JPH05310826A - Natural macromolecular substrate coated with polyolefin resin and its production - Google Patents

Abstract

PURPOSE:To produce the biodegradable macromolecular substance coated with a polyolefin resin simply and inexpensively by polymerizing an alpha-olefin in the presence of a product of contact between a specified highly active catalyst component and a natural macromolecular substance and an organoaluminum compound. CONSTITUTION:The biodegradable substance is produced by polymerizing an alpha-olefin in the presence of a product of contact between a highly active catalyst component containing a transition metal and being soluble in an organic in an organic solvent (e.g. a catalyst component comprising dicyclopentadienyltitanium chloride and trimethylaluminum) and a natural macromolecular substance (e.g. polysaccharide or protein) and an organoaluminum compound (e.g. trimethylaluminum). According to this process, the substance which has biodegradability can be produced simply and inexpensively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin-based resin-coated natural polymer substance, a process for producing the same, and a resin composition containing the same, and more particularly, to a biodegradable substance (biodegradable or biodegradable). The present invention relates to a novel polyolefin-based resin-coated natural polymer substance, a simple and inexpensive method for producing the same, and a resin composition containing the same.

[0002]

2. Description of the Related Art Plastic materials have been widely used for a wide variety of applications in recent years because of their excellent properties, but they have been discarded because of their excellent durability. In some cases, it is not easily decomposed, causing pollution problems. Therefore, urgent development of biodegradable plastics is desired.

For this reason, it has been proposed to blend biodegradable polysaccharides and proteins into plastics as a filler or an additive and mechanically knead the mixture (Japanese Patent Laid-Open No. Hei 2).
-14228, 4-114044, and 4
-114043 and 4-90339).
However, they have hygroscopicity or agglomerate, and cannot always be uniformly blended. Further, in order to disperse these uniformly, kneading must be sufficiently performed, and a large amount of energy is required, and there is a problem that the resin, the filler, and the additive are deteriorated by the kneading, and particularly polysaccharides and There is a problem that proteins are easily colored by heat. Furthermore, it is generally difficult to blend a large amount of filler by kneading or to blend a filler with a high molecular weight resin.

The present invention solves these conventional problems,
In addition to being able to uniformly disperse even heat-sensitive natural polymer substances without kneading, it is possible to prevent coloration due to thermal alteration, and to obtain a high-mixed amount of filler that is impossible to obtain by the kneading method. It is an object of the present invention to provide a method of producing very little production energy, and also to provide a novel biodegradable polyolefin resin-coated natural polymer substance obtained by this method.

[0005]

That is, the first aspect of the present invention is
And a polyolefin-based resin-coated natural polymer substance coated with a polyolefin-based resin.
In addition, the present invention secondly, a treated product containing a transition metal, which is soluble in an organic solvent, and which is obtained by previously subjecting the highly active catalyst component [A] to a natural polymer substance, and an organoaluminum compound. The present invention provides a method for producing a polyolefin-based resin-coated natural polymer substance, which comprises polymerizing an α-olefin in the presence of [B]. Further, the present invention thirdly provides a resin composition containing the first polyolefin resin-coated natural polymer substance of the present invention.

The first polyolefin resin-coated natural polymer substance of the present invention is a natural polymer substance (material to be coated) uniformly coated with a polyolefin resin, and its shape is a natural polymer substance. There are various types depending on the shape, but powdery, granular or fibrous ones are preferable.

Here, the natural high molecular substance is a biodegradable substance, and specifically, it is a biodegradable polysaccharide or protein. These are not only those obtained from natural products but also those produced by a fermentation method, which correspond to those that are not synthetic polymers.

The polysaccharide may be either homoglycan (single polysaccharide) or heteroglycan (complex polysaccharide). First, starch is mentioned as a homoglycan (single polysaccharide). Here, the starches may be unmodified or may be physically or chemically modified. More specifically as starches,
For example, potato starch, sweet potato starch, corn starch, cassava starch, tapioca starch, sorghum starch and the like can be mentioned. Next, examples of the homoglycan include celluloses. Examples of the celluloses include methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl methyl cellulose, carboxymethyl cellulose, acetyl cellulose and the like. Further, as homoglycans, fructans such as inulin and levan, mannans such as elephant palm mannan, seaweed mannan and yeast mannan, xylans such as xylan of rice straw, galacturonans such as pectic acid, mannuronans such as alginic acid, Examples thereof include N-acetylglucosamine polymers such as chitin.

On the other hand, examples of the heteroglycan (complex polysaccharide) include konjac mannan, gum arabic, gatch gum, meskit gum, and viscous substances such as funoli and agar.

Next, the protein may be animal or plant. Specific examples of the protein include proteins such as soybeans, leather powder, gelatin, collagens such as glue, casein, gluten, blood albumin and the like.

