JP4474544B2 - Polymer type nucleating agent and crystalline polymer composition containing the nucleating agent - Google Patents

Description

The present invention relates to a polymer nucleating agent that is excellent in dispersibility and miscibility in a crystalline polymer, has little bleed-out, and has little odor and taste transfer problems generated from the nucleating agent, and the nucleating agent The present invention relates to a crystalline polymer composition containing an agent. More specifically, the present invention relates to a polymer type nucleating agent having a specific structure and a crystalline polymer composition containing the nucleating agent.

Crystalline polymers, especially polyolefin polymers represented by polyethylene, polypropylene, and poly (1-butene), are high in hot melt molding such as injection molding, film processing, spinning processing, flat yarn molding, and hollow molding. There is a drawback that the crystallization speed of the molecule is slow. Therefore, there are problems that need to be improved, such as molding cycle, mechanical properties, transparency, and dimensional stability.

It has been reported that these problems can be improved by reducing the crystal size of the crystalline polymer and increasing the crystallization speed. In general, optimization of molding process conditions and improvement of characteristics of crystalline polymer compositions by addition of crystallization accelerators, nucleating agents, and the like have been studied.

As the above crystallization accelerator and nucleating agent, for example, low molecular organic compounds such as phosphate ester salts, carboxylic acid ester salts, and sorbitol, and inorganic compounds such as talc are generally used. For example, it is reported in the following Patent Documents 1 to 15. However, the nucleating agent has problems that the dispersibility and miscibility in the crystalline polymer are insufficient, bleed out easily, and the odor and taste generated from the nucleating agent are easily transferred. .
JP-A-55-12460 JP-A-58-1736 JP 58-80392 A JP 59-184252 A JP-A-6-340786 JP-A-7-11075 JP 7-48473 A JP-A-8-3364 JP-A-9-118776 Japanese Patent Laid-Open No. 10-25295 WO99 / 18108 JP 2001-59040 A JP 2003-313444 A JP 2003-335968 A JP 2004-83852 A Japanese Patent Laid-Open No. 3-166244

In addition, in order to compensate for the disadvantages of the above low molecular organic compounds, inorganic compound crystallization accelerators, and nucleating agents, for example, poly-3-methyl-1-butene, polyvinylcyclohexane, polycyclobutene, polycyclopentene, High molecular compounds such as tetrafluoroethylene have been studied, and reported in, for example, the following Patent Documents 16 to 22 and Non-Patent Document 1. However, although the polymer nucleating agent shows a nucleating effect when added to a crystalline polymer, its performance has not yet been satisfactory.
Japanese Examined Patent Publication No. 45-32430 Japanese Patent Publication No. 3-42298 Japanese Patent Publication No. 3-42298 JP-A-8-169960 JP-A-8-290536 JP-A-8-291236 Japanese Patent Laid-Open No. 9-249753 J. et al. Appl. Polym. Sci. Vol. 54, 1507-1511 (1994)

An object of the present invention is to provide a polymer-type nucleating agent that is excellent in dispersibility and miscibility in a crystalline polymer, has little bleed-out, and has little odor and taste transfer problems generated from the nucleating agent, and An object of the present invention is to provide a crystalline polymer composition containing a nucleating agent.

In view of the above problems, the present inventors have developed a polymer-type nucleating agent which is excellent in dispersibility and miscibility in a crystalline polymer and has little bleeding out, and a crystalline polymer containing the nucleating agent. We have been conducting intensive research to obtain the composition. As a result, the inventors have found that the above problems can be solved by a polymer-type nucleating agent having a specific structure and a crystalline polymer composition containing the nucleating agent, and have reached the present invention.

That is, the present invention provides a polymer type nucleating agent comprising a repeating unit represented by the following general formula (1), and a crystalline polymer composition containing the nucleating agent.
(1)
(In the formula, m is 1, and R1, R1 ′, R2, R2 ′ and R3, R3 ′ are hydrogen.)

Hereinafter, the best embodiment of the present invention will be described in detail.

