JP6794871B2 - A method for producing silylated polypropylene, a silylated polypropylene obtained from the method, and a resin composition containing the silylated polypropylene and a thermoplastic resin. - Google Patents

Description

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

Polyolefins such as polyethylene and polypropylene are widely used in daily life parts and industrial parts because they have excellent mechanical strength, workability, chemical resistance, electrical properties, light weight, and low cost. ing.
Properties that are expected to be improved with respect to polyolefins include surface properties such as water repellency, oil repellency, stain resistance, and non-adhesiveness. These performances are expected to be particularly improved in the fields of living industry materials such as toiletries and foods, and in the field of medical sanitary materials that require antifouling properties.

On the other hand, the polyolefin material is also desired to have improved gas permeability. For example, in the field of packaging materials for fruits and vegetables, polypropylene films with excellent transparency and good appearance are often used, but it is known that they have an adverse effect on maintaining the freshness of agricultural products due to their low gas permeability. , A polypropylene material having both good transparency and good gas permeability is desired.

Further, in applications of oxygen-enriched membranes for industrial use and medical use, silicone resin is conventionally known as a material having excellent oxygen permeability and separation ratio, but silicone resin is inferior in mechanical strength. In order to solve this problem, a composite film in which a non-porous ultra-thin layer portion having high gas permeability such as silicone and a porous portion of polypropylene that mechanically supports the ultra-thin layer portion are laminated has also been developed. However, these composite films tend to be expensive and have not been put into practical use very much. Therefore, it is desired to develop a material having excellent mechanical strength and cost, which can be independently molded by adding a material having excellent mechanical strength (for example, polypropylene).
By adding various modifiers to polyolefin, mechanical properties and surface properties, which are insufficient by themselves, may be improved. However, when the affinity between the material to be modified and the additive is low, not only the modification effect is limited, but also there is a concern that other properties such as transparency and mechanical properties may be deteriorated.

For example, as a method for improving surface properties such as water repellency, oil repellency, stain resistance, non-adhesiveness, and gas permeability of polyolefin, a method of adding a high molecular weight silicone to polyolefin, molding and processing is known. Although it is already on the market, 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. Further, since the added silicone easily floats on the surface of the material due to its low affinity, its gas permeability is easily lost. Further, since silicone is easily removed from the surface by physical contact with the surface, its surface modification property is easily lost, and it is difficult to maintain the surface modification performance for a long time. In particular, since silicone adheres to and migrates to substances that come into contact with it, it is contraindicated for use in electronic materials that may contaminate printed wiring boards, especially copper circuits.

In order to improve these problems, it is known to use a block copolymer of polyolefin and silicone as an additive. As an example of producing such a block copolymer, for example, application of hydrosilylation of hydrosilicone to an unsaturated bond at the end of a polyolefin is known. Patent Document 1 discloses a method for producing a branched copolymer of polypropylene and polysilane by a procedure including hydrosilylation of a molten layer. However, this method is specifically a method of silylated the terminal unsaturated group of the unsaturated polymer produced by radical decomposition in the process of the reaction, and its reaction controllability is low, and it is suitable for producing a block polymer having a specific structure. Is not suitable. In addition, 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 a hydrogen silicone, but the surface modification performance and gas permeability of the obtained block copolymer are completely different. There is no description.
Further, Patent Document 3 discloses a molded product formed from a composition containing a vinyl group-containing compound, particularly a silylated polyolefin obtained by reacting a low molecular weight polyethylene having a vinyl group at the terminal with a silicon compound. , It has been shown that addition to polypropylene improves wear resistance and gas permeability. However, the improvement effect is insufficient, and the transparency is particularly deteriorated, so that it is difficult to use it as an additive for polypropylene modification.

Patent Document 4 discloses a block copolymer containing at least one organosiloxane block and at least one polyolefin block, but the present disclosure technique focuses on controlling the molecular weight to the extent that solution coating is possible. In fact, a specific example of the surface modification effect of coating on a polyurethane film is disclosed. However, there is no description about the surface modification performance of polypropylene, and special substituents and low-reactive substituents are used for its production, so it cannot be said to be an efficient production method, and it is actually as expected. It is not described that the block polymer having the above structure is selectively obtained.

Patent Document 5 discloses a reaction product of a macromonomer having a vinyl group at the terminal and a polyalkylhydrosiloxane, but in the present disclosure technique, particular attention is paid to a siloxane having many reaction points, and very branching develops. Only techniques for the rheological properties of the polymer have been disclosed. However, there is no description about the surface modification performance and gas permeability of the obtained block copolymer, and it has been clarified that the material in the technique has a low surface modification performance.

Special Table 2002-522604 Japanese Unexamined Patent Publication No. 2004-196883 WO2012 / 098865 Special Table 2015-536376 Gazette WO2014 / 047482

The present invention has been made in view of such circumstances, and a silylated polypropylene having a high affinity with an industrially important polypropylene material as compared with a conventional material and an excellent surface modification effect is low. An object of the present invention is to provide a method for producing a block structure with high selectivity at a low cost and with high selectivity, a silylated polypropylene obtained from the manufacturing 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-mentioned problems can be achieved by adding a polysiloxane having a specific structure to polypropylene having a specific one-ended unsaturated bond.
That is, the gist of the present invention is as follows.
[1] (a) Polypropylene having a single-ended unsaturated bond with a terminal unsaturated bond rate> 90% and a number average molecular weight of 8,000 or more, and (b) the following structural units (I) and structural unit (II). A method for producing a silylated polypropylene, which comprises reacting with a siloxane copolymer having a siloxane.

