JP2017179344A - Manufacturing method of silanized polypropylene, silanized polypropylene obtained by the manufacturing method, resin composition containing silanized polypropylene and thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing silanized polypropylene higher in compatibility with a polypropylene material than conventional materials and excellent in surface modification effect at low cost, good energy efficiency and high selectivity of block structures, silanized polypropylene obtained by the manufacturing method, and a resin composition containing silanized polypropylene and a thermoplastic resin.SOLUTION: There is provided a manufacturing method of silanized polypropylene by reacting (a) polypropylene having one-terminal unsaturated bond with terminal unsaturated bond rate>90% and number average molecular weight of 8,000 or more, (b) a siloxane copolymer having the following structural unit (I) and structural unit (I). Rto Rrepresent each independently a hydrocarbon group having 1 to 10 carbon atoms.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a silylated polypropylene having a specific structure, a silylated polypropylene obtained from the method, and a resin composition containing the silylated polypropylene and a thermoplastic resin.

Polyolefins such as polyethylene and polypropylene have excellent mechanical strength and excellent processability, chemical resistance and electrical properties, and are widely used in daily life and industrial parts because of their light weight and low cost. ing.
Properties expected to be improved with respect to polyolefins include surface properties such as water repellency, oil repellency, antifouling properties, and non-adhesiveness. These performances are expected to be improved especially in the field of life industry materials such as toiletries and foods, and in the field of medical hygiene materials where antifouling properties are required.

  On the other hand, improvement in gas permeability is also desired for polyolefin materials. For example, in the field of packaging materials for fruits and vegetables, polypropylene films with excellent transparency and good appearance are used in many cases. However, it is known that the gas permeability is low, which adversely affects the maintenance of freshness of agricultural products. Therefore, a polypropylene material that satisfies both good transparency and good gas permeability is desired.

In industrial and medical oxygen-enriched membrane applications, silicone resins are conventionally known as materials having excellent oxygen permeability and separation ratio, but silicone resins have poor mechanical strength. In order to solve this problem, a composite film in which a non-porous ultrathin layer portion having high gas permeability, such as silicone, and a porous portion of polypropylene that mechanically supports the same are also developed. However, these composite membranes tend to be costly and are not practically used. Therefore, it is desired to develop a material excellent in mechanical strength and cost that can be independently molded as an additional product with a material having excellent mechanical strength (for example, polypropylene).
By adding various modifiers to the polyolefin, there are cases where mechanical properties, surface properties, etc., which are insufficient alone are improved. However, when the affinity between the material to be modified and the additive is low, the modification effect is not limited, but there is a concern that other properties such as transparency and mechanical properties may be deteriorated.

  For example, as a method for improving the surface properties of polyolefin such as water repellency, oil repellency, antifouling property, non-adhesiveness, and gas permeability, a method of adding high molecular weight silicone to polyolefin and molding and processing it is known. Although it is already commercially available, the affinity between polyolefin and silicone is generally low, and there is a concern that other properties such as transparency and mechanical properties may be deteriorated, and its use is limited. Moreover, since the silicone added due to its low affinity easily floats to the surface of the material, its gas permeability is easily lost. Further, since the silicone is easily removed from the surface by physical contact with the surface, the surface modification property is easily lost, and it has been difficult to maintain the surface modification performance for a long time. In particular, since silicone adheres to and migrates to the contacted substance, it is contraindicated for use in electronic materials where there is concern about contamination of printed circuit boards, particularly copper circuits.

In order to improve such problems, it is known to use a block copolymer of polyolefin and silicone as an additive. As an example of the production of such a block copolymer, for example, the application of hydrosilylation of a hydrosilicone to an unsaturated bond at the end of a polyolefin is known. Patent Document 1 discloses a technique for producing a branched copolymer of polypropylene and polysilane by a procedure including melt layer hydrosilylation. However, this method is a method that specifically silylates the terminal unsaturated group of an unsaturated polymer produced by radical decomposition in the course of the reaction, and its reaction controllability is low, making it possible to produce a block polymer having a specific structure. Is not suitable. Moreover, there is no description about the surface modification performance and gas permeability of the obtained block copolymer.

Patent Document 2 discloses a silicone polyethylene wax obtained by reacting a low molecular weight polyethylene oligomer with hydrogen silicone, but the surface modification performance and gas permeability of the obtained block copolymer are completely different. There is no description.
Patent Document 3 discloses a molded body formed from a composition containing a vinyl group-containing compound, particularly a silylated polyolefin obtained by reaction of a low molecular weight polyethylene having a vinyl group at the terminal and a silicon compound. It has been shown that the addition to polypropylene improves wear resistance and gas permeability. However, the improvement effect is inadequate, especially the deterioration of transparency has occurred, and it is difficult to use as an additive for polypropylene modification.

  Patent Document 4 discloses a block copolymer including at least one organosiloxane block and at least one polyolefin block. However, the disclosed technology focuses on controlling the molecular weight to such an extent that it can be solution-coated. In fact, specific examples of the surface modification effect by coating the polyurethane film are disclosed. However, there is no description on the surface modification performance of polypropylene, and the production uses special substituents or substituents with low reactivity, which is not an efficient production method, and as expected. It is not described that a block polymer having a structure of

  In Patent Document 5, a reaction product of a macromonomer having a vinyl group at a terminal and a polyalkylhydrosiloxane is disclosed. However, the disclosed technique focuses on a siloxane having a large number of reactive sites and develops a very branched structure. Only techniques on the rheological properties of the polymers made are disclosed. However, there is no description about the surface modification performance and gas permeability of the obtained block copolymer, and it has been revealed that the materials in the art have low surface modification performance.

JP 2002-522604 A Japanese Patent Application Laid-Open No. 2004-196883 WO2012 / 098865 JP-T-2015-536376 WO2014 / 047482 publication

  The present invention has been made in view of such circumstances, and silylated polypropylene having a high affinity with industrially important polypropylene materials as compared with conventional materials and having an excellent surface modification effect. An object of the present invention is to provide a method for producing a block structure with high cost and energy efficiency, a silylated polypropylene obtained from the production method, and a resin composition containing the silylated polypropylene and a thermoplastic resin. To do.

As a result of intensive studies, the present inventors have found that the above problem can be achieved by adding a polysiloxane having a specific structure to a polypropylene having a specific single-terminal unsaturated bond.
That is, the gist of the present invention is as follows.
[1] (a) Polypropylene having an unsaturated bond at one end> 90% and a number average molecular weight of 8,000 or more, and (b) the following structural unit (I) and structural unit (II): A process for producing a silylated polypropylene, which comprises reacting a siloxane copolymer with the siloxane copolymer.

(In the formula, R _{1 to} R ₃ each independently represents a hydrocarbon group having 1 to 10 carbon atoms.)
[2] The method for producing a silylated polypropylene according to [1], wherein (a) is an isotactic polypropylene having a mesotriad fraction> 94 mol% and Tm> 130 ° C.
[3] The method for producing a silylated polypropylene according to [1] or [2], wherein in (a), the unsaturated bond at one end is a vinyl group.
[4] The method for producing a silylated polypropylene according to any one of [1] to [3], wherein, in (b), R _{1 to} R ₃ are methyl groups.
[5] The method for producing a silylated polypropylene according to any one of [1] to [4], wherein in (a), the number average molecular weight of the polypropylene is 8,000 to 70,000.
[6] In the above (b), the ratio of structural unit (I) / {structural unit (I) + structural unit (II)} is 0.8 or less [1] to [5] The method for producing silylated polypropylene according to any one of the above.
[7] The method for producing a silylated polypropylene according to any one of [1] to [6], wherein (a) and (b) are reacted in the presence of a platinum catalyst.
[8] Any one of [1] to [7], wherein (a) is produced using a transition metal compound represented by the following general formula (3) as a catalyst. A process for producing silylated polypropylene.

