order to proceed with this reaction, temperatures of 120 ° C.
  • the organic peroxide is preferably one that decomposes in this temperature range to generate radicals, and one that has a one-minute half-life temperature of 140 to 270 ° C.
  • the reaction time or a residence time at which the decomposition of 40% or more of the organic peroxide is completed.
  • the decomposition time is represented by a value calculated using the Arrhenius equation, using the activation energy and frequency factor specific to each organic peroxide.
  • composition containing the reactive polyolefin of the present invention can be suitably used as an adhesive, a coating agent, a filler treatment agent, a paint, a dispersion, an ink, or a resin modifier.
  • the composition containing the reactive polyolefin of the present invention can be particularly suitably used as an adhesive (hereinafter also referred to as “adhesive composition”).
  • the adhesive composition of the present invention contains 100 parts by weight of the reactive polyolefin of the present invention, 0 to 200 parts by weight of a thermoplastic resin, and 0 to 100 parts by weight of oil.
  • the said thermoplastic resin is a thermoplastic composition except the reactive polyolefin of this invention, for example, is resin which provides adhesiveness to adhesive composition.
  • the tackifying resin is not particularly limited as long as it is a resin generally used in the related field of hot melt adhesives.
  • an aliphatic hydrocarbon resin an alicyclic hydrocarbon resin, an aromatic carbonization is used.
  • examples thereof include hydrogen resins, polyterpene resins, rosin resins, styrene resins, and coumarone indene resins.
  • Examples of the tackifying aliphatic hydrocarbon resin include polymers mainly composed of mono- or diolefins having 4 to 5 carbon atoms such as 1-butene, isobutylene, butadiene, 1,3-pentadiene, isoprene, piperidine and the like. Can be mentioned.
  • Examples of the tackifying alicyclic hydrocarbon resin include a resin obtained by polymerizing a diene component in a petroleum fraction having 4 to 5 carbon atoms after cyclization and dimerization, a resin obtained by polymerizing a cyclization monomer such as cyclopentadiene, Examples thereof include resins obtained by hydrogenating aromatic hydrocarbon resins.
  • tackifying aromatic hydrocarbon resin examples include resins mainly composed of a vinyl aromatic hydrocarbon having 9 to 10 carbon atoms such as vinyltoluene, indene and ⁇ -methylstyrene.
  • tackifying polyterpene resins include ⁇ -pinene polymers, diterpene polymers, terpene phenol copolymers, ⁇ -pinene-phenol copolymers, and the like.
  • the tackifying rosin resin is a rosin such as gum rosin, wood rosin, tall oil or a modified product thereof, and the modified product is a resin subjected to modification means such as hydrogenation, disproportionation, dimerization, esterification Can be illustrated.
  • tackifying rosin ester examples include esters such as ethylene glycol, diethylene glycol, glycerin and pentaerythritol.
  • tackifying styrene resin examples include polymers such as styrene, methylstyrene, ⁇ -methylstyrene, and isopropenyltoluene.
  • the content of the tackifying resin in the adhesive composition is 0 to 200 parts by weight, preferably 1 to 150 parts by weight, more preferably 2 to 100 parts by weight based on 100 parts by weight of the reactive polyolefin. Parts by weight.
  • the adhesive composition may become brittle and the adhesive strength may be reduced.
  • the oil contained in the adhesive composition of the present invention includes a wax, and the oil and the wax are not particularly limited as long as they are oils generally used in related fields of hot melt adhesives. can do.
  • the adhesive composition can achieve both good coatability and high heat resistance due to low viscosity.
  • the oil include paraffinic process oil, glycols, and naphthenic oil.
  • the wax include synthetic waxes such as Fischer-Tropsch wax, polyethylene wax, polypropylene wax, and atactic polypropylene, petroleum waxes such as paraffin wax and microcrystalline wax, and natural waxes such as wood wax, carnauba wax, and beeswax. It is done.