(In the formula, R _{1 to} R ₃ each independently represent a hydrocarbon group having 1 to 10 carbon atoms.)
[2] The method for producing a silylated polypropylene according to [1], wherein the (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 the unsaturated bond at one end is a vinyl group in the above (a).
[4] The method for producing a silylated polypropylene according to any one of [1] to [3], wherein R _{1 to} R ₃ are methyl groups in the above (b).
[5] The method for producing a silylated polypropylene according to any one of [1] to [4], wherein the number average molecular weight of polypropylene in (a) is 8,000 to 70,000.
[6] In the above (b), the ratio of the 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.
[7] The method for producing a silylated polypropylene according to any one of [1] to [6], which comprises reacting the above (a) with the above (b) in the presence of a platinum catalyst.
[8] Described in any one of [1] to [7], wherein the above (a) is produced by using a transition metal compound represented by the following general formula (3) as a catalyst. Method for producing silylated polypropylene.

(In the formula, R ¹⁵ and R ¹⁶ each independently represent a nitrogen, oxygen, or sulfur-containing heterocyclic group having 4 to 16 carbon atoms, and R ¹⁷ and R ¹⁸ independently represent, respectively. One or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, and halogens having 1 to 6 carbon atoms on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. Represents a hydrocarbon group, an aryl group having a halogen atom as a substituent, or a heterocyclic group having 6 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur, and X ¹² and Y ¹² are independent of each other. 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 group having 1 to 20 carbon atoms. group, an amino group or a nitrogen-containing hydrocarbon group having a carbon number of 1 to 20,, Q ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms, have a hydrocarbon group having 1 to 20 carbon atoms It represents a silylene group or a gelmilene group which may be used.)
[9] Cyrilized 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).

(In the formula, 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 the formula, R ₆ and R ₇ each independently represent a hydrocarbon group having 1 to 10 carbon atoms.)
[11] The silylated polypropylene according to [10], wherein R _{5 to} R ₇ are methyl groups.
[12] A resin composition containing 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], the silylated polypropylene of (A) is contained in an amount of 0.01 to 10,000 parts by weight with respect to 100 parts by weight of the thermoplastic resin (B). The resin composition described.

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

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

[polypropylene]
(A) Polypropylene having a one-ended unsaturated bond with a terminal unsaturated bond rate> 90% and a number average molecular weight of 8,000 or more In the present invention, polypropylene having a one-ended unsaturated bond (hereinafter, "one-ended unsaturated polypropylene") ”) Has an unsaturated bond at at least one end of the polypropylene structure and does not have an unsaturated bond at least one end. In the case of linear polypropylene, only one of the two ends has an unsaturated bond. In the case of branched polypropylene, at least one of the three or more ends has an unsaturated bond, and at least one end does not have an unsaturated bond.

Examples of the one-terminal unsaturated bond include a vinylidene group, a vinylene group, and a vinyl group, but a vinylidene group and a vinyl group are preferable, and a vinyl group is more preferable.
The 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 the general formula (1), R ₁ is preferably a hydrogen atom from the viewpoint of efficiency and selectivity of the modification reaction.

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

<What is obtained from 13C-NMR measurement>
Number of isobutyl terminals / 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 Sαα is H.I. N. According to the notation of "Macromopolymers 1984, 17, 1950" by Cheng.

Number of n-propyl terminals / 1,000 propylene monomers = 1000 * (average of integrated values of signals of 14.47, 30.48, 39.64 ppm) / integrated value of Sαα n-butyl terminals / 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, 42.99 ppm signal integrated value average) / Sαα integrated value Long chain branch number / 1,000 propylene monomers = 1000 * (31.60, 44.00, Integral value of 44.69ppm signal) / Integral value of Sαα

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

The endless bond ratio of the one-ended 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 rate, the higher the yield of the silylated polypropylene, and it is possible to produce the silylated polypropylene having a block structure at low cost, energy efficiency, and with high selectivity.
Further, the one-ended unsaturated polypropylene may be a branched one-ended unsaturated polypropylene having a polypropylene side chain as long as it does not impair rigidity and heat resistance.

(Number average molecular weight of one-ended 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 produced silylated polypropylene and the composition containing the same. It is preferably 9,000 or more, more preferably 10,000 or more. The number average molecular weight thereof is usually 200,000 or less, preferably 150,000 or less, more preferably 100,000 or less, and more preferably 70,000 or less. When it is less 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 based on the molecular weight from the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the produced silylated polypropylene and the composition containing the same, solvent resistance and reduction of bleed-out. Narrower 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 Mw / Mn, and is usually 10 or less, preferably 5 or less, and particularly preferably 3 or less.

(Tacticity of unsaturated polypropylene at one end)
The one-terminal unsaturated polypropylene preferably has a structure with high stereoregularity. "Triad fraction" is used as a factor indicating the high degree of stereoregularity of polypropylene. The triad indicates the continuity of the relative arrangement of adjacent side chain methyl groups in polypropylene, and the higher this value, the higher the stereoregularity. The mesotriad (mm) fraction is the ratio of the propylene unit at the center of the chain in which three propylene monomer units consisting of head-tail bonds are continuously mesobonded to the total propylene unit in the polymer chain. It is represented by. The triad can usually be determined by the signal of the methyl group in 13C-NMR. The attribution of the peak is, for example, A. It can be determined according to the peak attribution 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 central propylene of the three-chain head-to-tail bond centered on the propylene unit occur in three regions depending on its configuration.
mm: Approximately 24.3 to approximately 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 shifts slightly depending on the molecular weight and the copolymer composition, but the above three regions can be easily identified.
Here, mm, mr, and rr are each represented by the following structures.

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

(Melting point (Tm) of unsaturated polypropylene at one end)
The melting point (Tm) of the terminally unsaturated polypropylene used in the present invention is not particularly limited, but from the viewpoint of mechanical properties such as heat resistance and viscoelasticity of the produced silylated polypropylene and the composition containing the same. Therefore, the higher the temperature, the higher the temperature, 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 terminally unsaturated polypropylene is measured by a differential scanning calorimetry (DSC).
The 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 the silylated polypropylene produced and the composition containing the same may be contained. From the viewpoint of mechanical properties such as heat resistance and viscoelasticity, a polypropylene homopolymer is preferably used.