(Wherein, R ¹⁵ and R ¹⁶ each independently represent a heterocyclic group having 4 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur, and R ¹⁷ and R ¹⁸ are each independently, In the range of 6 to 16 carbon atoms, on the aryl cyclic skeleton, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogens having 1 to 6 carbon atoms A hydrocarbon group, an aryl group having a halogen atom as a substituent, or a heterocyclic group containing 6 to 16 carbon atoms containing nitrogen, oxygen, or sulfur, X ¹² and Y ¹² are each independently Hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon having 1 to 20 carbon atoms Group, amino group, or carbon number 1 Represents a nitrogen-containing hydrocarbon group having 20, Q ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group silylene group have or germylene groups, having 1 to 20 carbon atoms Represents.)
[9] Silylated polypropylene produced by the production method according to any one of [1] to [8].
[10] The silylated polypropylene according to [9], which has the following structural unit (III) and structural unit (IV).

(Wherein R ₄ is an isotactic polypropylene chain having a mesotriad fraction> 94 mol%, Tm> 130 ° C., and a number average molecular weight of 8,000 or more. R ₅ has 1 to 10 carbon atoms. Represents a hydrocarbon group.)

(In formula, R < ₆ >, R < ₇ > represents a C1-C10 hydrocarbon group each independently.)
[11] The silylated polypropylene according to [10], wherein R _{5 to} R ₇ are methyl groups.
[12] A resin composition comprising the silylated polypropylene according to any one of (A) [9] to [11], and (B) a thermoplastic resin.
[13] The resin composition according to [12], wherein the (B) thermoplastic resin is a polyolefin resin.
[14] In [12] or [13], 0.01 to 10,000 parts by weight of the silylated polypropylene of (A) is contained with respect to 100 parts by weight of the thermoplastic resin (B). The resin composition as described.

  According to the method for producing silylated polypropylene of the present invention, a silicone-polypropylene block copolymer having a high affinity for polypropylene and a high surface modification effect compared to conventional materials can be obtained at low cost and with high energy efficiency. In addition, the block structure can be manufactured with high selectivity.

  The method for producing silylated polypropylene of the present invention comprises (a) a terminal unsaturated bond ratio> 90%, a number average molecular weight of 8,000 or more, polypropylene having a single terminal unsaturated bond, and (b) the following structural unit (I And a siloxane copolymer having the structural unit (II).

[polypropylene]
(A) Polypropylene having a single-terminal unsaturated bond having a terminal unsaturated bond ratio> 90% and a number average molecular weight of 8,000 or more In the present invention, a polypropylene having a single-terminal unsaturated bond (hereinafter, “single-terminal unsaturated polypropylene”). ”) Has an unsaturated bond at least at one end of the polypropylene structure and at least has no unsaturated bond at one end. In the case of linear polypropylene, it has an unsaturated bond only at one of the two ends. In the case of a branched polypropylene, at least one of the three or more ends has an unsaturated bond, and at least one end has no unsaturated bond.

Examples of the one-terminal unsaturated bond include vinylidene group, vinylene group, vinyl group and the like, preferably vinylidene group and vinyl group, more preferably vinyl group.
One-terminal unsaturated polypropylene is preferably represented by the following general formula (1).

(In the formula, PP represents a polypropylene structure, and R ₁ is a hydrogen atom or a methyl group.)
In general formula (1), R ₁ is preferably a hydrogen atom from the viewpoint of the efficiency and selectivity of the modification reaction.

(Terminal unsaturated bond ratio)
The terminal unsaturated bond ratio of the one-terminal unsaturated polypropylene was determined based on the following formula from ¹³ C-NMR and ¹ H-NMR measurement results.
Terminal unsaturated bond percentage = number of unsaturated bond terminals / number of starting terminals
= Unsaturated bond terminal number / {(total terminal number-long chain branch number) / 2}
Total number of terminals = i-butyl terminal number + n-propyl terminal number + n-butyl terminal number + 2,3-dimethylbutyl terminal number + vinyl terminal number + vinylidene terminal number + vinylene terminal number unsaturated bond terminal number = vinyl terminal number + vinylidene Number of terminals + number of vinylene terminals

<Determined from 13C-NMR measurement>
Isobutyl terminal number / 1,000 propylene monomers = 1000 * (average of integrated values of signals of 22.52, 23.79, 25.76, 47.42 ppm) / integrated value of Sαα N. The notation of “Macromolecules 1984, 17, 1950” by Cheng is followed.

n-propyl terminal number / 1,000 propylene monomers = 1000 * (average of integrated values of signals of 14.47, 30.48, 39.64 ppm) / integral value of Sαα n-butyl terminal number / propylene monomer 1, 000 = 1000 * (average of integrated values of signals of 14.11, 23.21, 36.90 ppm) / integrated value of Sαα 2,3-dimethylbutyl terminal number / 1,000 propylene monomers = 1000 * (16 .23, 17.66, 36.42, average of integral values of signals of 49.99 ppm) / integral value of Sαα / number of long-chain branches / 1,000 propylene monomers = 1000 * (31.60, 44.00, 44.69ppm of signal integral value) / Sαα integral value

<Determined from 1H-NMR measurement>
Number of vinyl ends / 1,000 propylene monomers = 2000 * (integral value of vinyl signal in the range of 4.9-5.1, 5.7-5.9 ppm) / (main chain in the range of 3.0-0.2 ppm) Integrated value of the signal derived from)
Number of vinylidene terminals / 1,000 propylene monomers = 3000 * (integral value of 4.69, 4.74 ppm of vinylidene signal) / (integrated value of signal derived from main chain of 3.0-0.2 ppm region)
Number of vinylene terminals / 1,000 propylene monomers = 3000 * (integral value of vinylene signal in the 5.3-5.5 ppm region) / (integral value of signal derived from the main chain in the 3.0-0.2 ppm region)

The terminal unsaturated bond ratio of the one-terminal unsaturated polypropylene used in the present invention is usually 90% or more, preferably 92% or more, more preferably 95% or more, and most preferably 100%. The higher the terminal unsaturated bond ratio, the higher the yield of silylated polypropylene, and the lower cost, energy efficient, and block structured silylated polypropylene can be produced with high selectivity.
Further, the one-terminal unsaturated polypropylene may be a branched one-terminal unsaturated polypropylene having a polypropylene side chain as long as rigidity and heat resistance are not impaired.

(Number average molecular weight of one-end unsaturated polypropylene)
The number average molecular weight (Mn) of the terminal unsaturated polypropylene used in the present invention is 8,000 or more from the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the silylated polypropylene to be produced and the composition containing it. Preferably it is 9,000 or more, More preferably, it is 10,000 or more. The number average molecular weight is usually 200,000 or less, preferably 150,000 or less, more preferably 100,000 or less, and more preferably 70,000 or less. If it is not more than the above upper limit value, it is easy to achieve both mechanical properties and physical properties of silylated polypropylene. The number average molecular weight is determined by GPC measurement.

  The molecular weight distribution of this terminal unsaturated polypropylene is a precise physical property depending on the molecular weight from the viewpoint of mechanical properties such as heat resistance and viscoelasticity, solvent resistance and bleed-out reduction of the silylated polypropylene produced and the composition containing it. The narrower one is preferred to allow control. The molecular weight distribution of the terminal unsaturated polypropylene used in the present invention is usually 1 or more in terms of Mw / Mn, usually 10 or less, preferably 5 or less, particularly preferably 3 or less.

(Stereoregularity of one-end unsaturated polypropylene)
One-end unsaturated polypropylene preferably has a highly stereoregular structure. “Triad fraction” is used as a factor representing the high degree of stereoregularity of polypropylene. Triad indicates the continuity of the relative arrangement of adjacent side-chain methyl groups of polypropylene, and the higher this value, the higher the stereoregularity. The meso triad (mm) fraction is the percentage of the total propylene units of the propylene unit at the center of the chain in which three propylene monomer units consisting of head-to-tail bonds are continuously meso-bonded in the polymer chain. It is represented by. The triad can usually be determined by a methyl group signal in 13C-NMR. The assignment of peaks is, for example, A. It can be determined according to the assignment of the peak proposed in “Macromolecules 1975, 8, 687” by Zambelli et al.
A more specific method for determining the mm fraction will be described below.

Peaks derived from the methyl group of the three-chain central propylene bonded head-to-tail around the propylene unit occur in three regions depending on the configuration.
mm: about 24.3 to about 21.1 ppm
mr: about 21.2 to about 20.5 ppm
rr: about 20.5 to about 19.8 ppm
The chemical shift range of each region slightly shifts depending on the molecular weight and copolymer composition, but the above three regions can be easily identified.
Here, mm, mr, and rr are each represented by the following structure.