The polymer type nucleating agent of the present invention has a structure in which cyclopentane derivatives and methylene chains are alternately bonded, as represented by the general formula (1). In the general formula (1), m is 1, and R1, R1 ′, R2, R2 ′ and R3, R3 ′ are hydrogen.

Of the repeating units represented by the general formula (1), the cyclopentane structure is a 1,3-structure, m = 1 or 2, and R ₁ , R ₁ ′ R ₂ , R ₂ ′ and R ₃ , The following repeating unit No. 1 wherein R ₃ ′ is hydrogen: 1 and no. 2 is particularly preferred.

The production method of the polymer-type nucleating agent comprising the repeating unit represented by the general formula (1) is not particularly limited. For example, a method of hydrogenating a ring-opening metathesis polymer of a norbornene derivative, 1 , 5-hexadiene derivative with cycloaddition, cycloolefin and norbornene derivative ring-opening metathesis copolymer hydrogenation, ethylene and 1,5-hexadiene derivative with cycloaddition Is possible.

The number average molecular weight (Mn) and molecular weight dispersity (Mw / Mn) of the polymer type nucleating agent comprising the repeating unit represented by the general formula (1) are not particularly limited, but the nucleating agent In consideration of the workability of the crystalline polymer composition containing, usually, Mn is preferably in the range of about 500 to 1,000,000, more preferably about 1,000 to 100,000. Usually, Mw / Mn is preferably in the range of 1.5-20. In addition, about Mn and Mw / Mn, it is the value measured using the gel permeation chromatography, and what was calibrated with the standard polystyrene sample is used for a calibration curve.

The crystalline polymer used in the crystalline polymer composition containing the nucleating agent is not particularly limited, and examples thereof include low density polyethylene, linear low density polyethylene, high density polyethylene, , Isotactic polypropylene, syndiotactic polypropylene, hemiisotactic polypropylene, stereoblock polypropylene, poly (1-butene), poly (3-methyl-1-butene), poly (3-methyl-1-pentene), Polyolefin copolymers such as α-olefin polymers such as poly (4-methyl-1-pentene), ethylene / α-olefins, random copolymers of two or more α-olefins, and block copolymers. It is done.

As the crystalline polymer used in the crystalline polymer composition of the present invention, among these polyolefin-based (co) polymers, polypropylene, ethylene / propylene random copolymer or block copolymer, α-olefin / Polypropylene resins such as propylene random or block copolymers and mixtures of these propylene (co) polymers with other α-olefin polymers are particularly preferred.

The molecular weight of the crystalline polymer used in the crystalline polymer composition of the present invention is not particularly limited, but in consideration of processability, the intrinsic viscosity ([η]) is usually 0.5 to 3. Preferably there is. Usually, Mw / Mn is preferably in the range of 1.5-20.

The content of the polymer nucleating agent used in the crystalline polymer composition of the present invention is not particularly limited, but is 0.001 to 10 parts by weight with respect to 100 parts by weight of the crystalline polymer. Preferably, 0.01-5 weight part is more preferable. If it is less than 0.001 part by weight, a sufficient effect may not be obtained, and if it exceeds 10 parts by weight, no further effect is obtained, and the physical properties of the molded product obtained from the crystalline polymer composition are not obtained. It may have undesirable effects and is also meaningless from an economic point of view.

There are no particular restrictions on how the polymer type nucleating agent is incorporated into the crystalline polymer composition, and a blending method, a polymerization method, or the like can be used. Specifically, after synthesizing a polymer type nucleating agent in advance, a method of mixing in a solution of an appropriate solvent and a crystalline polymer, a method of mixing in a molten state using various kneaders, a polymer type Examples thereof include a method in which a nucleating agent is prepolymerized and then a crystalline polymer is main-polymerized to be mixed in a polymerization tank, and a block copolymer is formed.

In the crystalline polymer composition of the present invention, additives that are usually used in the crystalline polymer composition, for example, an antioxidant, a dispersant, a lubricant, are used as long as the effects of the present invention are not inhibited. In addition, an antistatic agent, an antiblocking agent, a colorant and the like, or a nucleating agent other than the polymer type nucleating agent may be blended.