(Manufacturing method of one-ended 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 the terminal unsaturated polypropylene can be appropriately used. In the prior art, there is also known a technique of introducing an unsaturated bond into one end or both ends of a polypropylene molecule by breaking a molecular chain by thermal decomposition or radical decomposition, but the terminal unsaturated of polypropylene used in the present invention is also known. The bond is preferably introduced into the terminal of the propylene-based polymer without using a pyrolysis method for reasons such as ease of controlling the molecular weight and improvement of the purity of the terminal olefin. More specifically, a method produced by coordinate polymerization of propylene using a transition metal compound and having a vinyl group at a high proportion of the polymerization-terminated ends is preferable from an economical point of view.

For example, a method of introducing a vinyl group at the terminal by utilizing the fact that β-methyl group elimination reaction occurs frequently by polymerizing propylene at high temperature using a stereorigid C2 symmetrical crosslinked metallocene catalyst (for example, Special Table 2001-). 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 determined. A method for producing while maintaining high stereoregularity by increasing (for example, JP-A-11-349634, JP-A-2009-299045, etc.), desorption of vinyl chloride, etc. in propylene using an isotactic structure-selective metallocene catalyst. A method of copolymerizing a vinyl comonomer having an easy functional group and causing β-functional elimination at the same time when this comonomer is inserted to selectively produce a macromonomer having a terminal vinyl group (Gaynor, SG Macromethylules 2003, 36). , 4692-4689) and a propylene polymerization catalyst in which 2,1-insertion of propylene is prioritized (for example, a late-periodic transition metal complex such as the pyridyldiimine iron (II) complex), which is relatively difficult β Examples thereof include a method of introducing a terminal vinyl group through β-hydrogen elimination without going through a-methyl group elimination process (Brookhard, M. et. Al. Macromethylules 1999, 32, 2120).

Among these, a method for producing while maintaining high stereoregularity by increasing the frequency of β-methyl elimination reaction at a relatively low temperature by using a complex having a heterocyclic group at a specific site (for example, JP-A-2009-). (299045) is preferable from the viewpoint of achieving both high stereoregularity and high vinyl selectivity, and a method of producing using a transition metal compound represented by the following general formula (2) is more preferable.

In the general formula (2), R ¹¹ and R ¹² each independently represent a nitrogen, oxygen, or sulfur-containing heterocyclic group having 4 to 16 carbon atoms. In addition, R ¹³ and R ¹⁴ may each independently contain at least one hetero atom selected from halogen, silicon, oxygen, sulfur, nitrogen, boron, and phosphorus having 6 to 16 carbon atoms. Represents an aryl group or a heterocyclic group containing 6 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur. Further, X ¹¹ and Y ¹¹ independently have 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, and a halogenation having 1 to 20 carbon atoms. hydrocarbon group, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group or a nitrogen-containing hydrocarbon group having a carbon number of 1 to 20,, Q ¹¹ is a divalent hydrocarbon group having 1 to 20 carbon atoms Represents a silylene group or a gelmilene group which may have a hydrocarbon group having 1 to 20 carbon atoms.

The nitrogen, oxygen, or sulfur-containing heterocyclic groups having 4 to 16 carbon atoms of R ¹¹ and R ¹² are preferably 2-furyl groups, substituted 2-furyl groups, and substituted 2-thienyl groups. , Or a substituted 2-furfuryl group, more preferably a substituted 2-furfuryl group.
By introducing a substituent of an appropriate size on the heterocyclic group, the coordination field on the heterocycle and the transition metal, and the relative positional relationship between the growing polymer chain can be made appropriate, and vinyl at the end can be made appropriate. It is possible to obtain a terminal unsaturated polypropylene in which a group is highly selectively introduced.

Further, as the substituent of the substituted 2-furyl group, the substituted 2-thienyl group and the substituted 2-furfuryl group, an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group can be used. , Halogen atoms such as fluorine atom and chlorine atom, alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, trialkylsilyl group and the like. Of these, a methyl group and a trimethylsilyl group are preferable, and a methyl group is particularly preferable.

In addition, R ¹¹ and R ¹² are particularly preferably 2- (5-methyl) -frill groups. Further, it is preferable that R ¹¹ and R ¹² are the same as each other.
The R ¹³ and R ¹⁴ are an aryl group 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 6 carbon atoms. ~ 16 heterocyclic groups containing nitrogen, oxygen, or sulfur, but in particular, by making R ¹³ and R ¹⁴ bulkier, terminal unsaturatedity with higher stereoregularity and less heterogeneous bonds is achieved. Polypropylene can be obtained.

Therefore, R ¹³ and R ¹⁴ have 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. A group, a halogen-containing hydrocarbon group having 1 to 6 carbon atoms, and an aryl group having a halogen atom as a substituent are preferable, and specific examples of such R ¹³ and R ¹⁴ are 4-isopropylphenyl group and 4-t-. It is 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.

Further, 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, and a phenyl group having a halogen atom as a substituent. Furthermore, the position to be substituted 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 as each other.

In the general formula (2), X ¹¹ and Y ¹¹ are co-ligands. Therefore, as long as this purpose is achieved, the types of X ¹¹ and Y ¹¹ are not limited, and each of them independently has a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, and 1 to 20 carbon atoms. Represents 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 the general formula (2), Q ¹¹ couples the two five-membered ring, a divalent hydrocarbon group having 1 to 20 carbon atoms, which may have a hydrocarbon group having 1 to 20 carbon atoms silylene Indicates either a group or a gelmilene group. When two hydrocarbon groups are present on the silylene group or the gelmilene group described above, 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 Alkyl silylene group such as, (alkyl) (aryl) silylene group such as methyl (phenyl) silylene; aryl silylene group such as diphenyl silylene; alkyloligosilylene group such as tetramethyldicyrylene; gelmilene group; the above divalent carbon Examples thereof include an alkyl gelmilene group in which silicon of a silylene group having a hydrocarbon group of several 1 to 20 is replaced with germanium; an (alkyl) (aryl) gelmillene group; and an aryl gelmilene group. Among these, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms or a gelmilene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group and an alkyl gelmilene group are particularly preferable.