The mm fraction is calculated from the following mathematical formula (1).
mm fraction = peak area of mm region / (peak area of mm region + peak area of mr region + peak area of rr region) × 100 [%] (1)
From the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the silylated polypropylene to be produced and the composition containing the same, one-terminal unsaturated polypropylene is preferably one having a high triad structure, and this triad is usually 90 mol%. It is above, Preferably it is 92 mol% or more, Especially preferably, it is 94 mol% or more.

(Melting point (Tm) of unsaturated polypropylene at one end)
The melting point (Tm) of the terminal unsaturated polypropylene used in the present invention is not particularly limited, but the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the silylated polypropylene to be produced and the composition containing the same. Therefore, the higher one is preferable, usually 100 ° C. or higher, preferably 110 ° C. or higher, more preferably 120 ° C. or higher, and further preferably 130 ° C. or higher. The melting point of the terminal unsaturated polypropylene is measured by a differential scanning calorimeter (DSC).
One-terminal unsaturated polypropylene may contain a segment derived from a comonomer other than propylene in the main chain as long as the effect of the present invention is not impaired, but a silylated polypropylene to be produced and a composition containing the same From the viewpoint of mechanical properties such as heat resistance and viscoelasticity, a propylene homopolymer is preferably used.

(Method for producing single-end unsaturated polypropylene)
The method for producing the terminal unsaturated polypropylene used in the present invention is not particularly limited, and a conventionally known method for producing terminal unsaturated polypropylene can be appropriately used. In the prior art, a technique of introducing an unsaturated bond at one end or both ends of a polypropylene molecule by cutting a molecular chain by thermal decomposition or radical decomposition is also known, but the terminal unsaturation of polypropylene used in the present invention is also known. The bond is preferably introduced at the end of the propylene-based polymer without using a thermal decomposition method for reasons such as ease of molecular weight control and improvement of the purity of the terminal olefin. More specifically, a method that is produced by the coordination polymerization of propylene using a transition metal compound and has a vinyl group at a high proportion of the terminal end of polymerization is preferable from an economical viewpoint.

For example, a method of introducing a vinyl group at the terminal by utilizing the fact that β-methyl group elimination reaction frequently occurs by polymerizing propylene at a high temperature using a stereorigid C2 symmetrically bridged metallocene catalyst (for example, JP 2001-2001). No. 525461), by using a complex having a bulky substituent at a specific site, or by using a complex having a heterocyclic group at a specific site, the frequency of β methyl elimination reaction at a relatively low temperature can be reduced. A method for producing a product while maintaining high stereoregularity by increasing the concentration (for example, JP-A-11-349634, JP-A-2009-299045, etc.), elimination of vinyl chloride, etc. in propylene by an isotactic structure selective metallocene catalyst. A vinyl comonomer with an easily functional group is copolymerized, and this comonomer undergoes β functional group elimination upon insertion. A method for selectively producing a macromonomer having a terminal vinyl group (Gaynor, SG Macromolecules 2003, 36, 4692-4698) or a propylene polymerization catalyst in which 2,1-insertion of propylene is preferred (for example, pyridyldiimine iron (II) A method of introducing a terminal vinyl group via β-hydrogen elimination without going through a relatively difficult β-methyl group elimination process using a late transition metal complex represented by a complex) (Brookhart, M. et. Al. Macromolecules 1999, 32, 2120).

  Among these, by using a complex having a heterocyclic group at a specific site, a method for producing while maintaining high stereoregularity by increasing the frequency of β methyl elimination reaction at a relatively low temperature (for example, JP-A-2009- No. 299045) is preferable from the viewpoint of achieving both high stereoregularity and high vinyl selectivity, and a method of manufacturing using a transition metal compound represented by the following general formula (2) is more preferable.

In General Formula (2), R ¹¹ and R ¹² each independently represent a heterocyclic group having 4 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur. R ¹³ and R ¹⁴ may each independently contain at least one heteroatom having 6 to 16 carbon atoms selected from halogen, silicon, oxygen, sulfur, nitrogen, boron, and phosphorus. An aryl group or a heterocyclic group having 6 to 16 carbon atoms and containing nitrogen, oxygen or sulfur. X ¹¹ and Y ¹¹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group having 1 to 20 carbon atoms, or a halogenated group having 1 to 20 carbon atoms. Represents a hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms. Represents a silylene group or a germylene group which may have a hydrocarbon group having 1 to 20 carbon atoms.

The heterocyclic group containing 4 to 16 carbon atoms of R ¹¹ and R ¹² and containing nitrogen, oxygen or sulfur is preferably a 2-furyl group, a substituted 2-furyl group, or a substituted 2-thienyl group. Or a substituted 2-furfuryl group, and more preferably a substituted 2-furyl group.
By introducing a substituent of an appropriate size on the heterocyclic group, the relative positional relationship between the heterocyclic ring, the coordination field on the transition metal, and the growing polymer chain can be made appropriate. A terminal unsaturated polypropylene having a group introduced with high selectivity can be obtained.

  In addition, the substituted 2-furyl group, substituted 2-thienyl group, and substituted 2-furfuryl group have a C 1-6 alkyl group such as a methyl group, an ethyl group, or a propyl group. A halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group, and a trialkylsilyl group. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.

Further, R ¹¹ and R ¹² are particularly preferably a 2- (5-methyl) -furyl group. R ¹¹ and R ¹² are preferably the same as each other.
R ¹³ and R ¹⁴ are aryl groups having 6 to 16 carbon atoms, which may contain at least one hetero element selected from halogen, silicon, oxygen, sulfur, nitrogen, boron, and phosphorus, or carbon atoms 6 -16, a heterocyclic group containing nitrogen, oxygen or sulfur, but in particular, by making R ¹³ and R ¹⁴ more bulky, the terminal unsaturation has higher stereoregularity and less heterogeneous bonds. Polypropylene can be obtained.

Therefore, R ¹³ and R ¹⁴ are one or more hydrocarbon groups having 1 to 6 carbon atoms and silicon-containing hydrocarbons having 1 to 6 carbon atoms on the aryl cyclic skeleton in the range of 6 to 16 carbon atoms. Group, a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and an aryl group having a halogen atom as a substituent. Specific examples of such R ¹³ and R ¹⁴ include 4-isopropylphenyl group, 4-t- A butylphenyl group, a 2,3-dimethylphenyl group, a 3,5-di-t-butylphenyl group, a 4-chlorophenyl group, a 4-trimethylsilylphenyl group, a 1-naphthyl group, and a 2-naphthyl group.

R ¹³ and R ¹⁴ are more preferably one or more hydrocarbon groups having 1 to 6 carbon atoms and silicon-containing hydrocarbon groups having 1 to 6 carbon atoms in the range of 6 to 16 carbon atoms. , A halogen-containing hydrocarbon group having 1 to 6 carbon atoms, or a phenyl group having a halogen atom as a substituent. Furthermore, the substituted position is preferably the 4-position on the phenyl group. Specific examples of such R ¹³ and R ¹⁴ are 4-isopropylphenyl group, 4-t-butylphenyl group, 4-biphenylyl group, 4-chlorophenyl group, and 4-trimethylsilylphenyl group. Further, it is preferable that R ¹³ and R ¹⁴ are the same.

In the general formula (2), X ¹¹ and Y ¹¹ are auxiliary ligands. Therefore, the types of X ¹¹ and Y ¹¹ are not limited as long as this object is achieved, and each independently represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number having 1 to 20 carbon atoms. A silicon-containing hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, or a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms.

In general formula (2), Q ¹¹ is a silylene having 1 to 20 carbon atoms or a hydrocarbon group having 1 to 20 carbon atoms, which bonds two five-membered rings. A group or a germylene group. When two hydrocarbon groups are present on the above-mentioned silylene group or germylene group, they may be bonded to each other to form a ring structure.
Specific examples of the above ^{Q 11,} methylene, methylmethylene, dimethylmethylene, 1,
Alkylene group such as 2-ethylene; arylalkylene group such as diphenylmethylene; silylene group; methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene Alkylsilylene groups such as methyl (phenyl) silylene; (alkyl) (aryl) silylene groups such as methyl (phenyl) silylene; Arylsilylene groups such as diphenylsilylene; Alkyl oligosilylene groups such as tetramethyldisilylene; Germylene group; Examples thereof include an alkylgermylene group in which silicon of a silylene group having a hydrocarbon group of 1 to 20 is substituted with germanium; an (alkyl) (aryl) germylene group; an arylgermylene group. In these, the silylene group which has a C1-C20 hydrocarbon group, or the germylene group which has a C1-C20 hydrocarbon group is preferable, and an alkylsilylene group and an alkylgermylene group are especially preferable.