  • the content of oil in the adhesive composition is 0 to 100 parts by weight, preferably 0 to 50 parts by weight, more preferably 0 to 20 parts by weight with respect to 100 parts by weight of the reactive polyolefin.
  • oil content is more than 100 parts by weight with respect to 100 parts by weight of the reactive polyolefin, the cohesive strength, heat resistance, creep resistance, etc. of the adhesive composition are greatly reduced, and the appearance is impaired by bleeding.
  • the adhesive may become sticky and cause rash.
  • the adhesive composition of the present invention is preferably an adhesive composition that further contains 1 ⁇ 10 ⁇ 6 to 0.5 parts by weight of a curing catalyst and is moisture curable in an atmosphere substantially containing moisture.
  • the atmosphere in which moisture substantially exists is, for example, a normal room temperature atmosphere, and when the curing rate is controlled, it is preferable that the humidity is controlled in a range of 30 to 90%. Moisture curing can also be performed by immersion in water.
  • the curing catalyst can impart high heat resistance to the adhesive, such as dibutyltin dilaurate, stannous acetate, dibutyltin diacetate, dibutyltin dioctoate, lead naphthenate, zinc caprylate, cobalt naphthenate, titanium And organic metal compounds such as acid tetrabutyl ester, lead stearate, zinc stearate, cadmium stearate, barium stearate and calcium stearate.
  • organic metal compounds such as acid tetrabutyl ester, lead stearate, zinc stearate, cadmium stearate, barium stearate and calcium stearate.
  • the content of the curing catalyst in the adhesive composition is preferably 1 ⁇ 10 ⁇ 6 to 0.5 part by weight, more preferably 1 ⁇ 10 ⁇ 4 to 0.4 part by weight based on 100 parts by weight of the reactive polyolefin. Part, more preferably 1 ⁇ 10 ⁇ 3 to 0.35 part by weight, particularly preferably 0.015 to 0.3 part by weight.
  • the content of the curing catalyst is less than 1 ⁇ 10 ⁇ 6 parts by weight with respect to 100 parts by weight of the reactive polyolefin, there is a possibility that sufficient crosslinking reaction does not proceed and heat resistance cannot be expressed.
  • the content of the curing catalyst is more than 0.5 parts by weight, the crosslinking reaction may proceed non-uniformly and the surface may be roughened.
  • the adhesive composition of the present invention preferably further contains a curing accelerator.
  • a curing accelerator specifically, additives such as amines shown below can be used.
  • Acidic substances such as hydrochloric acid, hydrogen peroxide, carbonic acid, ⁇ Carboxylic acid such as formic acid and acetic acid ⁇ Sulphonic acid such as benzene sulfonic acid ⁇ Phosphoric acid ⁇ Heteropoly acid ⁇ Inorganic solid acid
  • Basic substance ⁇ Ammonia base such as ammonia water ⁇ Amines
  • Amines are aliphatic or cycloaliphatic, saturated or unsaturated hydrocarbon groups; aromatic hydrocarbon groups: oxygen-containing, sulfur-containing and / or selenium-containing hydrocarbon groups bonded to one or more nitrogen atoms.
  • aromatic hydrocarbon groups oxygen-containing, sulfur-containing and / or selenium-containing hydrocarbon groups bonded to one or more nitrogen atoms.
  • each substituent for N may be the same or different, or may have one or more different substituents.