The transition metal compound represented by the general formula (2) is usually used in combination with a cocatalyst described later. Organoaluminium oxy compounds, ionic compounds capable of reacting with catalyst precursors and converting them into cations, Lewis acids, ion-exchange layered silicates and the like are preferably used as cocatalysts and are particularly preferably organic. Organoaluminium compounds and ion exchange layered silicates are used. Further, 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 aromatic hydrocarbon-based organic solvents such as toluene. It is preferable from the viewpoint of handling in purification of transition metal compounds and preparation of catalysts.

(In the formula, R ¹⁵ and R ¹⁶ each independently represent a nitrogen, oxygen, or sulfur-containing heterocyclic group having 4 to 16 carbon atoms, and R ¹⁷ and R ¹⁸ independently represent, respectively. One or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, and halogens having 1 to 6 carbon atoms on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. Represents a hydrocarbon group, an aryl group having a halogen atom as a substituent, or a heterocyclic group having 6 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur, and X ¹² and Y ¹² are independent of each other. 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 group having 1 to 20 carbon atoms. group, an amino group or a nitrogen-containing hydrocarbon group having a carbon number of 1 to 20,, Q ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms, have a hydrocarbon group having 1 to 20 carbon atoms It represents a silylene group or a gelmilene group which may be used.)

The method for producing the terminal unsaturated polypropylene used in the present invention is not limited, but as described above, it is preferably produced by coordination polymerization of propylene from an economical point of view. The polymerization conditions are not particularly limited as long as the desired product can be obtained, and solution polymerization, slurry polymerization, liquid phase no solvent polymerization (bulk polymerization) that does not use substantially a solvent, vapor phase polymerization, melt polymerization, etc. can be used. Yes, continuous polymerization, batch polymerization, and so-called multi-stage polymerization may be adopted.

The polymerization temperature, the polymerization pressure and the polymerization time are not particularly limited, but usually, they 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 in the range of 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, still more preferably 5 MPa or less. This is because, when produced by this method, the terminal of the terminal unsaturated polypropylene molecule usually has an alkyl group at the start end of the polymerization reaction and a vinyl group at the end end of the polymerization reaction. In this case, the possibility that both ends of the macromonomer molecule will be vinyl groups is usually extremely low.

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

(In the formula, R _{1 to} R ₃ each independently represent 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 above unit structures (I) and (II). The unit structure (I) is a unit structure required for the reaction with the terminal unsaturated polypropylene described above. The unit structure (II) is a unit structure necessary for exhibiting surface properties such as water repellency, oil repellency, antifouling property, and adhesiveness expected by silylation, and properties having excellent 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 large. If the number of structural units (I) is too large, side reactions often occur 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, the unit structure (II) is preferably larger 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 each structural unit (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 of siloxane copolymer Mn (g / mol) = molecular weight of both terminal sites + unit structure (I) (pieces) x molecular weight of unit structure (I) + unit structure (II) (pieces) x 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) (pieces), the number average molecular weight Mn of the siloxane copolymer, the molecular weights of both terminal sites, the molecular weight of the unit structure (I), and the molecular weight of the unit structure (II) are required. Here, a case where the substituents R _{1 to} R _{3 at} both terminal sites are all methyl groups will be briefly described. The molecular weights of both terminal sites, the unit structure (I), and the unit structure (II) can be expressed as the molecular weights of the 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, and Mn [c] = 74.15.

On the other hand, for the number average molecular weight Mn of the siloxane copolymers, the kinematic viscosity (cSt) η of each siloxane copolymer at 25 ° C. was used, and Barry's formula logη = 1.00 + 0.0123 × Mn ^0.5 (J. Appl. Physics). , 1946, 17, 1020) can be used for calculation. Here, η is the kinematic viscosity (cSt) at 25 ° C., and Mn is the number average molecular weight.

By substituting this Mn and the molecular weights of the unit structure (I) (pieces), both end sites, the unit structure (I), and the unit structure (II) into the formula (3), the unit structure (II) (pieces) can be obtained. Can be calculated.
The number of structural units (I) and (II) can also be calculated from the amount of structural units (I) and (II) charged.

In the above (b), the ratio of the structural unit (I) / {structural unit (I) + structural unit (II)} is preferably 0.6 or less, and more preferably 0.4 or less. Yes, usually 0.01 or more, preferably 0.05 or more. In the above range, it tends to be easy to obtain a good balance between the affinity with polypropylene and the effect of silylation.
The kinematic viscosity η of the siloxane copolymer used in this reaction at 25 ° C. is usually 1 or more, preferably 5 or more, more preferably 10 or more, and particularly preferably 50 or more. When the kinematic viscosity is in the above range, the molecular weight of the siloxane copolymer is sufficiently large, and the structural unit (II) is retained by that amount, and the surface properties such as water repellency, oil repellency, stain resistance, and adhesiveness, and 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 effects of surface properties such as water repellency, oil repellency, stain resistance and adhesiveness, and gas permeability.

[Reaction between one-ended unsaturated polypropylene and siloxane copolymer]
In one embodiment of the hydrosilylation reaction, a catalyst of a transition metal complex is used. As the catalyst, transition metal complexes of Groups 8 to 10 of the Periodic Table are preferable, and examples thereof include platinum complexes, rhodium complexes, cobalt complexes, palladium complexes and nickel complexes. In the present invention, a platinum catalyst is preferable, and a platinum complex such as a chloroplatinic acid and a platinum olefin complex is particularly preferable. The amount of the catalyst used is usually about 0.1 to 1000 mass ppm, preferably 1 to 500 mass ppm, and particularly preferably 5 to 100 mass ppm as a metal unit with respect to the terminal unsaturated polypropylene.