There are various shapes of these natural polymer substances, and any of them may be used, but powdery, granular or fibrous ones are particularly preferable. For example, if it is powdery or granular, the average particle size is preferably 1 to 1000 μm, more preferably 2 to 500 μm. The fibrous material preferably has a fiber diameter of 1 to 100 μm, more preferably 2 to 50 μm. In addition,
As the natural polymer substance, a substance whose maximum length in each shape does not exceed 5 mm, particularly 2 mm or less, is preferable from the viewpoint of the production method. Also, as a natural polymer substance,
Before use, it is sufficient to dry by heat drying under reduced pressure or azeotropic drying using a solvent, or a product treated with an organoaluminum compound such as trialkylaluminum or dialkylaluminum monohalide is used. Seeing is preferable. In particular, by using the one previously treated with the organoaluminum compound, it is possible to effectively prevent the activity decrease of the catalyst component due to the water content or the functional group in the natural polymer.

The polyolefin coated on the natural polymer is usually polyethylene, but a small amount (usually up to about 20% by weight) together with this ethylene.
Α-olefins such as propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1,
It may be a copolymer of decene and octadecene.

The first polyolefin-based resin-coated natural polymer substance of the present invention is the above-mentioned natural polymer substance coated on its surface with a polyolefin-based resin. 99% by weight, especially 2
What is contained in the ratio of -95 weight% is preferable. Polymerization (copolymerization) of monomers, especially coating of polyolefin resin
It is preferable that the coating is applied to form a coating.

The first polyolefin resin-coated natural polymer substance of the present invention as described above can be efficiently produced by, for example, the second (production method) of the present invention shown below. That is, the second aspect of the present invention is that the high activity catalyst component [A] containing a transition metal and soluble in an organic solvent.
In the presence of a treated product obtained by previously subjecting a natural polymer substance to a contact treatment, and an organoaluminum compound [B],
A method for producing a polyolefin-based resin-coated natural polymer substance, which comprises polymerizing an α-olefin.

In the second aspect of the present invention, first, a highly active catalyst component (soluble catalyst component) [A] that contains a transition metal and is soluble in an organic solvent, and a natural polymer substance (covering material) Is treated in advance to obtain a processed product. Examples of the highly active catalyst component [A] containing a transition metal and soluble in an organic solvent include those specifically shown below, and can be prepared by various methods. That is, a highly active catalyst component soluble in an organic solvent is obtained by adding a titanium compound to a higher fatty acid salt of magnesium or manganese, a higher alcohol salt, or a phosphate having a long-chain aliphatic hydrocarbon group, and reacting them. Examples thereof include a reaction product, a transition metal compound and an aluminoxane, or a transition metal compound, and a compound capable of reacting with the transition metal in the transition metal compound to form an ionic complex.

For example, regarding the catalyst component containing titanium as a transition metal, a higher fatty acid salt of magnesium or manganese, a higher alcohol salt, or a phosphate having a long-chain aliphatic hydrocarbon group is added to the general formula [I].

[Chemical 1] [In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms or an acyl group, and X ¹ represents a halogen atom. Further, n is a real number of 0 or more and 4 or less. ] The reaction product obtained by adding and reacting the titanium compound represented by
In particular, a reaction product obtained by adding a titanium compound to an organomagnesium compound, for example, a higher fatty acid salt of magnesium, and reacting it is suitable. At this time, the addition amount of the titanium compound is not particularly limited, but usually with respect to the above-mentioned higher fatty acid salt of magnesium or manganese, higher alcohol salt or phosphate having a long-chain aliphatic hydrocarbon group,
It is selected in the range of 0.5 or less (molar ratio), preferably 0.02 to 0.2 (molar ratio). Addition amount of titanium compound is 0.5
When it exceeds the (molar ratio), the catalytic activity is remarkably reduced, which is not preferable.

The higher fatty acid or higher alcohol constituting the above salt may be saturated or unsaturated as long as it has 10 or more carbon atoms, and particularly preferably has 16 or more carbon atoms. Specific examples of these include capric acid, lauric acid, myristic acid, palmitic acid,
Examples thereof include higher fatty acids such as stearic acid and oleic acid, and higher alcohols such as decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol and stearyl alcohol. The phosphoric acid that constitutes the phosphate having a long chain aliphatic hydrocarbon group may be phosphorous acid, and phosphoric acid or a mono- or dialkyl ester of phosphorous acid (ROPH ₂ O ₃ , (RO ) ₂
PHO ₂ , ROPH ₂ O _2, etc.) or mono- or dialkyl (sub) phosphoric acid (RPH ₂ O ₃ , R ₂ PHO ₂ , RP
H ₂ O _{2 and the} like). The long-chain aliphatic hydrocarbon group may be either a saturated or unsaturated group as long as it has 6 or more carbon atoms, and particularly preferably 8 or more. Specific examples thereof include hexyl group, heptyl group, octyl group, 2-ethyl-hexyl group, nonyl group,
Examples thereof include a decyl group, a lauryl group, a myristyl group, a heptadecyl group, a stearyl group, and an octadecenyl group.