The invention's effect

According to the present invention, a polymer-type nucleating agent that is excellent in dispersibility and miscibility in a crystalline polymer and has little bleeding out, and transparency, mechanical strength, and dimensional stability containing the nucleating agent. It is possible to provide a crystalline polymer composition excellent in the above.

Applications of the crystalline polymer composition obtained in the present invention include automobile parts, parts for household appliances, household goods, connecting parts, miscellaneous goods, medical equipment, building materials, wire covering materials, agricultural materials, food packaging Examples thereof include molded products and fibers including films and sheets such as materials.

Hereinafter, although a reference example, an example, and a comparative example are given and the present invention is explained in detail, the present invention is not restricted at all by these examples. The polymer type nucleating agent and the crystalline polymer composition obtained in the following Reference Examples, Examples and Comparative Examples were evaluated by the following methods.

(1) Differential scanning calorimetry (DSC measurement)
The measuring apparatus used was DSC8230 manufactured by Rigaku Corporation. About 4 mg of the sample was sealed in an aluminum sample pan, and an empty sample pan was used as a control substance. First, in order to remove the thermal history, the temperature was raised to 200 ° C. and held for 5 minutes. Next, it was cooled to 25 ° C. at 10 ° C./min. The temperature was further increased to 200 ° C. at 10 ° C./min. All measurements were performed under a nitrogen atmosphere. The crystallization temperature (T _c ) and crystallization enthalpy (ΔH _c ) were determined in the temperature lowering process, and the melting point (T _m ) and melting enthalpy (ΔH _m ) were determined in the temperature increasing process.

(2) Evaluation with a polarizing microscope Using a hot stage manufactured by METLER TOLEDO, a small amount of sample was placed on a slide glass, further covered with a cover glass, and the sample was heated to 200 ° C. at a heating rate of 20 ° C./min. The heat history was removed by holding for a minute. Next, it cooled to room temperature at 10 degreeC / min, the spherulite was observed using the polarizing microscope BX50 made from Olympus, and magnification was 200 times, and it image | photographed using digital camera DP11 made from Olympus.

(3) Gel permeation chromatography (GPC) measurement Showa Denko Co., Ltd. column GPC K-805L, and GPC made by JASCO Corporation equipped with intelligent differential refractometer RI-2031 were used as the solvent. Measurement was performed at 40 ° C. using chloroform as a standard substance and polystyrene.

Reference Example (Polypropylene Polymerization) 935.5 ml of toluene was placed in a 21-necked separable flask substituted with nitrogen and cooled to 0 ° C. in an ice bath. A separately prepared 100 ml two-necked flask was purged with nitrogen, 50 μmol of catalyst dimethylsilylenebis (2-methyl-4-phenylindenyl) zirconium dichloride was added, and 50 ml of toluene was added thereto and stirred to dissolve to prepare a catalyst solution. . The cooled 21-necked separable flask was degassed, and propylene gas was introduced to saturate with toluene. Thereto, 12.5 ml (1.0 M) of a toluene solution of triisobutylaluminum, 50 ml of a catalyst solution, and 2.0 ml (0.025 M) of a toluene solution of tritylpentafluorophenylborate were sequentially added to initiate polymerization. The polymerization was carried out for 150 minutes. After polymerization, 2-propanol was added to the flask to deactivate the catalyst. Thereafter, the produced polymer was placed in methanol, and further hydrochloric acid was added to remove the catalyst residue. The polymer was washed several times with water and methanol, and then dried under reduced pressure at 60 ° C. for 6 hours to obtain 57.3 g of polypropylene. The intrinsic viscosity measured in decalin at 135 ° C. is 2.9 (dl / g), T _c and ΔH _c are 112.4 ° C. and 91.3 J / g, respectively, T _m and ΔH _m are 157.2 ° C. and It was 91.0 J / g. The results are shown in Table 1, and a polarizing microscope photograph of the obtained polypropylene is shown in FIG.