  • Primary amines include monomethylamine, monoethylamine, monopropylamine, monobutylamine, monobenzoylamine, monohexylamine, monohexylamine, octylamine, nonylamine, 1-aminododecane, 1-aminoundecane, dodecylamine 1-aminotridecane, hexadecylamine, 1-aminoheptadecane, octadecylamine, 1-aminonanodecane, vinylamine, allylamine, butenylamine, pentenylamine, hexenylamine, bentadienylamine, hexadienylamine, Cyclopentylamine, cyclohexylamine, cyclooctylamine, p-menthylamine, cyclopentenylamine, cyclohexenylamine, cyclohexahexenylamine, aniline,
  • Secondary amines include dimethylamine, diethylamine, dibroviramine, dibutylamine, dipentylamine, dihexylamine, methylethylamine, methylbroviramine, methylbutylamine, methylpentylamine, methylhexylamine, ethyl propylamine, ethylbutylamine , Ethylpentylamine, propylbutylamine, propylpentylamine, bububilhexylamine, butylpentylamine, pentylhexylamine, divinylamine, diallylamine, dibutenylamine, dipentenylamine, dihexenylamine, methylvinylamine, methylallylamine, Methylbutenylamine, methylpentenylamine, methylhexenylamine, ethylvinylamine, ethylallylamine, ethylbutenyl Mine,
  • Tertiary amines include trimethylamine, triethylamine, tributylamine, tributylamine, tripentylamine, trihexylamine, dimethylethylamine, dimethylpropylamine, dimethylbutylamis, dimethylpentylamine, dimethylhexylamine, diethylpropylamine , Diethylbutylamine, diethylpentylamine, diethylhexylamine, dibutyl butylamine, dibromopentylamine, dibutyl hexylamine, dibutylpentylamine, dibutylhexylamine, dipentylhexylamine, methyldiethylamine, methyldibroviramine, Methyldibutylamine, methyldipentylamine, methyldihexylamine, ethyldiproviramine, ethyldibutylamine, eth
  • those compatible with the reactive polyolefin (1) are preferable from the viewpoint of promoting the curing reaction.
  • an adhesive composition since it does not evaporate by heating, what has a high boiling point is preferable.
  • the content of the curing accelerator in the adhesive composition is 0.05 to 5 parts by weight, preferably 0.07 to 4 parts by weight, and more preferably 0 to 100 parts by weight of the reactive polyolefin. 1 to 3 parts by weight.
  • the adhesive composition of the present invention can further contain a curing agent.
  • the curing agent is a compound having two or more crosslinking groups (for example, alkoxysilane groups or silanol groups) that can react with the reactive polyolefin.
  • Phenylalkoxysilanes such as dimethoxymethylphenylsilane, phenyltrimethoxysilane, diethoxymethylphenylsilane, phenyltriethoxysilane, diethoxydiphenylsilane, dimethoxydiphenylsilane
  • benzylalkoxysilanes such as benzyltriethoxysilane
  • methyltripropoxysilane methyltriisopropoxysilane, n-propyltriethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltriethoxysilane, Linear hydrocarbon alkoxysilanes such as diethoxyethyloctadecylsilane and octadecyltriethoxysilane
  • Tetraalkoxysilanes such as tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetraethoxysilane
  • a chain alkoxy oligomer having a viscosity of 5 to 200 mm 2 / s (25 ° C.) and an alkoxy group content of 10 to 70% by weight is preferable.
  • the alkoxy group is preferably a methoxy group or an ethoxy group.
  • a chain alkoxy oligomer containing a silicon atom and having a methyl group or a phenyl group as a substituent bonded to the silicon atom is preferable.
  • Examples of the curing agent having a silanol alkoxy group include a partial hydrolyzate or hydrolyzate of the above alkoxysilane.
  • the alkoxy group is a methoxy group, and the boiling point is 200 ° C. or higher.
  • the content of the curing agent in the adhesive composition is 0.01 to 5 parts by weight, preferably 0.05 to 4.5 parts by weight, and more preferably 0 to 100 parts by weight of the reactive polyolefin. 1 to 4 parts by weight.
  • the adhesive composition can contain an antioxidant, a pigment, an ultraviolet absorber and the like in addition to the above components.
  • the adhesive composition can be produced by adding other components to the reactive polyolefin.
  • curing agent and a hardening accelerator it can also mix at the time of manufacture of reactive polyolefin.
  • the adhesive composition of the present invention is preferably used as a reactive hot melt adhesive.
  • the reactive hot melt adhesive can be used, for example, for adhesion of automobile interior and exterior materials, adhesion in the field of construction and building materials, adhesion of furniture, and adhesion of home appliance OA equipment.