The higher fatty acid, higher alcohol, or magnesium salt or manganese salt of phosphoric acid having a long-chain hydrocarbon group can be obtained by various methods, or a commercially available product may be dried and used as it is. The above magnesium salt can be easily produced from higher fatty acid, higher alcohol or phosphoric acid having a long chain hydrocarbon group, alkyl magnesium and the like. Further, the above-mentioned magnesium salt or manganese salt (that is, higher fatty acid salt of magnesium or manganese, higher alcohol salt or the above-mentioned phosphate salt) may form a double salt with another metal.

On the other hand, the titanium compound used herein is represented by the general formula [I] as described above, and specifically, for example, titanium tetrahalide such as TiCl ₄ , TiBr ₄ , TiI _{4 and the} like. , Ti (OCH ₃ ) Cl ₃ , T
_{i (OC 2 H 5) Cl} 3, Ti (O-i-C 3 H 7) C
l ₃ , Ti (OC ₄ H ₉ ) Cl ₃ , Ti (OC ₂ H ₅ ) Br
Trihalogenated monoalkoxy titanium such as ₃ , Ti
_{(OCH 3) 2 Cl 2,} Ti (OC 2 H 5) 2 Cl 2, Ti
_{(O-i-C 3 H} 7) 2 Cl 2, Ti (OC 4 H 9) 2 Cl
₂ , Ti (OC ₂ H ₅ ) ₂ Br ₂ and other dihalogenated dialkoxy titanium, Ti (OCH ₃ ) ₃ Cl, Ti (OC _{2
H 5) 3 Cl, Ti (} O-i-C 3 H 7) 3 Cl, Ti (O
_{C 4 H 9) 3 Cl,} Ti (OC 2 H 5) 3 monohalogenated trialkoxy titanium such as _{Br, Ti (OCH 3) 4} , T
_{i (OC 2 H 5) 4} , Ti (O-i-C 3 H 7) 4, Ti
Tetraalkoxytitanium such as (OC ₄ H ₉ ) ₄ and further Ti (OCOCH ₃ ) ₄ and Ti (OCOCH ₃ ) ₂ Cl ₂
And so on.

In the present invention, among the highly active catalyst components containing a transition metal and soluble in an organic solvent, the catalyst component containing titanium as a transition metal is, as described above, a higher fatty acid such as magnesium or manganese. It can be obtained by reacting a salt, a higher alcohol salt or the above-mentioned phosphate with a titanium compound represented by the above general formula [I]. The reaction conditions at this time are various, but normally, these compounds may be mixed in a hydrocarbon solvent and reacted at a temperature in the range of 50 ° C. to the boiling point of the solvent for 10 minutes or more. In some cases, the above-mentioned higher fatty acid salt or higher alcohol salt or the above-mentioned phosphate salt is mixed with a natural polymer substance in a hydrocarbon solvent, and then the titanium compound represented by the general formula [I] is added. By reacting in addition,
A treated product composed of a catalyst component [A] containing titanium and a natural polymer substance may be prepared.

Further, in obtaining this titanium-containing catalyst component, the above-mentioned salt and titanium compound,
For example, VCl ₄ , VOCl ₃ , VO (OC ₂ H ₅ ) ₃ , V
When a vanadium compound such as O (OC ₄ H ₉ ) ₃ is used,
It is effective for expanding the molecular weight distribution of the obtained polymer and improving the copolymerizability.

Further, in the present invention, as the highly active catalyst component containing a transition metal and soluble in an organic solvent,
Some include transition metal compounds, especially compounds of transition metals belonging to Group IVB of the periodic table (for example, titanium, zirconium, etc.) and aluminoxane.

Among these, titanium-based materials include, for example, those composed of a cyclopentadienyl titanium compound or a dicyclopentadienyl titanium compound, and an aluminoxane. Here, the aluminoxane can be obtained by a known method such as reacting water with a trialkylaluminum such as trimethylaluminum or triethylaluminum, or a dialkylaluminum monohalide such as dimethylaluminum chloride or diethylaluminum chloride. Examples of the cyclopentadienyl titanium compound include dicyclopentadienyl titanium chloride and dimethyldicyclopentadienyl titanium.

The zirconium compound is prepared, for example, by mixing a cyclopentadienyl zirconium compound or this cyclopentadienyl compound with an aluminoxane obtained by the above-mentioned known method. Examples of cyclopentadienylzirconium include dichlorodicyclopentadienylzirconium and dimethyldicyclopentadienylzirconium. Further, in mixing these cyclopentadienyl dititanium compound or cyclopentadienyl zirconium compound with aluminoxane, these compounds are mixed in an aromatic hydrocarbon solvent such as benzene, toluene, xylene and other alkylbenzenes. It is preferable to mix with. At this time, it is not preferable to use an aliphatic hydrocarbon or an alicyclic hydrocarbon as the solvent because the above-mentioned zirconium compound and aluminoxane cannot be sufficiently dissolved. Moreover, it is preferable to mix these compounds before mixing with the natural polymer. However, it is also possible to mix these natural polymer substances at the same time.