The transition metal compound represented by the general formula (2) is usually used in combination with a cocatalyst described later. Preferably, an organoaluminum oxy compound, an ionic compound capable of reacting with a catalyst precursor to convert it to a cation, Lewis acid, ion-exchanged layered silicate, etc. are used as a cocatalyst, and particularly preferably an organic compound. Aluminum oxy compounds and ion exchange layered silicates are used. In the above combination, an organoaluminum compound may be further used in combination.
Among the transition metal compounds represented by the general formula (2), the transition metal compound represented by the following general formula (3) has good solubility in an aromatic hydrocarbon-based organic solvent such as toluene, It is preferable from the viewpoint of handling in purification of transition metal compounds and catalyst preparation.

(Wherein, R ¹⁵ and R ¹⁶ each independently represent a heterocyclic group having 4 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur, and R ¹⁷ and R ¹⁸ are each independently, In the range of 6 to 16 carbon atoms, on the aryl cyclic skeleton, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogens having 1 to 6 carbon atoms A hydrocarbon group, an aryl group having a halogen atom as a substituent, or a heterocyclic group containing 6 to 16 carbon atoms containing nitrogen, oxygen, or sulfur, X ¹² and Y ¹² are each independently Hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon having 1 to 20 carbon atoms Group, amino group, or carbon number 1 Represents a nitrogen-containing hydrocarbon group having 20, Q ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group silylene group have or germylene groups, having 1 to 20 carbon atoms Represents.)

  Although it does not restrict | limit as a manufacturing method of the terminal unsaturated polypropylene used in this invention, As above-mentioned, it is preferable to manufacture by coordination polymerization of propylene from an economical viewpoint. The polymerization conditions are not particularly limited as long as the target product is obtained, and solution polymerization, slurry polymerization, liquid phase solventless polymerization (bulk polymerization), gas phase polymerization, melt polymerization, etc., which do not substantially use a solvent, can be used. In addition, continuous polymerization, batch polymerization, and so-called multistage polymerization may be employed.

The polymerization temperature, polymerization pressure, and polymerization time are not particularly limited, but usually can be appropriately set in consideration of productivity and selectivity of the terminal vinyl group.
The polymerization temperature is usually 0 ° C. or higher, preferably 30 ° C. or higher, more preferably 50 ° C. or higher, particularly preferably 70 ° C. or higher, and usually 150 ° C. or lower, preferably 100 ° C. or lower. The polymerization pressure is usually 0.01 MPa or more, preferably 0.05 MPa or more, more preferably 0.1 MPa or more, and usually 100 MPa or less, preferably 20 MPa or less, more preferably 5 MPa or less. This is because, when produced by this method, the terminal end of the terminal unsaturated polypropylene molecule is usually an alkyl group at the start of the polymerization reaction and a vinyl group with a high probability of the end of the polymerization reaction. In this case, the possibility that both ends of the macromonomer molecule are vinyl groups is usually extremely low.

[Siloxane copolymer]
(B) Siloxane copolymer having the following structural unit (I) and structural unit (II)

(In the formula, R _{1 to} R ₃ each independently represents a hydrocarbon group having 1 to 10 carbon atoms.)
R _{1 to} R ₃ are each independently a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 6 or less carbon atoms. R _{1 to} R ₃ are preferably methyl groups.
The siloxane copolymer used in this reaction contains the unit structures (I) and (II). Unit structure (I) is a unit structure necessary for the reaction with the above-mentioned terminal unsaturated polypropylene. The unit structure (II) is a unit structure that is necessary for exhibiting surface properties such as water repellency, oil repellency, antifouling property, and adhesiveness expected in silylation and properties excellent in gas permeability. As the siloxane polymer used in the present invention, the unit structure (I) may be contained in an amount necessary for the reaction with the terminal unsaturated polypropylene, and the unit structure (I) is preferably not too much. When the amount of the structural unit (I) is excessive, side reactions are frequently caused during the reaction between the terminal unsaturated polypropylene and the siloxane copolymer, which is not preferable from the viewpoint of selectivity. On the other hand, a larger amount of unit structure (II) is preferable in order to enhance the properties expected in silylation.

From such a viewpoint, the siloxane copolymer used in this reaction preferably satisfies the following formula (2).
Structural unit (I) (pieces) / {Structural unit (I) (pieces) + Structural unit (II) (pieces)} ≦ 0.8 (2)
In the formula (2), the method for calculating the number of the respective structural units (I) and (II) is as follows.

First, the unit structure (I) (pieces) and the unit structure (II) (pieces) have the relationship of the following formula (3).
Number average molecular weight Mn (g / mol) of siloxane copolymer = molecular weight of both terminal sites + unit structure (I) (number) × molecular weight of unit structure (I) + unit structure (II) (number) × unit structure (II) Molecular weight of (3)

The unit structure (I) (pieces) can be calculated from the Si—H reactive group substitution ratio (mmol / g) of each siloxane copolymer. In order to calculate the unit structure (II) (number), the number average molecular weight Mn of the siloxane copolymer, the molecular weight of both terminal sites, the molecular weight of the unit structure (I), and the molecular weight of the unit structure (II) are required. Here, the case where all the substituents at both terminal sites, R _{1 to} R ₃ are methyl groups, will be described. The molecular weights of both terminal sites, unit structure (I), and unit structure (II) can be expressed as molecular weights of structural units represented by [a], [b], and [c], respectively. The molecular weights corresponding to these structures are Mn [a] = 162.38, Mn [b] = 60.13, Mn [c] = 74.15.

On the other hand, for the number average molecular weight Mn of the siloxane copolymer, using the kinematic viscosity (cSt) η of each siloxane copolymer at 25 ° C., the Barry equation log η = 1.00 + 0.0123 × Mn ^0.5 (J. Appl. Physics) , 1946, 17, 1020). Here, η is a kinematic viscosity (cSt) at 25 ° C., and Mn is a number average molecular weight.

By substituting the molecular weight of Mn, unit structure (I) (units), both terminal sites, unit structure (I), and unit structure (II) into formula (3), unit structure (II) (units) Can be calculated.
The number of structural units (I) and (II) can also be calculated from the charged amounts of structural units (I) and (II).

In the above (b), the ratio of structural unit (I) / {structural unit (I) + structural unit (II)} is preferably 0.6 or less, more preferably 0.4 or less. Yes, usually 0.01 or more, preferably 0.05 or more. Within the above range, the affinity with polypropylene and the effect of silylation tend to be easily obtained in a balanced manner.
The kinematic viscosity η at 25 ° C. of the siloxane copolymer used in this reaction is usually 1 or more, preferably 5 or more, more preferably 10 or more, and particularly preferably 50 or more. If the kinematic viscosity is in the above range, the molecular weight of the siloxane copolymer is sufficiently large, so that it has a lot of structural units (II). The effect of gas permeability is increased.
The number average molecular weight range of the siloxane copolymer used in this reaction is usually 500 or more, preferably 1000 or more. For the same reason as the kinematic viscosity, the higher the molecular weight of the siloxane copolymer, the greater the surface properties such as water repellency, oil repellency, antifouling properties, and adhesion, and the gas permeability effect.

[Reaction of single-end unsaturated polypropylene and siloxane copolymer]
In the hydrosilylation reaction, in one embodiment, a transition metal complex catalyst is used. The catalyst is preferably a transition metal complex of Groups 8 to 10 of the periodic table, and examples thereof include a platinum complex, a rhodium complex, a cobalt complex, a palladium complex, and a nickel complex. In the present invention, platinum catalysts are preferable, and platinum complexes such as chloroplatinic acid and platinum olefin complexes are particularly preferable. The usage-amount of a catalyst is about 0.1-1000 mass ppm normally as a metal unit with respect to a terminal unsaturated polypropylene, Preferably it is 1-500 mass ppm, Most preferably, it is 5-100 mass ppm.