  • the polymerization temperature was set to 67 ° C., and propylene and hydrogen were continuously fed so that the hydrogen concentration in the gas phase part of the reactor was 0.74% and the total pressure in the reactor was maintained at 0.75 MPa ⁇ G.
  • a polymerization reaction was performed. Irganox 1010 (manufactured by Ciba Specialty Chemicals), which is a stabilizer, is added to the resulting polymerization solution so that its content is 500 ppm by mass, and n-heptane, which is a solvent, is removed to reduce the content. Crystalline polypropylene was obtained. This low crystalline polypropylene was made into resin pellets by underwater cutting.
  • the physical properties of the resulting low crystalline polypropylene were as follows: Stereoregularity [mmmm]: 46 mol% Weight average molecular weight (Mw): 131000 Molecular weight distribution (Mw / Mn): 1.9 Number of terminal unsaturated groups: 0.97 / molecule
  • Production Example 2 The polymerization temperature was set to 75 ° C., propylene and hydrogen were continuously fed so that the hydrogen concentration in the gas phase of the reactor was 2.6 mol% and the total pressure in the reactor was maintained at 0.79 MPa ⁇ G.
  • the physical properties of the resulting low crystalline polypropylene were as follows: Stereoregularity [mmmm]: 46 mol% Weight average molecular weight (Mw): 74200 Molecular weight distribution (Mw / Mn): 1.9 Number of terminal unsaturated groups: 0.98 per molecule
  • the physical properties of the obtained low crystalline polypropylene were as follows. Incidentally, “not observed” of the number of terminal unsaturated groups means that it is at least less than 0.05 per molecule. : Stereoregularity [mmmm]: 47 mol% Weight average molecular weight (Mw): 72000 Molecular weight distribution (Mw / Mn): 1.8 Number of terminal unsaturated groups: not observed
  • Example 1 90.0 g of the low crystalline polyolefin synthesized in Production Example 1 was put into a 300 ml separable flask equipped with a stirrer, a thermometer, and an inlet, and dry nitrogen was circulated to sufficiently substitute the nitrogen. The following reactions were all carried out under a nitrogen atmosphere. The separable flask was immersed in a heated oil bath to melt the low crystalline polyolefin, and then the temperature was controlled at 170 ° C. with stirring. A previously prepared uniform solution of 9 g of trimethoxyvinylsilane and 0.9 g of dicumyl peroxide was dropped from the dropping funnel over 45 minutes, and the reaction was further continued for 5 minutes.
  • the mesopentad fraction, B viscosity, molecular weight distribution, heat resistant creep temperature, open time and adhesive strength of the obtained reactive polyolefin were evaluated.
  • the evaluation method is as follows. The results are shown in Table 1.
  • B viscosity According to JISK-6862, the reactive polyolefin melted at 190 ° C was measured by using a Brookfield viscometer.
  • a viscometer As a viscometer, a TVB-10 type viscometer manufactured by Toki Sangyo Co., Ltd. and an M2 rotor (No. 21) were used, and an H-2 type small sample adapter was used.
  • the heat resistant creep temperature was measured in accordance with JIS K6833. Specifically, the lower part of the test piece was cut off so that the length of the bonded portion was 25 mm, and a 500 g weight was attached to the lower end of the test piece suspended in the thermostat. The temperature of the thermostatic bath was maintained at 38 ° C. for 15 minutes, and then the temperature was increased at a rate of 2 ° C. for 5 minutes. The temperature when the weight dropped was defined as the heat-resistant creep temperature.
  • Example 2 The same procedure as in Example 1 was repeated except that the low crystalline polyolefin of Production Example 2 was used instead of the low crystalline polyolefin of Production Example 1 and the dropping time of the uniform solution of trimethoxyvinylsilane and dicumyl peroxide was 20 minutes. Reactive polyolefin was prepared (yield 95.1 g) and evaluated. The results are shown in Table 1.