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 one-ended unsaturated polypropylene and a siloxane copolymer are reacted 1: 1 it is necessary to charge more siloxane copolymer than one-ended unsaturated polypropylene.
The hydrosilylation reaction may be carried out 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 melting 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 carried out under normal pressure, but may be carried out under pressure.

A typical processing device (for example, an extruder, a batch mixer, a hot press, etc.) can be used for the 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 sequentially added to the reactor.

In the above solution reaction, the reaction apparatus is not particularly limited, and for example, a tank-type reactive group having a batch type or continuous type stirring device can be used. Examples of the reaction solvent used in the solution reaction include a hydrocarbon solvent and ether. 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. Be done. As the solvent, a hydrocarbon solvent is preferable, and a saturated alicyclic hydrocarbon and an aromatic hydrocarbon are more preferable.
The amount of the solvent used may be any amount as long as the one-ended unsaturated polypropylene and the siloxane copolymer are in a dissolved state, and is not particularly limited, but usually, the total concentration of the one-ended unsaturated polypropylene and the siloxane copolymer is 5 to 5 The amount is 50% by mass, preferably 10 to 40% by mass.

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

(In the formula, 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 the formula, R ₆ and R ₇ each independently represent a hydrocarbon group having 1 to 10 carbon atoms.)
R ₄ above for (III), meso triad fraction, Tm, and method for measuring the number average molecular weight, the preferred range is the same as one end unsaturation polypropylene as defined above.
The hydrocarbon group of R _{5 in} (III) above is the same as that in R ₁ above.
R ₆ and R ₇ of (IV) above are the same as R ₂ and R ₃ of the above.

The 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, preferably 10,000 or more. The number average molecular weight thereof is usually 250,000 or less, preferably 200,000 or less, and more preferably 100,000 or less.

[Use of silylated polypropylene]
The silylated polypropylene of the present invention modifies polypropylene materials, particularly surface properties such as water repellency, oil repellency, stain resistance, and adhesiveness of polypropylene materials, or compatibility with various resins including polar resins, or It can be suitably used for improving mechanical properties by combining with various inorganic materials.

Further, the silylated polypropylene of the present invention has the same heat resistance, transparency and molding processability as polypropylene as a single molded product, but has water repellency, antifouling property, releasability, gas permeability and the like as silicone. As a material having peculiar physical properties, it can be used for various purposes. For example, its excellent gas permeability makes it suitable for gas separation membranes such as oxygen-enriched membranes, and its excellent transparency makes it suitable for packaging materials for wrapping foods such as fruits and vegetables.

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

(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, silicone resin and the like. Each of these thermoplastic resins can be used individually by 1 type, or can be used in combination of 2 or more types. Of these, polyolefin resins are preferably used.

The polyolefin resin used in the present invention is not particularly limited, and conventionally known polyolefin resins can be used. Specific examples thereof 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 / methacrylate acrylate copolymers. Of these, low-density polyethylene, high-density polyethylene, and polypropylene resin are preferably used.

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

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

In addition, as additives, various heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, antioxidants, nucleating agents, plasticizers, impact improvers, compatibilizers, defoamers, and increase agents. Examples thereof include thickeners, cross-linking agents, surfactants, lubricants, blocking inhibitors, processing aids, antistatic agents, flame retardants, flame retardant aids, fillers, colorants, inorganic crystal nucleating agents and the like.

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

Fillers are roughly classified into organic fillers and inorganic fillers. Examples of the organic filler include naturally-derived polymers such as starch, cellulose fine particles, wood powder, okara, rice husks, and bran, and modified products thereof. Inorganic fillers include talc, calcium carbonate, zinc carbonate, wallastonite, 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 whiskers, ceramic whiskers, potassium titanate, boron nitride, graphite, carbon fiber and the like.

As the nucleating agent, sorbitol compound and its metal salt; benzoic acid and its metal salt; phosphoric acid ester metal salt; ethylene bisoleic acid amide, methylene bisacrylic acid amide, ethylene bisacrylic acid amide, hexamethylene bis-9,10 -Dihydroxystearic acid bisamide, p-xylylenebis-9,10-dihydroxystearic acid amide, decandycarboxylic acid dibenzoylhydrazide, hexanedicarboxylic acid dibenzoylhydrazide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, 2,6-naphthalenedicarboxylic acid Dianilide, N, N', N''-tricyclohexyltrimethic acid amide, trimethicate tris (t-butylamide), 1,4-cyclohexanedicarboxylic acid dianilide, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, N, N' -Dibenzoyl-1,4-diaminocyclohexane, N, N'-dicyclohexanecarbonyl-1,5-diaminonaphthalene, ethylenebisstearic acid amide, N, N'-ethylenebis (12-hydroxystearic acid) amide, octanedicarboxylic Examples thereof include amide compounds such as acid dibenzoylhydrazide. Examples of the inorganic crystal nucleating agent include talc, kaolin, silica and the like.

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 preferably 10% by weight or less, preferably 5% by weight or less.

(Mixing 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. It contains 0.01 part by weight or more, preferably 0.1 part 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 or more. Hereinafter, it is more preferably contained in an amount of 20 parts by weight or less. When the content ratio of (A) silylated polypropylene is less than the lower limit, the uniformity of the resin composition tends to decrease. On the other hand, when the content ratio of (A) silylated polypropylene exceeds the upper limit value, the mechanical strength of the resin composition may decrease.