In the second aspect of the present invention, the transition metal compound and the transition metal in the transition metal compound react as a highly active catalyst component [A] containing a transition metal and soluble in an organic solvent. It is also possible to use a compound capable of forming an ionic complex, that is, a transition metal compound and a coordination complex compound composed of a cation and an anion in which a plurality of groups are bound to an element, in combination. Here, the transition metal compound is a compound containing a transition metal selected from Group IVB of the periodic table, that is, a compound containing titanium (Ti), zirconium (Zr) or hafnium (Hf), and a cyclo group containing these transition metals. If it is a pentadienyl compound,
Either one can be used.

Examples of such compounds include zirconium compounds shown below and compounds obtained by substituting zirconium in these compounds with titanium or hafnium. That is, specifically as a zirconium compound,
For example, (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) (Enyl) tribenzylzirconium, (methylcyclopentadienyl) trimethylzirconium, (methylcyclopentadienyl) tribenzylzirconium,
(Tetramethylcyclopentadienyl) trimethylzirconium, (Trimethylsilylcyclopentadienyl)
Trimethylzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium, bis (cyclopentadienyl) dichlorozirconium, bis (cyclopentadienyl) dimethylzirconium, bis ( Cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzylzirconium,
Bis (methylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dibenzylzirconium, bis ( Pentamethylcyclopentadienyl) chloromethylzirconium, bis (pentamethylcyclopentadienyl) hydridomethylzirconium, ethylenebis (indenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) ) Dimethylzirconium, isopropyl- (cyclopentadienyl)-(9-
Examples thereof include fluorenyl) -zirconium dichloride.

The compound capable of reacting with the transition metal in the above transition metal compound to form an ionic complex is not particularly limited, but specifically, the following compounds are particularly preferably used. You can That is, triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, triethylammonium tetra (pentafluorophenyl) borate, tri (n-butyl) ammonium tetra (pentafluorophenyl) borate, Hexafluoroarsenate triethylammonium, tetra (pentafluorophenyl) borate dimethylanilium, tetra (pentafluorophenyl) borate trimethylanilium, tetraphenylborate ferrocenium, tetra (pentafluorophenyl) borate decamethylferrocenium, tetra (penta Fluorophenyl) acetylferrocenium borate, tetra (pentafluorophenyl)
Formylferrocenium borate, cyanoferrocenium tetra (pentafluorophenyl) borate, tetraphenylborate, silver tetra (pentafluorophenyl) borate, trityl tetraphenylborate, trityl tetra (pentafluorophenyl) borate, hexafluoroarsenic acid Examples thereof include silver, silver hexafluoroantimonate, and silver tetrafluoroborate.

The contact conditions of the above two are not particularly limited, but usually, the ratio of the former: the latter is 1: 0.01 to 1: 1.
00, particularly preferably 1: 1 to 1:10. The temperature can be set in the range of -100 ° C to + 250 ° C, and the pressure and the time can be set arbitrarily.

The thus obtained transition metal-containing catalyst component [A] is a component soluble in organic solvents such as aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons. Further, this component has a high activity such that 10 kg or more of polyethylene can be produced per 1 atmospheric pressure of ethylene and 1 g of transition metal atom in low-pressure polymerization of ethylene using the catalyst component and the organoaluminum compound [B]. Is preferred. If the activity of the component is low, a large amount of the component must be added to the reaction system, and as a result, a deashing step is required after the polymerization reaction, and post-treatment becomes extremely complicated, which is not preferable.

In the second aspect of the present invention, as described above,
A treated product containing a transition metal and soluble in an organic solvent and having a high activity catalyst component [A] previously contacted with a natural polymer substance is used as one component and an organoaluminum compound is used as the other component. [B] is used.

As the natural polymer substance, the above-mentioned ones are used here. The shape of these natural polymeric substances is
There are various types as described above, and any shape can be used, but powdery, granular or fibrous ones are particularly preferable. For example, if it is powdery or granular, the average particle size is preferably 1 to 1000 μm,
It is more preferably 2 to 500 μm. In addition, the fibrous material preferably has a fiber diameter of 1 to 100 μm.
It is more preferably ˜50 μm.