  • Example 3 Reactive polyolefin in the same manner as in Example 1 except that instead of a uniform solution of trimethoxyvinylsilane and dicumyl peroxide, a solution obtained by adding 4.5 g of 2-ethylhexyl acrylate to the uniform solution was added dropwise over 75 minutes. (Yield 97.3 g) and evaluated. The results are shown in Table 1.
  • Example 4 instead of the low crystalline polyolefin of Production Example 1, a mixture of 81.0 g of the low crystalline polyolefin of Production Example 3 and 9.0 g of polypropylene wax was used, and the dropping time of the uniform solution of trimethoxyvinylsilane and dicumyl peroxide was 45.
  • a reactive polyolefin was produced in the same manner as in Example 1 except that the amount was 9% (yield 91.4 g) and evaluated. The results are shown in Table 1.
  • the polypropylene wax is 330-P (mesopentad fraction: 85.4 mol%) manufactured by Sanyo Chemical Industries, and corresponds to the crystalline polyolefin (2) of the present invention.
  • Example 5 In a 2 liter cylindrical container under a nitrogen atmosphere, a homogeneous solution consisting of 90 g of trimethoxyvinylsilane, 44.3 g of 2-ethylhexyl acrylate, and 9.0 g of dicumyl peroxide was added to 900 g of the low crystalline polyolefin of Production Example 1. After sealing, it was spun for mixing. After 3 hours, no residual liquid material or adhesion was observed in the low crystalline polyolefin pellets. Impregnated pellets with good flowability were obtained.
  • the discharge thing which is reactive polyolefin was extract
  • the obtained reactive polyolefin was evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 6 Impregnated pellets and reactive polyolefin were produced and evaluated in the same manner as in Example 5 except that the amount of trimethoxyvinylsilane used was 45 g. The results are shown in Table 1. The impregnated pellets obtained were free from residual liquid matter and adhesion as in Example 5, had good fluidity, and the discharge amount during melt extrusion was 1480 grams / hour.
  • Example 7 Impregnated pellets and reactive polyolefin were produced and evaluated in the same manner as in Example 5 except that the amount of trimethoxyvinylsilane used was 45 g and the amount of 2-ethylhexyl acrylate used was 88.6 g. The results are shown in Table 1. The impregnated pellets obtained were free from residual liquid matter and adhesion as in Example 5, had good fluidity, and had a discharge amount of 1280 grams / hour during melt extrusion.
  • Example 8 Impregnated pellets and reactive polyolefin were produced and evaluated in the same manner as in Example 5 except that the amount of trimethoxyvinylsilane used was 45 g and the amount of 2-ethylhexyl acrylate used was 73.6 g. The results are shown in Table 1. The impregnated pellets obtained were free from residual liquid matter and adhesion as in Example 5 and had good fluidity. Further, the melt extrusion was carried out by changing the barrel temperature to 190 ° C. and the die temperature to 190 ° C., and the extrusion was carried out at a discharge amount of 2450 g / hour.
  • Comparative Example 1 (1) Production of silane-modified polypropylene Heat-dried 1 liter autoclave was charged with 400 ml of heptane, 0.5 mmol of triisobutylaluminum, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3- 0.2 micromol of trimethylsilylmethylindenyl) zirconium dichloride and 0.8 micromol of dimethylanilinium tetrakispentafluorophenylborate are added, 0.2 MPa of hydrogen is further introduced, and 0.6 MPa of propylene is introduced to bring the total pressure to 0. Polymerization was carried out at a polymerization temperature of 70 ° C.
  • Comparative Example 2 A reactive polyolefin was produced and evaluated in the same manner as in Example 2 except that methacryloxypropyltrimethoxysilane was used instead of trimethoxyvinylsilane. The results are shown in Table 1.
  • Comparative Example 3 A silane-modified polyolefin commercial product A (Best Plast V206, manufactured by Evonik Degussa) was evaluated in the same manner as in Example 1. The results are shown in Table 1. In addition to the above, the primary structure of the commercial product A was measured by 13 C-NMR, microscopic FTIR (infrared spectroscopy), and GPC.