The charging ratio of the one-terminal unsaturated polypropylene and the siloxane copolymer is usually 1: 0.1 to 30, preferably 1: 0.5 to 10. In order to obtain a silylated polypropylene in which the one-end unsaturated polypropylene and the siloxane copolymer are reacted at 1: 1, it is necessary to charge the siloxane copolymer in excess as compared with the one-end unsaturated polypropylene.
The hydrosilylation reaction may be performed in a molten state or in a solution state (hereinafter may be referred to as “melting reaction” and “solution reaction”, respectively). In the case of a melt reaction, the reaction temperature needs to be equal to or higher than the melting temperature of the terminal unsaturated polypropylene, and is usually about 100 to 250 ° C, preferably 150 to 200 ° C. In the case of a solution reaction, the reaction temperature is usually about −30 to 150 ° C., preferably 30 to 140 ° C. The reaction time is about 1 minute to 20 hours. The hydrosilylation reaction is usually performed at normal pressure, but may be performed under pressure.

  A typical processing apparatus (for example, an extruder, a batch mixer, a hot press, etc.) can be used for the said melting reaction. The reaction may be carried out batchwise or continuously. This melting reaction is carried out in the molten phase of terminally unsaturated polypropylene. In this case, the terminal unsaturated polypropylene, the siloxane copolymer, and the transition metal complex as a catalyst may be mixed before the reaction or may be sequentially added to the reactor.

In the solution reaction, the reaction apparatus is not particularly limited. For example, a tank type reaction group having a batch type or continuous type stirring apparatus can be used. Examples of the reaction solvent used in the solution reaction include hydrocarbon solvents and ethers. Examples of the hydrocarbon solvent include saturated aliphatic hydrocarbons such as hexane, heptane, octane and decane, saturated alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, and aromatic hydrocarbons such as benzene, toluene and xylene. It is done. The solvent is preferably a hydrocarbon solvent, more preferably a saturated alicyclic hydrocarbon and an aromatic hydrocarbon.
The amount of the solvent used is not particularly limited as long as it is a state in which the one-end unsaturated polypropylene and the siloxane copolymer are dissolved. Usually, the total concentration of the one-end unsaturated polypropylene and the siloxane copolymer is 5 to 5. The amount is 50% by mass, preferably 10 to 40% by mass.

[Silylated polypropylene]
The silylated polypropylene produced by the production method of the present invention preferably has the following structural unit (III) and structural unit (IV).

(Wherein R ₄ is an isotactic polypropylene chain having a mesotriad fraction> 94 mol%, Tm> 130 ° C., and a number average molecular weight of 8,000 or more. R ₅ has 1 to 10 carbon atoms. Represents a hydrocarbon group.)

(In formula, R < ₆ >, R < ₇ > represents a C1-C10 hydrocarbon group each independently.)
The measurement method and preferred range of the mesotriad fraction, Tm, and number average molecular weight of R _{4 in} (III) are the same as those for the above-mentioned one-terminal unsaturated polypropylene.
The hydrocarbon group of R _{5 in} (III) is the same as R ₁ described above.
R ₆ and R _{7 in} the above (IV) are the same as R ₂ and R ₃ described above.

R _{5 to} R ₇ are preferably methyl groups.
The number average molecular weight range of the silylated polypropylene obtained by the hydrosilylation reaction is usually 8,500 or more, and preferably 10,000 or more. The number average molecular weight is usually 250,000 or less, preferably 200,000 or less, more preferably 100,000 or less.

[Uses of silylated polypropylene]
The silylated polypropylene of the present invention is a modification of polypropylene material, particularly modification of surface properties such as water repellency, oil repellency, antifouling property and adhesion of polypropylene material, or compatibilization with various resins including polar resin, or It can be suitably used for improvement of mechanical properties by compounding with various inorganic materials.

  In addition, the silylated polypropylene of the present invention has water resistance, antifouling property, releasability, gas permeability, etc. as silicone while having heat resistance, transparency and molding processability similar to polypropylene as a single molded body. It can be used for various applications as a material having specific physical properties. For example, it is suitable for gas separation membranes such as oxygen-enriched membranes due to its excellent gas permeability, and it is also suitable for packaging materials that wrap foods such as fruits and vegetables due to its excellent transparency.

[Resin composition]
For the purpose of improving the mechanical properties and the like of existing resins, the silylated polypropylene can be used as a composition with various resins.
The resin composition of the present invention is a resin composition containing (A) a silylated polypropylene, (B) a thermoplastic resin, and optionally other components, and (B) a thermoplastic resin and other components. Details are described.

(B) Thermoplastic resin The thermoplastic resin used in the present invention is not particularly limited. For example, polyolefin resin, polycarbonate resin, thermoplastic polyester resin, ABS resin, polyacetal resin, polyamide resin, polyphenylene oxide resin, polyimide resin, polyurethane resin. , Polylactic acid resin, furan resin, and silicone resin. Each of these thermoplastic resins can be used alone or in combination of two or more. Of these, polyolefin resins are preferably used.

There is no restriction | limiting in particular in the polyolefin resin used by this invention, A conventionally well-known polyolefin resin can be used. Specific examples include polyethylene resins such as low density polyethylene and high density polyethylene, polypropylene resins, polyethylene terephthalate resins, vinyl chloride resins, ethylene / vinyl acetate copolymers, and ethylene / methacrylic acid acrylate copolymers. Among these, low density polyethylene, high density polyethylene, and polypropylene resin are preferably used.

(Other ingredients)
In the composition of the present invention, resins and additives other than (A) silylated polyolefin and (B) thermoplastic resin can be blended as long as the effects of the present invention are not significantly impaired. Other components may be used alone or in combination of two or more in any combination and ratio.

  (B) Specific examples of resins other than thermoplastic resins include, for example, polyolefins not included in polyolefin resins; polyphenylene ether resins; polyamide resins such as nylon 6, nylon 66, and nylon 11; polycarbonate resins; polyethylene Examples thereof include polyester resins such as terephthalate and polybutylene terephthalate; (meth) acrylic resins such as polymethyl methacrylate; styrene resins such as polystyrene; and various thermoplastic elastomers.

  Examples of additives include various heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, anti-aging agents, nucleating agents, plasticizers, impact modifiers, compatibilizers, antifoaming agents, Examples thereof include a sticking agent, a crosslinking agent, a surfactant, a lubricant, an antiblocking agent, a processing aid, an antistatic agent, a flame retardant, a flame retardant aid, a filler, a colorant, and an inorganic crystal nucleating agent.

  Examples of the heat stabilizer and the antioxidant include hindered phenols, phosphorus compounds, hindered amines, sulfur compounds, copper compounds, alkali metal halides, and the like. Flame retardants are roughly classified into halogen-based flame retardants and non-halogen-based flame retardants, and non-halogen-based flame retardants are preferable in terms of the environment. Non-halogen flame retardants include phosphorus flame retardants, hydrated metal compounds (aluminum hydroxide and magnesium hydroxide) flame retardants, nitrogen-containing compounds (melamine and guanidine) flame retardants and inorganic compounds (borate and molybdenum) Compound) flame retardant and the like.

  Fillers are roughly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally occurring polymers such as starch, cellulose fine particles, wood flour, okara, fir husk, bran, and modified products thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wollastonite, silica, alumina, magnesium oxide, calcium silicate, sodium aluminate, calcium aluminate, sodium aluminosilicate, magnesium silicate, glass balloon, carbon Examples thereof include black, zinc oxide, antimony trioxide, zeolite, hydrotalcite, metal fiber, metal whisker, ceramic whisker, potassium titanate, boron nitride, graphite, and carbon fiber.

Examples of nucleating agents include sorbitol compounds and metal salts thereof; benzoic acid and metal salts thereof; phosphoric acid ester metal salts; ethylene bisoleic acid amide, methylene bisacrylic acid amide, ethylene bisacrylic acid amide, hexamethylene bis-9,10 -Dihydroxystearic acid bisamide, p-xylylene bis-9,10-dihydroxystearic acid amide, decanedicarboxylic acid dibenzoyl hydrazide, hexanedicarboxylic acid dibenzoyl hydrazide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 2,6-naphthalenedicarboxylic acid Dianilide, N, N ′, N ″ -tricyclohexyltrimesic acid amide, trimesic acid tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, 2,6-naphthalenedicarboxylic acid Cyclohexylamide, N, N′-dibenzoyl-1,4-diaminocyclohexane, N, N′-dicyclohexanecarbonyl-1,5-diaminonaphthalene, ethylenebisstearic acid amide, N, N′-ethylenebis (12-hydroxy) And amide compounds such as stearic acid) amide and octanedicarboxylic acid dibenzoylhydrazide. Examples of the inorganic crystal nucleating agent include talc, kaolin, and silica.