Example 1
(Metathesis polymerization of norbornene) 20.3 mmol of norbornene and 6 ml of dioxane were placed in a nitrogen-substituted 50 ml two-necked flask. A separately prepared 50 ml two-neck flask was purged with nitrogen, 25.2 mmol of WCl ₆ and 3.28 μmol of co-catalyst tetramethyltin were added, and ₆ ml of dioxane was further added and stirred to prepare a catalyst solution. The catalyst solution was added to the reaction vessel to initiate polymerization. After reacting at room temperature for 24 hours, the entire polymerization solution was poured into methanol to deactivate the catalyst, and then the polymer was filtered off and dried under reduced pressure at room temperature for 6 hours to obtain 1.0 g of polynorbornene. Mn was 63000 and Mw / Mn was 2.8.

(Hydrogenation of polynorbornene; synthesis of poly (ethylene-1,3-cyclopentane)) 0.5 g of synthesized polynorbornene, 4.1 g of p-toluenesulfonyl hydrazide and 30 ml of xylene were placed in a nitrogen-substituted 300 ml three-necked flask. , And stirred at 135 ° C. for 4 hours. After completion of the reaction, a small amount of distilled water was added to the reaction system to stop the reaction. Next, the entire reaction solution was poured into methanol, the polymer was precipitated, filtered, and dried under reduced pressure at room temperature for 6 hours to obtain hydrogenated polynorbornene (H-PNB) almost quantitatively.

(Evaluation of nucleation of hydrogenated polynorbornene (H-PNB)) About 1 g of the polypropylene synthesized in Reference Example and 1.0 mg (0.1 wt%) of hydrogenated polynorbornene were dissolved at 180 ° C. using orthodichlorobenzene as a solvent. Allowed to mix. After 2 hours, the solution was poured into methanol to precipitate the mixture, filtered off and dried under reduced pressure at 60 ° C. for 6 hours. _{T c} and [Delta] H _c of polypropylene mixed with synthesized hydrogenated polynorbornene (H-PNB) in this embodiment, respectively _{112.8 ℃, 132.3J / g, T} m and [Delta] H _m are respectively 153.3 ° C. , 116.5 J / g. The results are shown in Table 1, and a polarizing microscope photograph of polypropylene mixed with hydrogenated polynorbornene (H-PNB) is shown in FIG.

Example 2
(Metathesis polymerization and hydrogenation of norbornene)
Polymerization was carried out in the same manner as in Example 1 except that the temperature at the time of metathesis polymerization of norbornene was changed to 60 ° C. in Example 1. 0.97 g of polynorbornene was obtained, Mn was 75200, and Mw / Mn was 2.6. The obtained polynorbornene was hydrogenated in the same manner as in Example 1.

(Nucleation evaluation of hydrogenated polynorbornene (H-PNB))
The same method as in Example 1 was used. _{T c} and [Delta] H _c of synthetic polypropylene mixed with hydrogenated polynorbornene in this embodiment, respectively _{114.8 ℃, 111.4J / g, T} m and [Delta] H _m are respectively 155.3 ℃, 103.8J / g. The results are shown in Table 1.

Example 3
(Cyclopolymerization of 1,5-hexadiene; synthesis of poly (methylene-1,3-cyclopentane) (PMCP)) 25.0 mmol of 1,5-hexadiene and 35.4 ml of toluene in a nitrogen-substituted 100 ml two-necked flask And cooled to -25 ° C. A 50 ml two-necked flask prepared separately was purged with nitrogen, and 10 μmol of catalyst bis (pentamethylcyclopentadienyl) zirconium dichloride and 5 ml of toluene were added and stirred to prepare a catalyst solution. The catalyst solution was added to a 100 ml two-necked flask, and 6.6 mL (3.01 M) of a toluene solution of methylaluminoxane was added to initiate polymerization. The polymerization was carried out for 8 hours. After the reaction, the polymerization solution was poured into a large amount of methanol to deactivate the catalyst, and then the polymer was separated by filtration. The obtained polymer was extracted with a Soxhlet type extractor using orthodichlorobenzene as a solvent to remove the catalyst residue. Further, the solvent was distilled off with an evaporator. Methanol was poured and the resulting polymer was filtered off, followed by drying under reduced pressure at 60 ° C. for 6 hours to obtain 0.12 g of poly (methylene-1,3-cyclopentane) (PMCP).