  • the molecular weight distribution determined from GPC was 4.2.
  • trimethoxyvinylsilane (TMVS), 2-ethylhexyl acrylate (EHA), polypropylene wax (PPW), methacryloxypropyltrimethoxysilane (100% by weight) in reactive polyolefin (100% by weight) MPTMS) content was measured by infrared absorption spectroscopy. The results are also shown in Table 1.
  • Example 9 Reactive polyolefin of Example 1 20 g, Imabe P-100 (made by Idemitsu Petrochemical Co., Ltd.) as a tackifying resin (hydrogenated product of C5 / aromatic copolymer petroleum resin) (thermoplastic resin), phenolic Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd.) as an antioxidant is blended in an amount of 0.3 g, placed in a 0.1 liter sample tube, heated to 180 ° C. in an oil bath, and stirred and mixed in a molten state. A resin composition for hot melt adhesive was prepared.
  • 35 g of the obtained resin composition for adhesive was melted by heating at 180 ° C., 0.07 g of dibutyltin (IV) dilaurate was added as a curing catalyst, and the mixture was sufficiently stirred.
  • 0.5 g of this molten resin is uniformly applied with a stainless steel spatula to 80 mm from the end of a cotton canvas (JIS No. 10) having a width of 25 mm and a length of 200 mm, and a polypropylene having a width of 25 mm, a length of 100 mm, and a thickness of 2 mm. Overlaid on the board.
  • a 2 kg weight was placed on the bonded portion and heat-sealed in an oven at 120 ° C. for 10 minutes, taken out as it was, and cooled to room temperature.
  • the bonded test pieces were cured for 7 days in an atmosphere of 23 ° C. and 50% RH and moisture-cured.
  • Example 10 After a glass cylinder with a 2 liter screw cap was dried and purged with nitrogen, 900 g (100 parts by weight) of low crystalline polyolefin pellets of Production Example 1 were added. Trimethoxyvinyl silane 6 parts by weight, organic peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Nippon Yushi Co., Ltd., trade name Perhexa 25B) 0.20 part by weight The homogeneous solution consisting of was put in, sealed, and rotated on a roller and mixed.
  • Examples 11 to 21 A reactive polyolefin was produced and evaluated in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 2. The results are shown in Table 2.
  • Examples 22 to 26 A reactive polyolefin was produced and evaluated in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 3 and the rotational speed was changed to 180 rpm. The results are shown in Table 3. As is apparent from Table 3, if the organic peroxide decomposes in the temperature range where polyolefin radicals are generated, the viscosity can be controlled by the amount of organic peroxide charged and the temperature.
  • Comparative Examples 4 and 5 A reactive polyolefin was produced and evaluated in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 4. The results are shown in Table 4. In addition, tr in the table indicates that absorption of a trace level (less than 0.1% by weight) was observed. Even when radicals were generated, the decomposition reaction of the low-order polyolefin did not proceed at low temperatures, and the addition reaction of vinyl alkoxysilane hardly proceeded.
  • the one-minute half-life temperatures of azobisisobutyronitrile and diisopropyl peroxide are 120.2 ° C. and 85.1 ° C., respectively.
  • One minute half-life temperature of azobisisobutyronitrile is the frequency factor and activity shown in J. Am. Chem. Soc., 80, 779 (1958). J. P. Van Hook and A. v. Tobolsky. Using the value of chemical energy, it was calculated by the Arrhenius equation.
  • the one-minute half-life temperature of diisobutyl peroxide is a value described in the trade name Parroyl IB of the organic peroxide published by NOF Corporation.
  • Impregnated pellets were prepared in the same manner as in Example 10 except that the raw material and melt extrusion conditions were changed as shown in Table 5. That is, after a glass cylinder with a 2 liter screw cap was dried and purged with nitrogen, 900 g (100 parts by weight) of the low crystalline polyolefin pellets of Production Example 1 and the polyolefin (2) shown in Table 5 were charged. A homogeneous solution consisting of 6 parts by weight of trimethoxyvinylsilane and the amount of organic peroxide (t-butylperoxyisopropyl monocarbonate (trade name: Perbutyl I, manufactured by NOF Corporation)) shown in Table 5 was added to this and sealed. Then, it was rotated on a roller and mixed. The obtained impregnated pellets were melt extruded under the following conditions to obtain reactive polyolefins and evaluated. The results are shown in Table 5.