  When these “other components” are used in the resin composition in the present invention, the content thereof is not limited, but is usually 0.01% by weight or more, preferably 0.2% by weight or more in the resin composition, It is usually 10% by weight or less, preferably 5% by weight or less.

(Blend ratio of resin composition)
The content ratio of (A) silylated polypropylene and (B) thermoplastic resin constituting the resin composition is not limited, but (A) silylated polypropylene is usually 0 with respect to 100 parts by weight of (B) thermoplastic resin. 0.01 parts by weight or more, preferably 0.1 parts by weight or more, more preferably 1 part by weight or more, while usually 10,000 parts by weight or less, preferably 1,000 parts by weight or less, more preferably 100 parts by weight. The content is more preferably 20 parts by weight or less. (A) When the content rate of silylated polypropylene is less than the said lower limit, the uniformity of a resin composition tends to fall. On the other hand, when the content ratio of (A) silylated polypropylene exceeds the upper limit, the mechanical strength of the resin composition may be lowered.

(Preparation of resin composition)
The resin composition in the present invention containing a silylated polypropylene and a thermoplastic resin can be obtained by blending the above-described components as raw materials and molding as it is to obtain a molded body. It is preferable that a molded product obtained by molding the resin composition is produced and used as a resin composition. The resin composition of the present invention can be obtained by mixing the above-described components at a predetermined ratio. The mixing method is not particularly limited as long as the raw material components can be uniformly dispersed and mixed. That is, a composition in which each component is uniformly distributed can be obtained by mixing the above-described raw material components simultaneously or in any order.
For more uniform mixing / dispersion, it is preferable to melt and mix a predetermined amount of the raw material components. Specifically, for example, the raw material components and the like of the resin composition may be mixed and heated in an arbitrary order, or may be mixed while sequentially melting all the raw material components and the like. Furthermore, only a part of the above-described components may be left as a resin composition, and this resin composition and other components may be blended and used for molding of the resin composition.

  The mixing method and mixing conditions are not particularly limited as long as each raw material component is uniformly mixed, but from the viewpoint of productivity, the raw materials are mixed using, for example, a tumbler blender, V blender, ribbon blender, Henschel mixer, etc. A melt kneading method using a continuous kneader such as a single screw extruder or a twin screw extruder and a batch kneader such as a mill roll, a Banbury mixer, or a pressure kneader is preferable. The temperature at the time of melt mixing may be a temperature at which at least one of the respective raw material components is in a molten state, but usually a temperature at which all the components used are melted is selected, and generally it is carried out at 150 to 250 ° C.

(Measurement of number average molecular weight of single-end unsaturated polypropylene)
First, about 20 mg of a sample was collected in a vial for a high temperature GPC pretreatment device PL-SP260VS manufactured by Polymer Laboratories, and o-dichlorobenzene containing BHT as a stabilizer (BHT concentration = 0.5 g / L). ) Was added, and the polymer concentration was adjusted to 0.1 (% by weight). The polymer was heated to 135 ° C. with the pretreatment device for high temperature GPC PL-SP260VS to be dissolved, and filtered through a glass filter to prepare a sample. In the GPC measurement in the present invention, no polymer was captured by the glass filter.

Next, GPC measurement was performed using Tosoh's TSKgel GMH-HT (30 cm × 4) and a Waters V2000 equipped with an RI detector. As measurement conditions, sample solution injection amount: 524.5 (μl), column temperature: 135 ° C., solvent:
o-Dichlorobenzene, flow rate: 1.0 (ml / min) was employed. The molecular weight was calculated as follows. That is, a commercially available monodispersed polystyrene is used as a standard sample, a calibration curve relating to the retention time and molecular weight is created from the polystyrene standard sample and the viscosity formula of the propylene polymer, and the molecular weight is calculated based on the calibration curve. went.
As the viscosity formula, [η] = K × M ^α is used, for polystyrene, K = 1.38E-4, α = 0.70 is used, and for propylene-based polymer. , K = 1.03E-4, α = 0.78.

(One-end unsaturated polypropylene NMR measurement)
200-300 mg of a sample was placed in an NMR sample tube having an inner diameter of 10 mmφ together with 2.4 ml of o-dichlorobenzene / deuterated benzene bromide (C6D5Br) = 4/1 (volume ratio) and hexamethyldisiloxane which is a chemical shift reference material. The mixture was purged with nitrogen, sealed, heated and dissolved, and subjected to NMR measurement as a uniform solution. NMR measurement was carried out using an NMR apparatus AVANCE III400 manufactured by Bruker BioSpin Co., Ltd. equipped with a 10 mmφ cryoprobe.
The measurement of ¹ H-NMR was performed at a sample temperature of 80 ° C., a pulse angle of 4.5 °, a pulse interval of 2 seconds, and an integration count of 512 times.
^{The 13} C-NMR measurement was performed by the reverse gate decoupling method with the sample temperature of 80 ° C., the pulse angle of 90 °, the pulse interval of 51.5 seconds, and the number of integrations of 1024 times.

(Measurement of melting point of single-end unsaturated polypropylene (Tm))
Using a PYRIS Diamond DSC differential scanning calorimeter manufactured by Perkin Elmer, the sample (about 5 mg) was melted at 210 ° C. for 5 minutes, then cooled to −20 ° C. at a rate of 10 ° C./minute, and 5 ° C. at −20 ° C. After the minute holding, the melting curve was obtained by raising the temperature to 210 ° C. at a rate of 10 ° C./min. The peak top temperature of the main exothermic peak in the temperature lowering stage was defined as the crystallization temperature Tc. In addition, the peak top temperature of the main endothermic peak in the final temperature increase stage performed to obtain the melting curve was defined as the melting point Tm.
(Siloxane copolymer material)

  In the siloxane copolymer, the unit structure (I) / {unit structure (I) + unit structure (II)} was calculated from the unit structure (I) (units) and the unit structure (II) (units). In the table.

(Water contact angle measurement)
The polymer was pressed at 190 ° C. and 100 kgf using a 12 cm × 12 cm × 300 μm spacer to process a film having a thickness of 300 μm. The water contact angle of the obtained film was measured in a temperature-controlled room with a temperature of 23 ° C. and a humidity of 50% using a dynamic contact angle / surface tension measuring device FTA125 manufactured by First Ten Angstroms. did. Pure water was used as water. As the volume of the water droplets to be dropped, those in the range of 3.5 to 4.0 μL were used. The measurement of each sample was repeated 5 times or more, and the average value was taken as the contact angle.

(Adhesion test)
A film processed to a thickness of 300 μm was used as a substrate. The sheet having a thickness of 300 μm was prepared by pressing the polymer at 190 ° C. and 100 kgf using a spacer of 12 cm × 12 cm × 300 μm. The cellophane tape used was a commercially available transparent beauty color manufactured by 3M. First, the cellophane tape cut | disconnected to length 5cm was affixed on the base material, and it left still for 1 minute. Thereafter, the substrate was fixed by hand, one end of the cellophane tape was grasped and lifted, and the strength of the adhesion was evaluated with three qualitative indicators.
Adhesive index: 1 (adhesive), 2 (weakly adhesive), 3 (non-adhesive)

(Production Example 1)
[Method for producing rac-dimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-isopropylphenyl) indenyl] hafnium dichloride (complex Mx)]
A complex Mx having the following structure was synthesized according to the method described in Example 11 of Japanese Patent Application Laid-Open No. 2009-299045.