As the natural polymer substance, the maximum length of each shape does not exceed 5 mm, especially 2 m.
It is preferably m or less. If a large one having a maximum length of more than 5 mm is used in each shape, agglomeration is severe during the polymerization of ethylene and the like, large lumps are formed to cause clogging of pipes and the like, and the obtained coating is unsatisfactory. It will be homogeneous. In addition, as the natural polymer substance, before use, it is sufficiently dried by drying under reduced pressure or azeotropic drying using a solvent, or treated with an organoaluminum compound such as trialkylaluminum and dialkylaluminum monohalide. It is preferable to use one. In particular, by using the one previously treated with the organoaluminum compound, it is possible to effectively prevent the activity decrease of the catalyst component due to the water content or the functional group in the natural polymer.

There is no particular limitation on the contact treatment of such a natural polymer substance with a highly active catalyst component [A] which contains a transition metal and is soluble in an organic solvent. For example, an aliphatic hydrocarbon, It may be determined using various solvents such as alicyclic hydrocarbons and aromatic hydrocarbons within a range of room temperature to the boiling point of the solvent used. The aging time is usually 1 at room temperature.
As a guide, it is time or more.

The mixing ratio of the two in the contact treatment is
It depends on various conditions and is difficult to set uniquely. In short, according to the method of the present invention, when the α-olefin is polymerized or copolymerized, the natural polymer in the target polyolefin-based resin-coated natural polymer substance is selected so that the polymerization or copolymerization proceeds efficiently. It may be appropriately determined in consideration of the amount of the substance. Usually, as mentioned above,
Due to the polymerization, the total amount of polyolefin resin is 0.5 to 9
It is preferable to add 9% by weight, particularly 2 to 95% by weight.

Next, in the second aspect of the present invention, an organoaluminum compound is used as the other component (component [B]). Here, there are various kinds of organic aluminum compounds, and there is no particular limitation. Usually the following general formula (II)

[Chemical 2] Those represented by are preferred. R ² in the formula has 1 to 1 carbon atoms.
10, preferably 1 to 6 alkyl, cycloalkyl or aryl groups, and X ² is a halogen atom.
In addition, m is a positive real number of 3 or less, specifically m = 1,1.5
, 2 or 3.

Examples of such an organoaluminum compound are trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trioctylaluminum, diethylaluminum monochloride, diethylaluminum monobromide, diethylaluminum monoio. Dialkyl aluminum monohalides such as daid, diisopropyl aluminum monochloride, diisobutyl aluminum monochloride, dioctyl aluminum monochloride, and alkyl aluminum sesquihalides such as methyl aluminum sesquichloride, ethyl aluminum sesquichloride, ethyl aluminum sesquibromide, and butyl aluminum sesquichloride are suitable. And Mixtures of these were also preferably used.

Particularly when a mixture of trialkylaluminum and dialkylaluminum halide, alkylaluminum dihalide or alkylarnium sesquihalide contains titanium as a constituent component of the catalyst component [A]. Good to use. In addition, an organolithium aluminum compound, and an alkyl group-containing aluminoxane produced from trialkylaluminum and water can also be used. In particular, this aluminoxane is preferable when the one containing a cyclopentadienyl titanium or cyclopentadienyl zirconium compound is used as a constituent component of the catalyst component of the above-mentioned [A] component.

In the method of the present invention, the contact-treated product as described above and the organoaluminum compound [B] are used,
Polymerization of α-olefin is performed. Here, ethylene is usually used as the α-olefin as described above, but together with this ethylene, a small amount (usually a maximum of 20% by weight) is used.
Degree) α-olefins such as propylene, butene-
It can also be copolymerized with 1, hexene-1, octene-1,4-methylpentene-1, decene, octadecene and the like.

As for the amount of polymerization, the composition of a coating obtained by coating a natural polymer with a polyolefin resin is: polyolefin resin: natural polymer = 0.5 to 99: 99.5 to 1 (% by weight), preferably 2 to It may be performed so as to be 95:98 to 5 (% by weight). The polymerization method and conditions are not particularly limited, and either slurry polymerization or gas phase polymerization is possible, and either continuous polymerization or discontinuous polymerization is possible.
The ethylene pressure of the reaction system is atmospheric pressure to 50 kg / cm ² · G, and the reaction temperature is 10 to 150 ° C., preferably 20 to 12
Set to 0 ° C. Molecular weight control during polymerization is a known means,
For example, hydrogen can be used.

According to the second (production method) of the present invention, after carrying out the polymerization or copolymerization reaction, in the case of slurry polymerization, operations such as flashing and centrifugation are carried out, and further drying is carried out to remove the solvent and the like. If removed, the desired polyolefin resin-coated natural polymer substance can be obtained in the form of powder, particles or fibers. This polyolefin-based resin-coated natural polymer substance may be one in which polyolefin powder is mixed in part, or coated particles are aggregated. In this manner, a coating product obtained by coating the biodegradable natural polymer substance with the polyolefin resin, that is, the first polyolefin resin-coated natural polymer substance of the present invention is obtained. The polyolefin-based resin-coated natural polymer substance thus obtained may be used as biodegradable plastic for various purposes as it is, or may be molded into films, containers, containers, non-woven fabrics, etc. by various molding methods. You may use it.