  • the ethylene octene copolymer is Affinity 1900 manufactured by Dow
  • the ethylene vinyl acetate copolymer is Ultrasen 725 manufactured by Tosoh.
  • the temperatures were: C1 / 160 ° C., C2-C5 and dice / 180 ° C., and the rotation speed was 180 rpm.
  • glass transition temperature (Tg), gel, etc. were evaluated as follows.
  • the glass transition temperature (Tg) of the reactive polyolefin was measured using an EXSTAR DMS6100 viscoelastic spectrometer manufactured by SII Nanotechnology.
  • a measurement sample was prepared by preparing a sheet having a thickness of about 1 mm by hot pressing and cutting it into a strip shape having a length of 20 mm and a width of 9 mm.
  • Loss elasticity is measured by applying dynamic strain with a frequency of 1 Hz to the sample and measuring the storage elastic modulus (E ′) and loss elastic modulus (E ′′) at a measurement temperature of ⁇ 90 ° C. to 200 ° C. and a heating rate of 2 ° C./min
  • the glass transition temperature (Tg) was obtained from the temperature giving the maximum value of the rate (E ′′).
  • the amount of gel at the time when 24 hours have passed after the addition of the curing catalyst is shown in Table 5 as the gel fraction for 24 hours. Further, the amount of gel was measured over time, and the final reached gel fraction was listed in Table 5 as a value at which the amount of gel did not change with time.
  • Acetone soluble part (actual measured value and calculated value) The calculated value was obtained from the following formula. 0.95 ⁇ TMVS content The measured value was measured by the method described in the above embodiment.
  • Example 39 A reactive polyolefin composition was obtained and evaluated in the same manner as in Example 32 except that the polyolefin (2) shown in Table 5 was added. The results are shown in Table 5.
  • Example 40 100 parts by weight of the reactive olefin of Example 24 and 20 parts by weight of ethylene octene copolymer (manufactured by Dow Co., Ltd., affinity 1900) were melt-kneaded at 160 ° C. and 100 rpm for 10 minutes using a Toyo Seiki Laboplast Mill to obtain a composition. . The results are shown in Table 5. The reactive olefin of Example 24 was similarly evaluated and the results are shown in Table 5.
  • Example 41 700 g (100 parts by weight) of the low crystalline polypropylene of Production Example 1 was put into a 2-liter glass cylindrical container with a screw cap and purged with nitrogen, and then 6 parts by weight of trimethoxyvinylsilane and 2,5 as an organic peroxide. -A uniform solution consisting of 0.81 part by weight of dimethyl-2,5-di (t-butylperoxy) hexane (trade name Perhexa 25B, manufactured by Nippon Oil & Fats Co., Ltd.) was charged, sealed, and rotated on a roller. Mixed. After 3 hours, no residual liquid or deposits were observed on the pellets, and impregnated pellets with good fluidity were obtained.
  • dimethyl-2,5-di (t-butylperoxy) hexane trade name Perhexa 25B, manufactured by Nippon Oil & Fats Co., Ltd.
  • Example 42 A reactive polyolefin was produced and evaluated in the same manner as in Example 41 except that the low crystalline polypropylene of Production Example 1 was changed to the low crystalline polypropylene of Production Example 3. The results are shown in Table 6. Comparison with Examples 41 and 42 showed that the amount of gel required for improving heat resistance was high when low crystalline polypropylene having a terminal vinylidene group was used.