(Production Example 2)
[Production Method of Polypropylene (Mn10,600)]
Purified hexane (10,000 mL) and a toluene solution of modified methylaluminoxane (Tosoh Finechem “MMAO-3A” 2.1 mmol [Inductive stirring autoclave with internal volume of 24 L substituted with purified nitrogen] 60 mL of Al equivalent atoms]) was introduced. The reaction vessel was heated to 85 ° C., propylene was introduced to 0.80 MPa, and the toluene solution of the complex Mx (43.7 μmol) obtained in Production Example 1 was pumped into the reaction vessel to start the polymerization reaction. During the reaction, propylene was added to keep the reactor pressure at 0.80 MPa. After 80 minutes, ethanol was introduced to stop the reaction. The obtained polymer was collected by filtration and dried under reduced pressure until a constant amount was obtained, to obtain 2211 g of polymer. The number average molecular weight ([Mn (GPC)]) of the obtained macromonomer was 10,600, and the isotactic pentad fraction (mmmm) measured by 13C-NMR was 0.91. The melting point (Tm) measured by DSC was 138.0 ° C. The physical property values of the obtained isotactic polypropylene macromonomer are shown in Table 1.

(Production Example 3)
[Production Method of Polypropylene (Mn8,900)]
Into a 5 L separable flask equipped with a stirring blade and a reflux apparatus, 1,698 g of pure water was added, and 501 g of 98% sulfuric acid was added dropwise. Further, 300 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 19.5 μm) was added and stirred. Thereafter, the mixture was reacted at 90 ° C. for 2 hours. This slurry was washed with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. A 900 mL aqueous solution of 324 g of lithium sulfate monohydrate was added to the recovered cake and reacted at 90 ° C. for 2 hours. This slurry was washed to pH> 4 with an apparatus in which an aspirator was connected to Nutsche and a suction bottle. The collected cake was dried at 120 ° C. overnight. As a result, 275 g of chemically treated montmorillonite was obtained.

  500 mg of the chemically treated montmorillonite obtained above was weighed into a flask with an internal volume of 50 mL. Under purified nitrogen, 2.0 mL of a toluene solution (0.5 mmol / mL) of triisobutylethylaluminum (TIBA) manufactured by Nippon Alkyl Aluminum Co., Ltd. (corresponding to 2 mmol of TIBA per 1 g of montmorillonite) was added and reacted at room temperature for 30 minutes. After that, the supernatant was extracted. To this, 20 mL of toluene was added and stirred for 10 minutes, and the work of extracting the supernatant was further carried out twice.

A mixed toluene solution containing triisobutylaluminum (30 μmol / mL) and the complex Mx (3.0 μmol / mL) synthesized in Production Example 12 was added to the washed montmorillonite so that the complex Mx was 30 μmol with respect to 1 g of montmorillonite. Stir at room temperature for 1 hour.
1,000 mL of purified hexane and 1 mL of a toluene solution of triisobutylaluminum (0.5 mol / L) were introduced into a 2 L induction-stirring autoclave (AC) that had been replaced with purified nitrogen and contained a stirring blade. The temperature of AC was raised to 85 ° C. and propylene was introduced, and the introduction was continued until the pressure in the AC was stabilized at 0.8 MPa. Thereafter, 200 mg of the catalyst slurry was injected, and the AC internal temperature was raised to 90 ° C. to initiate polymerization. During polymerization, the AC internal temperature was maintained at 90 ° C., and the introduction of propylene was continued so that the pressure was maintained at 0.8 MPa. After 30 minutes, propylene inside the AC was purged to complete the polymerization. When the polymer yield was weighed, 288 g of polypropylene was obtained.
The number average molecular weight measured by GPC was 8,900 g / mol. The Tm measured by DSC was 145.2 ° C.

(Production Example 4)
[Production Method of Polypropylene (Mn 6,300)]
In Production Example 2, the same procedure as in Production Example 3 was carried out except that the AC internal temperature during polymerization was 95 ° C., to obtain 219 g of polypropylene.
The number average molecular weight measured by GPC was 6,300 g / mol. The Tm measured by DSC was 140.0 ° C.

[Example 1]
In a 300 mL four-necked flask equipped with a mechanical stirrer, polypropylene (Mn 10,600, 10.6 g, 1.0 mmol), silicone XL-110 (Mn1,047, 1.0 g, 1.0 mmol) and cyclohexane produced in Production Example 2 were used. 100 mL was added and nitrogen bubbled for 15 minutes. Then, after heating up to 80 degreeC and stirring uniformly, platinum catalyst SIP6832.2 (2 wt% platinum containing, 0.003 mL) was supplied, and it stirred at 80 degreeC for 5 hours. Thereafter, the reaction solution was cooled to 40 ° C. with stirring, and ethanol (100 mL) was added until the polymer precipitated. The precipitated polymer was collected by filtration and washed with acetone (100 mL × 3). The obtained polymer was dried under reduced pressure at 70 ° C. (yield 11.0 g).
As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. Further, GPC measurement confirmed that the molecular weight was increased, and it was revealed that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

[Example 2]
A polymer was produced in the same manner as in Example 1 except that the silicone XL-110 was changed to silicone XL-115 (Mn 3,229, 1.8 g, 0.6 mmol) (yield 12.4 g).
As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. Further, GPC measurement confirmed that the molecular weight was increased, and it was revealed that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

[Example 3]
The same as Example 1 except that the polypropylene was changed to the polypropylene (Mn8,900) produced in Production Example 3 and the silicone XL-110 was changed to silicone XL-116 (Mn6,610, 7.5 g, 1.1 mmol). To produce a polymer (yield 13.9 g).
As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. Further, GPC measurement confirmed that the molecular weight was increased, and it was revealed that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

[Example 4]
In a 1,000 mL four-necked flask equipped with a mechanical stirrer, the polypropylene produced in Production Example 2 (Mn 10,600, 126.0 g, 11.9 mmol) and silicone XL-116 (Mn 6,610, 89.25 g, 13.5 mmol) And 700 mL of cyclohexane were added, and nitrogen was bubbled for 15 minutes. Then, after heating up to 80 degreeC and stirring uniformly, platinum catalyst SIP6832.2 (2 wt% platinum content, 0.07 mL) was supplied, and it stirred at 80 degreeC for 5 hours. Thereafter, the reaction solution was cooled to 40 ° C. with stirring, and ethanol (300 mL) was added until the polymer precipitated. The precipitated polymer was collected by filtration and washed with acetone (500 mL × 3). The obtained polymer was dried under reduced pressure at 70 ° C. (yield 191.5 g).
As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. Further, GPC measurement confirmed that the molecular weight was increased, and it was revealed that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

[Comparative Example 1]
A polymer was produced in the same manner as in Example 1 except that the silicone XL-110 was changed to silicone HMS-991 (Mn 1,800, 1.0 g, 0.6 mmol) (yield 10.8 g).
As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. Further, GPC measurement confirmed that the molecular weight was increased, and it was revealed that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

[Comparative Example 2]
A polymer was produced in the same manner as in Example 1 except that the silicone XL-110 was changed to silicone HMS-991 (Mn 1,800, 3.0 g, 1.7 mmol) (yield 11.6 g).
As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. Further, GPC measurement confirmed that the molecular weight was increased, and it was revealed that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

[Comparative Example 3]
The same as Example 1 except that the polypropylene was changed to the polypropylene (Mn 6,300) produced in Production Example 5 and the silicone XL-110 was changed to the silicone XL-116 (Mn 6,610, 7.5 g, 1.1 mmol). To produce a polymer (yield 11.0 g).
As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. Further, GPC measurement confirmed that the molecular weight was increased, and it was revealed that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

  About the polymer manufactured in Examples 1-4 and Comparative Examples 1-3, the water contact angle measurement and the adhesiveness test were done. The results are shown in Table 4.

The following raw materials were used for evaluation of the resin composition in the present invention.
<(A) Silylated polypropylene>
(A) -1: Silylated polypropylene obtained in Example 4 <(B) thermoplastic resin>
(B) -1: Polypropylene (manufactured by Nippon Polypro, product name Novatec FW4B: propylene / ethylene / butene copolymer, MFR (230 ° C., load 2.16 kg) 7 g / 10 min, density 0.90 g / cm 3, ethylene (Content 1.5% by weight, butene content 2.3% by weight)

<Example 5>
(A) -1: 1 part of silylated polypropylene and 100 parts of (B) -1: polypropylene were dry blended, and the resin temperature was 220 ° C. using an extruder having a diameter of 15 mmφ (“KZW15” manufactured by Technobel Co., Ltd.). It was melt-extruded into a film having a width of 100 mm from the die to obtain a single layer film having a layer thickness of 30 μm.