Further, a third aspect of the present invention is a resin composition containing the above polyolefin-based resin-coated natural polymer substance. That is, the above polyolefin-based resin-coated natural polymer substance can be mixed with another thermoplastic resin, thermosetting resin, rubber or the like to be used as a (composite) resin composition. In this case, mixing into a solution is also possible.
The blending amount of the polyolefin-based resin-coated natural polymer substance varies depending on the amount of the coated polyolefin-based resin, but the amount of the natural polymer substance in the entire resin composition is usually 1
The amount is -80% by weight, preferably 2-60% by weight.

[0042]

EXAMPLES Next, the present invention will be described with reference to examples. Example 1 (1) Preparation of Titanium-Containing Soluble System Catalyst Component In a flask having an internal volume of 500 ml and purged with argon, 150 ml of dehydrated n-heptane was added at room temperature, 10.0 g (17 mmol) of magnesium stearate, and 0.1 ml of titanium tetrachloride. 33 g (1.7 mmol) was added. Then, the temperature was raised and the reaction was carried out for 2 hours under reflux of the solvent to obtain a viscous translucent titanium-containing soluble catalyst component. (2) Evaluation of activity of titanium-containing soluble catalyst component In an autoclave having an internal volume of 1 liter and having been replaced with argon, 400 ml of dehydrated n-hexane, 0.5 mmol of triethylaluminum, 0.5 mmol of diethylaluminum monochloride and the above (1) 0.005 millimole of the titanium-containing soluble catalyst component obtained as described above as titanium atoms was collected and supplied to the autoclave. Next, the temperature is raised to 90 ° C., hydrogen is supplied to increase the pressure to 4 kg / cm ² · G, and then ethylene is continuously supplied so that the total pressure can be maintained at 9 kg / cm ² · G. Polymerization was carried out. The amount of polyethylene obtained was 58 g, and the polymerization activity was 242 kg /
It was g.Ti.hr.

(3) Contact Treatment of Titanium-Containing Soluble Catalyst Component with Natural Polymeric Substance In an autoclave having an internal volume of 1 liter which was replaced with argon, 650 ml of dehydrated hexane at room temperature and starch powder (potato starch) Powder, average particle size 20 to 200 μm) (30 g) was added, diethylaluminum monochloride 3 mmol was added dropwise with stirring, and 40 ° C.
Was treated for 1 hour. Next, 0.03 mmol of the titanium-containing soluble catalyst component obtained in (1) above was added as a titanium atom, and contact was carried out at 40 ° C. for 1 hour to obtain a contact-treated product. (4) Polymerization of ethylene After the contact treatment in (3) above, the temperature was raised to 90 ° C. After that, 3 mmol of triethylaluminum was added, and then hydrogen was supplied at 0.5 kg / cm ² · G, and then the total pressure was adjusted to 4.5.
Ethylene was continuously supplied so as to maintain the pressure at kg / cm ² · G (the total pressure at this time was adjusted so that the ethylene partial pressure was 2 kg / cm ² · G), and polymerization was performed for 17 minutes. .. The amount of the polyethylene-based resin-coated natural polymer substance obtained was 62 g, and the content of the starch powder, which was a natural polymer substance, was 48% by weight. As a result of observing the dried powder with an electron microscope, the particles of starch powder were uniformly coated with polyethylene. The weight average molecular weight of polyethylene was 93,000 as determined by GPC analysis. The results are shown in Table 1. The content of starch powder was calculated from the amount of starch powder charged and the yield.

Example 2 In place of the starch powder of Example 1 (3) in Example 1, cellulose (microcrystals, particle size 20-200 μm) 3 was used.
Polymerization was carried out in the same manner as in Example 1 except that 0 g was used, and the polymerization was carried out for 3 minutes. The amount of the polyethylene-based resin-coated natural polymer substance obtained was 63 g, and the content of cellulose as the natural polymer substance was 48% by weight.
As a result of observing the dried powder with an electron microscope, polyethylene was uniformly coated on the cellulose microcrystals. The results are shown in Table 1.

Example 3 Polymerization was carried out in the same manner as in Example 1 except that 30 g of agar powder (particle size 20 to 200 μm) was used in place of the starch powder of Example 1 (3). Go 4
Polymerization was carried out for 5 minutes. The amount of the polyethylene-based resin-coated natural polymer substance obtained was 63 g, and the content of the agar powder, which was a natural polymer substance, was 48% by weight. As a result of observing the dried powder with an electron microscope, the agar powder was uniformly coated with polyethylene. The results are shown in Table 1.