(Preparation of resin composition)
The resin composition of the present invention containing silylated polypropylene and a thermoplastic resin can be obtained as a molded product by blending each of the above-mentioned components as a raw material and molding as it is, but these are previously obtained as a molded product. It is preferable to prepare a molded product obtained by molding the resin composition and use it as a resin composition. The resin composition of the present invention can be obtained by mixing the above-mentioned components in 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, by mixing the above-mentioned raw material components and the like at the same time or in an arbitrary order, a composition in which each component is uniformly distributed can be obtained.
For more uniform mixing and dispersion, it is preferable to melt and mix a predetermined amount of the above raw material components. Specifically, for example, each raw material component of the resin composition may be mixed in an arbitrary order and then heated, or all the raw material components and the like may be mixed while being sequentially melted. Further, only a part of each of the above-mentioned components may be prepared as a resin composition, and this resin composition and other components may be mixed and used for molding 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, a V blender, a ribbon blender, a Henschel mixer, or the like. However, a method of melt-kneading with a continuous kneader such as a single-screw extruder or a twin-screw extruder and a batch-type kneader such as a mill roll, a Banbury mixer, or a pressure kneader is preferable. The temperature at the time of melting and mixing may be a temperature at which at least one of the raw material components is in a molten state, but a temperature at which all the components to be used are melted is usually selected, and is generally 150 to 250 ° C.

(Measurement of number average molecular weight of one-ended unsaturated polypropylene)
First, about 20 (mg) of a sample was collected in a vial for the high-temperature GPC pretreatment device PL-SP260VS manufactured by Polymer Laboratory, 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 dissolved by heating to 135 ° C. with the above-mentioned pretreatment device for high temperature GPC PL-SP260VS, and filtered through a glass filter to prepare a sample. In the GPC measurement in the present invention, no polymer was trapped in the glass filter.

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

(One-end unsaturated polypropylene NMR measurement)
200 to 300 mg of the sample was placed in an NMR sample tube having an inner diameter of 10 mmφ together with o-dichlorobenzene / deuterated bromide benzene (C6D5Br) = 4/1 (volume ratio) 2.4 ml and hexamethyldisiloxane, which is a reference substance for chemical shift. It was put in, replaced with nitrogen, sealed, and dissolved by heating to be used for NMR measurement as a uniform solution. For the NMR measurement, an NMR apparatus AVANCE III400 of Bruker Biospin Co., Ltd. equipped with a 10 mmφ cryoprobe was used.
^{1 1} H-NMR was measured at a sample temperature of 80 ° C., a pulse angle of 4.5 °, a pulse interval of 2 seconds, and a total of 512 times.
¹³ C-NMR was measured at a sample temperature of 80 ° C., a pulse angle of 90 °, a pulse interval of 51.5 seconds, and an integration number of 1024 times, and was measured by the reverse gate decoupling method.

(Measurement of melting point of one-ended unsaturated polypropylene (Tm))
Using a Perkin Elmer PYRIS Diamond DSC differential scanning calorimetry device, the sample (about 5 mg) is thawed at 210 ° C. for 5 minutes, then cooled to -20 ° C. at a rate of 10 ° C./min and 5 at -20 ° C. After holding for minutes, the temperature was raised to 210 ° C. at a rate of 10 ° C./min to obtain a melting curve. The peak top temperature of the main exothermic peak in the temperature lowering stage was defined as the crystallization temperature Tc. Further, the peak top temperature of the main endothermic peak in the final temperature rising step performed to obtain the melting curve was defined as the melting point Tm.
(Siloxane copolymer material)

In the above siloxane copolymer, the result of calculating the unit structure (I) / {unit structure (I) + unit structure (II)} from the unit structure (I) (pieces) and the unit structure (II) (pieces) is as follows. Described in the table.

(Water contact angle measurement)
The polymer was pressed at 190 ° C. and 100 kgf using a spacer of 12 cm x 12 cm x 300 μm to process a film having a thickness of 300 μm. The water contact angle of the obtained film was measured in a constant temperature room at room temperature of 23 ° C. and humidity of 50% using a dynamic contact angle / surface tension measuring device FTA125 manufactured by First Ten Angstroms after fixing the film on a glass substrate. did. Pure water was used as the water. The volume of the water droplet to be dropped was in the range of 3.5 to 4.0 μL, respectively. 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 base material. A 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. For the cellophane tape, a commercially available transparent beauty color manufactured by 3M was used. First, a cellophane tape cut to a length of 5 cm was attached to the base material, and the mixture was allowed to stand for 1 minute. Then, the base material was fixed by hand, one end of the cellophane tape was grasped and lifted, and the adhesive strength was evaluated by a three-stage qualitative index.
Adhesive index: 1 (adhesive), 2 (weakly adhered), 3 (non-adhesive)

(Manufacturing Example 1)
[Method for producing hafnium dichloride (complex Mx)] rac-dimethylsilylenebis [2- (5-methyl-2-furyl) -4- (4-isopropylphenyl) indenyl]
The 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.

(Manufacturing Example 2)
[Manufacturing method of polypropylene (Mn10,600)]
A toluene solution of purified hexane (10,000 mL) and modified methylaluminoxane (Tosoh Finechem Co., Ltd. "MMAO-3A" 2.1 mmol [in an inductive autoclave with an internal volume of 24 L and a built-in stirring blade, which was replaced with purified nitrogen. Al-converted atom]) was introduced in 60 mL. 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 the polymer. The number average molecular weight ([Mn (GPC)]) of the obtained macromonomer was 10,600, and the isotactic pentad fraction (mm mm) measured by 13C-NMR was 0.91. The melting point (Tm) measured by DSC was 138.0 ° C. Table 1 shows the physical property values of the obtained isotactic polypropylene macromonomer.