<Example 6>
(A) -1: 5 parts of silylated polypropylene and (B) -1: 100 parts of polypropylene were dry blended and T was used at a resin temperature of 220 ° C. using an extruder having a diameter of 15 mmφ (“KZW15” manufactured by Technobel Co., Ltd.). It was melt-extruded into a film having a width of 100 mm from the die to obtain a single layer film having a layer thickness of 30 μm.

<Comparative Example 4>
The same operation as in Example 6 was performed except that silylated polypropylene was not added, and melt-extruded into a film having a width of 100 mm to obtain a single-layer film having a layer thickness of 30 μm.

<Comparative Example 5>
A film having a width of 100 mm was prepared in the same manner as in Example 6 except that 5 parts of fatty acid bisamide mainly composed of behenic acid bisamide used in Example 1 of Japanese Patent No. 6047964 was used instead of silylated polypropylene. A single layer film having a layer thickness of 30 μm was obtained.

<Heat seal strength against polypropylene>
The films obtained in Examples 5 to 6 or Comparative Examples 4 to 5 were cut into a width of 15 mm and overlapped with a sheet having a thickness of 0.3 mm consisting only of (B) -1 obtained in Comparative Example 4. Under the conditions that the pressure was changed to 0.2 MPa, the time was 1.0 second, and the sealing temperature was changed from 140 ° C. to 180 ° C. every 20 ° C., they were respectively pressed by a heat seal bar to perform heat bonding. Using the tensile tester (manufactured by A & D Co., Ltd., Tensilon Universal Tester (RTG1225)), the peel strength of the heat-bonded portion of the test piece was measured at a peel rate of 300 mm / min and 180 ° peel. It was measured. The results are shown in Table 5.

<Measurement of water contact angle of composition>
The water contact angles of the films obtained in Examples 5 to 6 and Comparative Examples 4 to 5 were fixed on a glass substrate, and the room temperature was 23 ° C. using Kyowa Interface Science Co., Ltd. (Dropmaster DN300). , And measured in a constant temperature room with a humidity of 50%. Pure water was used as water. As the volume of the water droplets to be dropped, those in the range of 3.5 to 4.0 μL were used. The measurement of each sample was repeated 5 times or more, and the average value was taken as the contact angle. The results are shown in Table 5.
Moreover, about the film obtained in Example 6 and Comparative Examples 4-5, as an ethanol washing | cleaning operation, after rubbing the film surface 3 times with the Kim wipe soaked with ethanol, water contact angle was set by the same operation as the above. It was measured. The results are shown in Table 5.

<Measurement of oil contact angle of composition>
The oil contact angles of the films obtained in Examples 5 to 6 and Comparative Examples 4 to 5 were fixed on a glass substrate, and the room temperature was 23 ° C. using Kyowa Interface Science Co., Ltd. (Dropmaster DN300). , And measured in a constant temperature room with a humidity of 50%. Olive oil was used as the oil. As the volume of oil droplets to be dropped, those having a range of 3.5 to 4.0 μL were used. The measurement of each sample was repeated 5 times or more, and the average value was taken as the contact angle. The results are shown in Table 5.

The following raw materials were used for evaluating the peel strength of the composition containing silylated polypropylene obtained in the present invention.
Adhesive film: Acrylic adhesive tape cut to a width of 15 mm (Nitto Denko Corporation, No. 31B)

<Releasability evaluation: peel strength>
The films obtained in Examples 5 to 6 or Comparative Examples 4 to 5 were cut to a width of 15 mm and overlapped with the adhesive surface of an adhesive film (manufactured by Nitto Denko Corporation, product name: NO.31B thickness 0.025 mm). In addition, a 2 kg rubber roller was reciprocated once on the adherend from the top to adhere the film. Using the tensile tester (manufactured by A & D Co., Ltd., Tensilon Universal Tester (RTG1225)), the peel strength was measured at 180 ° peel with a peel rate of 300 mm / min. did. The results are shown in Table 5.

  From the result of Table 4, the Example of this invention had a large contact angle with water with respect to the comparative example, and showed the improvement of peelability. A high contact angle indicates a high affinity with polyolefins such as polypropylene. From the results of Table 5, it was shown that the contact angle with water / oil also increased in the polypropylene resin composition of silylated polypropylene. From the results of Example 5 and Comparative Example 4, it was confirmed that the composition had no influence on the heat seal strength. From the results of Example 5 and Example 6, it was shown that the contact angle of oil increased with the addition amount of the silylated polypropylene of the present invention. In addition, from the results of Example 6 and Comparative Example 5, it was found that the surface of the surface of the composition of the present invention was maintained before and after the cleaning without any significant decrease in the contact angle with water after the surface was washed with ethanol. Indicated.

Claims (14)

(A) a terminal unsaturated bond ratio> 90%, a number average molecular weight of 8,000 or more, polypropylene having a single terminal unsaturated bond, and (b) a siloxane copolymer having the following structural unit (I) and structural unit (II) A process for producing silylated polypropylene, characterized in that

(In the formula, R _{1 to} R ₃ each independently represents a hydrocarbon group having 1 to 10 carbon atoms.)   The method for producing silylated polypropylene according to claim 1, wherein (a) is an isotactic polypropylene having a mesotriad fraction> 94 mol% and Tm> 130 ° C.   The method for producing a silylated polypropylene according to any one of claims 1 and 2, wherein in (a), the unsaturated bond at one end is a vinyl group. In the said (b), R < ₁ > -R < ₃ > is a methyl group, The manufacturing method of the silylated polypropylene of any one of Claims 1-3 characterized by the above-mentioned.   In the said (a), the number average molecular weights of a polypropylene are 8,000-70,000, The manufacturing method of the silylated polypropylene of any one of Claims 1-4 characterized by the above-mentioned.   In said (b), ratio of structural unit (I) / {structural unit (I) + structural unit (II)} is 0.8 or less, The any one of Claims 1-5 characterized by the above-mentioned. The manufacturing method of the silylated polypropylene as described in 1 above.   The method for producing silylated polypropylene according to any one of claims 1 to 6, wherein the (a) and the (b) are reacted in the presence of a platinum catalyst. The silylation according to any one of claims 1 to 7, wherein (a) is produced by using a transition metal compound represented by the following general formula (3) as a catalyst. A method for producing polypropylene.

(Wherein, R ¹⁵ and R ¹⁶ each independently represent a heterocyclic group having 4 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur, and R ¹⁷ and R ¹⁸ are each independently, In the range of 6 to 16 carbon atoms, on the aryl cyclic skeleton, one or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, halogens having 1 to 6 carbon atoms A hydrocarbon group, an aryl group having a halogen atom as a substituent, or a heterocyclic group containing 6 to 16 carbon atoms containing nitrogen, oxygen, or sulfur, X ¹² and Y ¹² are each independently Hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, silicon-containing hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing hydrocarbon having 1 to 20 carbon atoms Group, amino group, or carbon number 1 Represents a nitrogen-containing hydrocarbon group having 20, Q ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms, a hydrocarbon group silylene group have or germylene groups, having 1 to 20 carbon atoms Represents.)   The silylated polypropylene manufactured with the manufacturing method of any one of Claims 1-8. The silylated polypropylene according to claim 9, which has the following structural unit (III) and structural unit (IV).

(Wherein R ₄ is an isotactic polypropylene chain having a mesotriad fraction> 94 mol%, Tm> 130 ° C., and a number average molecular weight of 8,000 or more. R ₅ has 1 to 10 carbon atoms. Represents a hydrocarbon group.)

(In formula, R < ₆ >, R < ₇ > represents a C1-C10 hydrocarbon group each independently.) The silylated polypropylene according to claim 10, wherein R _{5 to} R ₇ are methyl groups. (A) A resin composition comprising the silylated polypropylene according to any one of claims 9 to 11 and (B) a thermoplastic resin.   The resin composition according to claim 12, wherein the (B) thermoplastic resin is a polyolefin resin.   The resin composition according to claim 12 or 13, wherein the resin composition contains 0.01 to 10,000 parts by weight of the silylated polypropylene of (A) with respect to 100 parts by weight of the thermoplastic resin (B). .