Example 4 In Example 1, 30 g of soybean protein powder (particle size 20 to 200 μm) was used instead of the starch powder of Example 1 (3).
Polymerization was performed in the same manner as in Example 1 except that the above was used, and the polymerization was performed for 24 minutes. The amount of the obtained polyethylene-based resin-coated natural polymer substance was 62 g, and the content of the protein powder which was a natural polymer substance was 48% by weight. As a result of observing the dried powder with an electron microscope, the protein powder was uniformly coated with polyethylene. The results are shown in Table 1.

Example 5 (1) Preparation of Titanium-Containing Soluble System Catalyst Component 50 ml of dehydrated n-heptane, 5.64 g (10 mmol) of magnesium stearyl alcohol salt and 0.19 g (1 mmol) of titanium tetrachloride was added. Then, the temperature was raised and the reaction was carried out for 3 hours under reflux of the solvent to obtain a viscous translucent titanium-containing soluble catalyst component. (2) Evaluation of activity of titanium-containing soluble catalyst component In an autoclave having an internal volume of 1 liter replaced with argon, dehydrated n-hexane (400 ml), triethylaluminum (1 mmol), diethylaluminum monochloride (1) was added.
0.01 mmol of the titanium-containing soluble catalyst component obtained in (1) and the titanium-containing soluble catalyst component were sampled and supplied to the autoclave. Next, the temperature is raised to 90 ° C., hydrogen is supplied to increase the pressure to 4 kg / cm ² · G, and then the total pressure is 9 kg.
/ Cm ² · G was continuously fed with ethylene so that the polymerization was carried out for 1 hour. The polyethylene obtained is 6
It was 0 g, and the polymerization activity was 126 kg / g.Ti.hr.

(3) Contact Treatment of Titanium-Containing Soluble Catalyst Component with Natural Polymeric Material The same as Example 1 (3) except that the titanium-containing soluble catalyst component prepared in (1) above was used. The contact-treated product was obtained. (4) Polymerization of ethylene Polymerization was carried out for 33 minutes in the same manner as in Example 1 (4) except that the contact-treated product obtained in (3) above was used. The obtained polyethylene-based resin-coated natural polymer substance was 63 g, and the content of starch powder, which is a natural polymer substance, was 4 g.
It was 8% by weight. As a result of observing the dried powder with an electron microscope, the starch powder was uniformly coated with polyethylene. The results are shown in Table 1.

Example 6 (1) Preparation of aluminoxane 100 ml of dehydrated toluene and 71 mmol of commercially available copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) were placed at room temperature in a flask having an inner volume of 500 ml which had been replaced with argon. A toluene solution of 246 mmol of trimethylaluminum (2 mol / liter) was added dropwise at 20 ° C. for 30 minutes. After reacting at room temperature for 24 hours and filtering, toluene was removed from the filtrate under reduced pressure to obtain 4.2 g of a colorless solid component (molecular weight 763 by benzene freezing point depression method). Then, toluene was added to this solid again to prepare a 2 mol / liter solution with an aluminum equivalent. (2) Activity Evaluation of Zirconium-Containing Soluble Catalyst Component In an autoclave having an internal volume of 1 liter replaced with argon, 400 ml of dehydrated toluene, the aluminoxane obtained in (1) above, 6 mmol of aluminum equivalent (hereinafter the same), and bis ( Cyclopentadienyl) dichlorozirconium was added in an amount of 0.003 mmol and the temperature was raised to 50 ° C.
Ethylene was continuously fed so as to keep the total pressure at 8 kg / cm ² · G, and polymerization was carried out for 5 minutes to obtain 16.4 g.
Of polyethylene was obtained. The catalytic activity of this product is 719
It was kg / g · Zr · hr.

(3) Contact between zirconium-containing soluble catalyst component and natural polymer substance In an autoclave having an internal volume of 1 liter and which was replaced with argon, 650 ml of dehydrated toluene at room temperature and starch powder (potato starch powder, particle size 20 to 20). 200 μm) 30
1 g of diethylaluminum monochloride was added dropwise with stirring, and the mixture was treated at 40 ° C. for 1 hour.
Next, 0.005 mmol of the zirconium-containing soluble catalyst component used in (2) above was added as a zirconium atom, and contact was carried out at 20 ° C. for 1 hour to obtain a contact-treated product. (4) Polymerization of ethylene In Example 1 (4), the polymerization temperature was 50 ° C.,
And 10 mmol of the aluminoxane prepared in (1) above was used instead of triethylaluminum.
Polymerization was carried out for 20 minutes in the same manner as in Example 1 (4). 64 g of the obtained polyethylene-based resin-coated natural polymer substance
The content of starch powder, which is a natural polymer, was 47% by weight. As a result of observing the dried powder with an electron microscope, the starch powder was uniformly coated with polyethylene. The results are shown in Table 1.