(Manufacturing Example 3)
[Manufacturing method of polypropylene (Mn8,900)]
1,698 g of pure water was put into a 5 L separable flask equipped with a stirring blade and a reflux device, and 501 g of 98% sulfuric acid was added dropwise. Further, 300 g of commercially available granulated montmorillonite (manufactured by Mizusawa Industrial Chemicals, Inc., Benclay SL, average particle size: 19.5 μm) was added thereto, and the mixture was stirred. Then, the reaction was carried out at 90 ° C. for 2 hours. This slurry was washed with a device in which an aspirator was connected to a nutche 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 a device in which an aspirator was connected to a nutche and a suction bottle. The recovered 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 in a flask having a content of 50 mL. Under purified nitrogen, add 2.0 mL (equivalent to 2 mmol of TIBA to 1 g of montmorillonite) of a toluene solution (0.5 mmol / mL) of triisobutylethylaluminum (TIBA) manufactured by Nippon Aluminum Alkyls, Inc., and react at room temperature for 30 minutes. After that, the supernatant was extracted. 20 mL of toluene was added thereto, and the mixture was stirred for 10 minutes, and the work of extracting the supernatant was carried out twice more.

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. The mixture was stirred 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 an induction stirring autoclave (AC) having an internal volume of 2 L and having a built-in stirring blade, which was replaced with purified nitrogen. The temperature of AC was raised to 85 ° C. to introduce propylene, and the introduction was continued until the pressure in AC became stable at 0.8 MPa. After that, 200 mg of the above catalyst slurry was press-fitted, and the temperature inside the AC was raised to 90 ° C. to initiate polymerization. During the 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, the propylene inside the AC was purged to terminate the polymerization. When the yield of the polymer 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.

(Manufacturing Example 4)
[Manufacturing method of polypropylene (Mn6,300)]
In Production Example 2, 219 g of polypropylene was obtained in the same manner as in Production Example 3 except that the temperature inside the AC during polymerization was set to 95 ° C.
The number average molecular weight measured by GPC was 6,300 g / mol. The Tm measured by DSC was 140.0 ° C.

[Example 1]
Polypropylene (Mn10,600, 10.6 g, 1.0 mmol), silicone XL-110 (Mn1,047, 1.0 g, 1.0 mmol) and cyclohexane produced in Production Example 2 in a 300 mL four-necked flask with a mechanical stirrer. 100 mL was added and nitrogen bubbling was performed for 15 minutes. Then, the temperature was raised to 80 ° C., and after uniformly stirring, a platinum catalyst SIP6832.2 (containing 2 wt% platinum, 0.003 mL) was added, and the mixture was stirred at 80 ° C. for 5 hours. Then, the reaction solution was cooled to 40 ° C. with stirring, and ethanol (100 mL) was added until the polymer was precipitated. The precipitated polymer was recovered by filtration and washed with acetone (100 mLx3). The obtained polymer was dried under reduced pressure at 70 ° C. (yield 11.0 g).
¹ As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. In addition, it was confirmed by GPC measurement that the molecular weight was increased, and it was clarified 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 silicone XL-110 was changed to silicone XL-115 (Mn 3,229, 1.8 g, 0.6 mmol) (yield 12.4 g).
¹ As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. In addition, it was confirmed by GPC measurement that the molecular weight was increased, and it was clarified that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

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

[Example 4]
Polypropylene (Mn 10,600, 126.0 g, 11.9 mmol) and silicone XL-116 (Mn 6,610, 89.25 g, 13.5 mmol) produced in Production Example 2 in a 1,000 mL four-necked flask with a mechanical stirrer. And 700 mL of cyclohexane were added and nitrogen bubbling was performed for 15 minutes. Then, the temperature was raised to 80 ° C., and after uniformly stirring, a platinum catalyst SIP6832.2 (containing 2 wt% platinum, 0.07 mL) was added, and the mixture was stirred at 80 ° C. for 5 hours. The reaction solution was then 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 mLx3). The obtained polymer was dried under reduced pressure at 70 ° C. (yield 191.5 g).
¹ As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. In addition, it was confirmed by GPC measurement that the molecular weight was increased, and it was clarified 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).
¹ As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. In addition, it was confirmed by GPC measurement that the molecular weight was increased, and it was clarified 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).
¹ As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. In addition, it was confirmed by GPC measurement that the molecular weight was increased, and it was clarified that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

[Comparative Example 3]
Same as in Example 1 except that polypropylene was changed to polypropylene (Mn6,300) produced in Production Example 5 and silicone XL-110 was changed to silicone XL-116 (Mn6,610, 7.5 g, 1.1 mmol). The polymer was produced ((yield 11.0 g).
¹ As a result of ¹ H NMR measurement, it was confirmed that the terminal vinyl group had disappeared. In addition, it was confirmed by GPC measurement that the molecular weight was increased, and it was clarified that the hydrosilylation reaction proceeded by combining these results and that silicone and polypropylene were bonded.

The polymers produced in Examples 1 to 4 and Comparative Examples 1 to 3 were subjected to water contact angle measurement and adhesiveness test. The results are shown in Table 4.

The following raw materials were used for the evaluation of the resin composition in the present invention.
<(A) Cyrilized polypropylene>
(A) -1: Cyrilized polypropylene obtained in Example 4 <(B) thermoplastic resin>
(B) -1: Polypropylene (manufactured by Japan Polypropylene Corporation, product name Novatec FW4B: propylene / ethylene / butene copolymer, MFR (230 ° C., load 2.16 kg) 7 g / 10 minutes, density 0.90 g / cm3, ethylene Content 1.5% by weight, butene content 2.3% by weight)

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

<Example 6>
T A single-layer film having a layer thickness of 30 μm was obtained by melt extrusion from a die into a film having a width of 100 mm.

<Comparative example 4>
The same operation as in Example 6 was carried out except that silylated polypropylene was not added, and melt extrusion was performed 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>
The same operation as in Example 6 was performed except that 5 parts of the fatty acid bisamide containing behenic acid bisamide as a main component used in Example 1 of Patent No. 6047964 was used instead of the silylated polypropylene, and a film having a width of 100 mm It was melt-extruded into a single layer film having a layer thickness of 30 μm.