  • Comparative Example 6 30 g of the propylene polymer produced in Comparative Example 1 (1) and 250 ml of toluene were placed in a 1000 ml separable three-necked flask equipped with a stirring blade, and the temperature was raised to 110 ° C., followed by 0.2 g of di-t-butyl peroxide, 5 g of methacryloxypropyltrimethoxysilane was added dropwise over 1 hour. After completion of the dropwise addition, the reaction solvent toluene was almost distilled off by distillation under reduced pressure after stirring at 110 ° C. for about 240 minutes. Further, it was heated to 140 ° C.
  • the yield of the obtained silane-modified polypropylene was 31.4 g, and the methacryloxypropyltrimethoxysilane content calculated from the weight increase was 4.5% by weight.
  • the silane-modified polypropylene was subjected to an acetone extraction operation according to the method described in the above embodiment.
  • the content of methacryloxypropyltrimethoxysilane in the acetone-insoluble part was 0.05% by weight. All the above operations were performed using a dehydrating reagent in a nitrogen atmosphere.
  • the temperature of the low stereoregular polyolefin injection site was controlled at room temperature, the supply site of trimethoxyvinylsilane and organic peroxide was 100 ° C., and the reaction zone was controlled at 190 ° C. The temperature after venting was set to 150 ° C. Table 7 shows the evaluation results of the reactive polyolefin.
  • Example 45 Production of polyolefin (1) In a heat-dried stainless steel autoclave with an internal volume of 5 L, dried heptane 2.5 L, triisobutylaluminum 1.4 mmol heptane solution 1.4 ml, dimethylanilinium tetrakis (pentafluorophenyl) 2 ml of 15.4 ⁇ mol of heptane slurry of borate was added and stirred for 10 minutes while controlling at 50 ° C.
  • the weight average molecular weight (Mw) of polypropylene is 109000, the molecular weight distribution (Mw / Mn) is 1.84, the stereoregularity [mmmm] is 58.2 mol%, the number of terminal unsaturated groups is 0.95 vinylidene group / molecule. Met.
  • the reactive polyolefin of the present invention comprises a reactive hot melt adhesive, a sealing agent, a resin / elastomer modifier, a wax blend agent, a filler blend agent, a resin modifier, a paint component, an ink component, an adhesive component, and a primer component. It can be suitably used for high-performance wax and the like.

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  • Graft Or Block Polymers (AREA)
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Abstract

La présente invention concerne une polyoléfine réactive présentant une structure (A) dérivée d'un alkoxysilane de vinyle, et une structure (B) qui est une chaîne dérivée de la polymérisation d'au moins un parmi un éthylène et une α-oléfine ayant au moins 3 à 20 atomes de carbone, sauf dans le cas d'une chaîne polyéthylénique, et la polyoléfine réactive satisfait les conditions suivantes: (1) la fraction méso en pentade (mmmm) indiquant la stéréorégularité moyenne est comprise entre 25 et 85 moles % ; (2) la quantité de structure (A) contenue est comprise entre 0,1 et 20% en poids ; (3) la distribution de poids moléculaire (Mw/Mn) est comprise entre 1,5 et 10 ; et (4) la viscosité à l'état fondu mesurée à 190°C estentre 2,000 et 80,000 mPas.
PCT/JP2012/001838 2011-03-16 2012-03-16 Polyoléfine réactive, son procédé de production, et composition contenant une telle polyoléfine WO2012124345A1 (fr)

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JP2020093541A (ja) * 2018-12-03 2020-06-18 トヨタ紡織株式会社 積層体及びその製造方法
JP2020094204A (ja) * 2018-12-03 2020-06-18 トヨタ紡織株式会社 二剤型ホットメルト接着剤、固化物及び架橋時間の制御方法
CN111868015A (zh) * 2018-02-09 2020-10-30 瑞南科技私人有限公司 智能释放型钾肥颗粒
WO2023068204A1 (fr) * 2021-10-19 2023-04-27 東洋紡株式会社 Résine durcissable

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JP2020094204A (ja) * 2018-12-03 2020-06-18 トヨタ紡織株式会社 二剤型ホットメルト接着剤、固化物及び架橋時間の制御方法
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