Example 7 In Example 1, the diethylaluminum monochloride of Example 1 (3) was set to 1 mmol, and the soluble catalyst component containing titanium was set to 0.01 mmol as a titanium atom. Polymerization was carried out in the same manner as in Example 1 except that the polymerization temperature of (4) was 40 ° C., triethylaluminum was 1 mmol, and hydrogen was not added, and the polymerization was carried out for 55 minutes. .. The amount of the polyethylene-based resin-coated natural polymer substance obtained was 60 g, and the content of starch powder, which is a natural polymer substance, was 50% by weight.
Met. As a result of observing the dried powder with an electron microscope,
The starch powder was uniformly coated with polyethylene. In addition, the weight average molecular weight of polyethylene by GPC analysis is
It was 1,050,000. The results are shown in Table 1.

Example 8 In Example 1, 90% of the starch powder of Example 1 (3) was used.
1 g of diethyl aluminum monochloride
Example 1 (4), in which the amount of the soluble catalyst component containing titanium was 0.01 mmol of titanium atom.
To triethylaluminum was 1 mmol, that the hydrogen partial pressure and 0.2kg / cm ² · G, and except that the ethylene partial pressure and 1kg / cm ² · G in the same manner as in Example 1 10 Polymerization was carried out for a minute. The amount of the obtained polyethylene-based resin-coated natural polymer substance was 95 g, and the content of the starch powder which was a natural polymer substance was 95% by weight. As a result of observing the dried powder with an electron microscope, the starch powder was uniformly coated with polyethylene. The results are shown in Table 1.

[0053]

[Table 1]

Application Example 1 The polyethylene resin-coated natural polymer substances obtained in Examples 1 to 4 were press-molded under the conditions of 190 ° C. and 50 kg / cm ² · G to obtain a film having a thickness of 100 μm. ..

Example 9 The polyethylene-based resin-coated natural polymer substances obtained in Examples 1, 2, and 4 were mixed in powder high-density polyethylene in an amount of 5 to 20% by weight to prepare 6 types. A composite resin composition of Then, this composite resin composition is added to 190
Press-molded under conditions of ℃ and 50kg / cm ² · G, thickness 10
A 0 μm film was obtained.

[0056]

The first novel polyethylene-based resin-coated natural polymer substance of the present invention is a naturally biodegradable polysaccharide,
A natural high molecular substance such as protein is uniformly coated with a polyethylene resin. The first novel polyethylene-based resin-coated natural polymer substance of the present invention, when molded, is a biodegradable (biodegradable) natural polymer substance that is uniformly dispersed, resulting in biodegradation. The subsequent polyethylene-based resin is easily miniaturized, and there is no risk of causing waste pollution after use.

According to the second (manufacturing method) of the present invention, the novel polyethylene resin-coated natural polymer substance having biodegradability as described above can be manufactured easily and at low cost. Further, according to the second aspect of the present invention, the natural polymer substance can be uniformly dispersed without kneading,
It is possible to effectively prevent coloring due to thermal alteration during kneading. Moreover, according to the second aspect of the present invention, the content of the natural polymer substance and the molecular weight of the polyethylene resin can be arbitrarily controlled, and a high compounding amount product of the natural polymer substance which cannot be obtained by the kneading method. It is also possible to combine ultra-high molecular weight resins and natural polymer substances. Further, according to the second aspect of the present invention, blending and kneading energy is unnecessary, and production energy can be extremely reduced. Therefore, the novel polyethylene resin-coated natural polymer substance of the present invention can be used as a biodegradable plastic film,
It can be effectively used in various fields such as packaging fields such as containers, containers, and non-woven fabrics, fishing lines, agriculture, gardening, etc. without causing pollution.

[Brief description of drawings]

FIG. 1 is a drawing showing a preparation process of a catalyst used in the method of the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location C08L 23/02 LCW 7107-4J // C08L 1:00 7415-4J 3:00 7415-4J 5: 00 7415-4J 89:00 7415-4J

Claims (5)

[Claims] 1. A natural polymer substance coated with a polyolefin resin, which is coated with a polyolefin resin. 2. The polyolefin resin-coated natural polymer substance according to claim 1, which has a powdery, granular or fibrous shape. 3. A processed product containing a transition metal, which is soluble in an organic solvent, and which is obtained by subjecting a highly active catalyst component [A] to a natural polymer substance in advance, and an organoaluminum compound [B]. A method for producing a polyolefin-based resin-coated natural polymer substance, which comprises polymerizing an α-olefin in the presence thereof. 4. A highly active catalyst component soluble in an organic solvent is a higher fatty acid salt of magnesium or manganese, a higher alcohol salt or a phosphate having a long-chain aliphatic hydrocarbon group,
A reaction product obtained by adding and reacting a titanium compound,
The polyolefin-based resin-coated natural polymer substance according to claim 3, which is a compound capable of reacting with a transition metal compound and an aluminoxane, or a transition metal compound, and a transition metal in the transition metal compound to form an ionic complex. Production method. 5. A resin composition containing the polyolefin-based resin-coated natural polymer substance according to claim 1.