<Heat seal strength against polypropylene>
The film obtained in Examples 5 to 6 or Comparative Examples 4 to 5 was cut to a width of 15 mm and superposed on a sheet having a thickness of 0.3 mm consisting of only (B) -1 obtained in Comparative Example 4. , The pressure was 0.2 MPa, the time was 1.0 second, and the sealing temperature was changed from 140 ° C. to 180 ° C. in every 20 ° C., and the film was pressed by a heat seal bar to perform heat bonding. The heat-bonded portion of the test piece is peeled off at a peeling speed of 300 mm / min and 180 ° using a tensile tester (A & D Co., Ltd., Tencilon Universal Testing Machine (RTG1225)) to increase the peeling strength. 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 used by Kyowa Interface Science Co., Ltd. (Dropmaster DN300) at room temperature of 23 ° C. , Measured in a constant temperature room with a humidity of 50%. Pure water was used as the water. The volume of the water droplet to be dropped was in the range of 3.5 to 4.0 μL, respectively. 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.
For the films obtained in Example 6 and Comparative Examples 4 to 5, the film surface was rubbed three times with an ethanol-impregnated Kimwipe as an ethanol cleaning operation, and then the water contact angle was adjusted by the same operation as 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 used by Kyowa Interface Science Co., Ltd. (Dropmaster DN300) at room temperature of 23 ° C. , Measured in a constant temperature room with a humidity of 50%. Olive oil was used as the oil. The volume of the oil droplets to be dropped was in the range of 3.5 to 4.0 μL, respectively. 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 the silylated polypropylene obtained in the present invention.
Adhesive film: Acrylic adhesive tape cut to a width of 15 mm (manufactured by Nitto Denko KK, No. 31B)

<Evaluation of releasability: Peeling strength>
The film obtained in Examples 5 to 6 or Comparative Examples 4 to 5 was cut to a width of 15 mm and laminated with the adhesive surface of an adhesive film (manufactured by Nitto Denko KK, trade name: NO.31B, thickness 0.025 mm). In combination, a 2 kg rubber roller was reciprocated once on the adherend to adhere the film. The adhesive part of the test piece is peeled off at a peeling speed of 300 mm / min and 180 ° using a tensile tester (A & D Co., Ltd., Tencilon Universal Testing Machine (RTG1225)). did. The results are shown in Table 5.

From the results shown in Table 4, the examples of the present invention had a larger contact angle with water than the comparative examples, and showed improvement in peelability. A high contact angle indicates that it has a high affinity with polyolefins such as polypropylene. From the results in Table 5, it was shown that the contact angle with respect to water and 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 effect on the heat seal strength. From the results of Example 5 and Example 6, it was shown that the contact angle of the oil was increased by the amount of the silylated polypropylene of the present invention added. Further, from the results of Example 6 and Comparative Example 5, it was found that the composition of the present invention did not show a large decrease in the contact angle with water after the surface was washed with ethanol, and the state of the surface was maintained before and after washing. Indicated.

Claims (14)

(A) Polypropylene having a single-ended unsaturated bond with a terminal unsaturated bond rate> 90% and a number average molecular weight of 8,000 or more, and (b) a siloxane copolymer having the following structural units (I) and structural unit (II). A method for producing a silylated polypropylene, which comprises reacting with.

(In the formula, R _{1 to} R ₃ each independently represent a hydrocarbon group having 1 to 10 carbon atoms.) The method for producing a silylated polypropylene according to claim 1, wherein the (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 or 2, wherein the unsaturated bond at one end is a vinyl group in (a). The method for producing a silylated polypropylene according to any one of claims 1 to ₃ , wherein in the above (b), R _{1 to} R ₃ are methyl groups. The method for producing a silylated polypropylene according to any one of claims 1 to 4, wherein the number average molecular weight of polypropylene in (a) is 8,000 to 70,000. In the above (b), any one of claims 1 to 5, wherein the ratio of the structural unit (I) / {structural unit (I) + structural unit (II)} is 0.8 or less. The method for producing silylated polypropylene according to. The method for producing a 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 the (a) is produced by using a transition metal compound represented by the following general formula (3) as a catalyst. How to make polypropylene.

(In the formula, R ¹⁵ and R ¹⁶ each independently represent a nitrogen, oxygen, or sulfur-containing heterocyclic group having 4 to 16 carbon atoms, and R ¹⁷ and R ¹⁸ independently represent, respectively. One or more hydrocarbon groups having 1 to 6 carbon atoms, silicon-containing hydrocarbon groups having 1 to 6 carbon atoms, and halogens having 1 to 6 carbon atoms on the aryl cyclic skeleton within the range of 6 to 16 carbon atoms. Represents a hydrocarbon group, an aryl group having a halogen atom as a substituent, or a heterocyclic group having 6 to 16 carbon atoms and containing nitrogen, oxygen, or sulfur, and X ¹² and Y ¹² are independent of each other. 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 group having 1 to 20 carbon atoms. group, an amino group or a nitrogen-containing hydrocarbon group having a carbon number of 1 to 20,, Q ¹² is a divalent hydrocarbon group having 1 to 20 carbon atoms, have a hydrocarbon group having 1 to 20 carbon atoms It represents a silylene group or a gelmilene group which may be used.) Cyrilized polypropylene produced by the production method according to any one of claims 1 to 8. The silylated polypropylene according to claim 9, which has the following structural unit (III) and structural unit (IV).

(In the formula, 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 the formula, R ₆ and R ₇ each independently represent a hydrocarbon group having 1 to 10 carbon atoms.) The silylated polypropylene according to claim 10, wherein R _{5 to} R ₇ are methyl groups. A resin composition comprising (A) 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 thermoplastic resin (B) is a polyolefin resin. The resin composition according to claim 12 or 13, wherein 0.01 to 10,000 parts by weight of the silylated polypropylene of the above (A) is contained with respect to 100 parts by weight of the thermoplastic resin (B). ..