(Nucleation evaluation of poly (methylene-1,3-cyclopentane) (PMCP))
The same method as in Example 1 was used. _{T c} and [Delta] H _c of the synthesized poly polypropylene mixed with (methylene-1,3-cyclopentane) (PMCP) in this embodiment, respectively _{115.4 ℃, 117.5J / g, T} m and [Delta] H _m is They were 153.7 ° C. and 106.3 J / g, respectively. The results are shown in Table 1, and a polarizing microscope photograph of polypropylene mixed with poly (methylene-1,3-cyclopentane) is shown in FIG.

Example 4
(Cyclopolymerization of 1, -5-hexadiene; synthesis of poly (methylene-1,3-cyclopentane) (PMCP)) In Example 3, the catalyst was diphenylmethylene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride. Polymerization was carried out in the same manner as in Example 3 except that the polymerization temperature was 50 ° C. and the polymerization time was 2 hours to obtain 1.15 g of poly (methylene-1,3-cyclopentane) (PMCP).

(Nucleation evaluation of poly (methylene-1,3-cyclopentane) (PMCP))
The same method as in Example 1 was used. _{T c} and [Delta] H _c of the synthesized poly polypropylene mixed with (methylene-1,3-cyclopentane) (PMCP) in this embodiment, respectively _{113.3 ℃, 114.1J / g, T} m and [Delta] H _m is They were 154.0 ° C. and 104.4 J / g, respectively. The results are shown in Table 1.

Comparative Example 1
(Nucleation Evaluation of Phosphate Ester Sodium Salt (NA-11 (Asahi Denka Kogyo Co., Ltd.))) Hot 1 g of polypropylene synthesized in Reference Example 1 and 1.0 mg (0.1 wt%) of NA-11 It was melt-kneaded at 200 ° C. on the plate. _{T c} and [Delta] H _c of polypropylene mixed with NA-11, respectively _{118.8 ℃, 104.9J / g, T} m and [Delta] H _m are respectively 153.6 ° C., was 101.3J / g. The results are shown in Table 1.

As is clear from the results shown in Table 1, the crystalline polymer compositions (Examples 1 to 4) containing the polymer type nucleating agent of the present invention do not contain a nucleating agent (reference examples), and compared to the general-purpose low-molecular organic compound nucleating agent (NA-11) to include (Comparative example 1), high values of [Delta] H _c and [Delta] H _m, polymeric nucleating agent of the present invention has excellent nucleating It became clear to show the effect. Also in the deflection microscope observation, in the crystalline polymer compositions (Examples 1 and 3) to which the polymer type nucleating agent was added, spherulite refinement due to the nucleating effect was confirmed (FIGS. 2 and 3). .

  FIG. 1 is a deflection micrograph of polypropylene obtained in a reference example.   FIG. 2 is a deflection micrograph of polypropylene obtained by mixing hydrogenated polynorbornene (H-PNB) obtained in Example 1.   FIG. 3 is a deflection micrograph of polypropylene obtained by mixing poly (methylene-1,3-cyclopentane) (PMCP) obtained in Example 3.

Claims (4)

A polymer type nucleating agent comprising a repeating unit represented by the following general formula (1).
(1)
(In the formula, m is 1, and R1, R1 ′, R2, R2 ′ and R3, R3 ′ are hydrogen.)   A crystalline polymer composition comprising the nucleating agent according to claim 1.   The crystalline polymer composition according to claim 2, wherein the crystalline polymer is a polyolefin polymer.   The crystalline polymer composition according to claim 3, wherein the polyolefin polymer is a polypropylene resin.