JP4313618B2 - Modified propylene polymer and process for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a modified propylene polymer and a method for producing the same.
[0002]
[Prior art]
An acid-modified product obtained by adding an unsaturated carboxylic acid or an anhydride thereof to a propylene polymer and a method for producing the acid-modified product are known. Many of such acid-modified products have a high acid addition amount, but their molecular weight is extremely low, so their uses are limited.
On the other hand, an acid-modified product having an excellent balance between molecular weight and acid addition amount (high molecular weight and high acid addition amount) is desired in the development of new composite materials such as polypropylene nanocomposite materials. Several attempts have already been made to produce such acid-modified products. For example, a method for improving the balance of the acid-modified product using ultrahigh molecular weight polypropylene as a starting material is disclosed (see Patent Document 1).
However, it is considered that such special polypropylene is not only difficult to use for general purposes but also has problems in terms of production stability and the like. In this method, the molecular weight distribution of the obtained acid-modified product is usually extremely low, and when used for a film or the like, it causes a decrease in moldability.
Therefore, in order to avoid such a problem, it has been desired to develop an acid-modified product having an excellent balance and a wide molecular weight distribution using generally used polypropylene.
[0003]
On the other hand, a considerable amount of unreacted acid remains in the acid-modified product obtained by the usual production method, which causes problems such as deterioration of physical properties and odor. As a technique for reducing unreacted substances that adversely affect such products, a technique of removing modified polypropylene by dissolving it in a solvent and then precipitating it in a poor solvent or by extracting it while refluxing with a specific solvent is disclosed. (See Patent Document 2).
In addition, a technique for removing unreacted unsaturated carboxylic acid or anhydride thereof at a high temperature of 120 ° C. using a 30-fold larger amount of diketone compound relative to modified polypropylene is disclosed (see Patent Document 3).
Furthermore, a technique for removing unreacted unsaturated carboxylic acid or its anhydride at a high temperature of 90 to 110 ° C. by using a mixed solvent of a large amount of diketone and aromatic hydrocarbon 7 times larger than that of modified polypropylene is disclosed. (See Patent Document 4).
However, in addition to the drawback of using a large amount of solvent, these methods are processed at a high temperature in a solvent, so that the modified propylene polymer may be fused.
As described above, an acid-modified propylene polymer with excellent balance between molecular weight and acid addition, wide molecular weight distribution, and low content of unreacted acid components, general polypropylene, and a small amount of solvent are used. As a result, there is almost no technology that can be manufactured simply (economically).
[0004]
[Patent Document 1]
JP 2002-20436 A
[Patent Document 2]
JP-A 63-90511
[Patent Document 3]
JP-A-2-185505
[Patent Document 4]
JP-A-4-202202
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the above circumstances, and is a modified propylene polymer having an excellent balance between the molecular weight and the content of the acid component, a wide molecular weight distribution, and a low content of the unreacted acid component, and a method for producing the same. The purpose is to provide.
[0006]
In order to achieve the above object, as a result of intensive research, the present inventors have thoroughly mixed polymer raw materials having specific physical properties under specific temperature conditions, and under temperature conditions where the progress of the decomposition reaction of polypropylene is small. The present inventors have found that melt kneading is effective and completed the present invention.
[0007]
[Means for Solving the Problems]
According to the first aspect of the present invention, a modified propylene polymer satisfying the following (1) to (4) is provided.
(1) Intrinsic viscosity [η] measured in tetralin at 135 ° C._aIs 0.5-2.5 dl / g
(2) Molecular weight distribution (Mw / Mn) is 3 or more
(3) The content [b] of the polar group part derived from the compound containing the ethylenic double bond and the polar group in the same molecule, contained in the modified propylene polymer, and
(4) The content [B] of the polar group part derived from the compound grafted in the modified propylene-based polymer and containing an ethylenic double bond and a polar group in the same molecule,
([B]-[B]) × 100 / [b] ≦ 2
Satisfy the relationship.
[0008]
According to the second aspect of the present invention, (A) Intrinsic viscosity [η] measured in tetralin at 135 ° C._rIs 1 to 4 dl / g, and the amount of the component having a molecular weight of 1 million or more is 10 to 50% by weight of a propylene polymer,
(B) a compound containing an ethylenic double bond and a polar group in the same molecule, and
(C) a radical initiator,
Mixing at a temperature of 40 to (melting point of propylene-based polymer (A) -50) ° C,
Melting and kneading at a temperature of the melting point of the propylene polymer (A) to 180 ° C.
And a method for producing the modified propylene-based polymer.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the modified propylene polymer of the present invention will be described.
The modified propylene polymer of the present invention has an intrinsic viscosity ([η]) measured at 135 ° C. in tetralin._a) Is 0.5 to 2.5 dl / g, preferably 0.8 to 2.0 dl / g. When this value is less than 0.5 dl / g, when used for resin modification, physical properties are likely to deteriorate. On the other hand, if it exceeds 2.5 dl / g, stable production becomes difficult and molding processing becomes difficult.
[0010]
In addition, the above intrinsic viscosity ([η]_a) And the intrinsic viscosity ([η]) measured in tetralin at 135 ° C. of the propylene-based polymer that is the raw material of the modified polymer of the present invention._r)) ([Η]_a/ [Η]_r) Is preferably 0.3 or more, more preferably 0.4 or more. When this ratio is less than 0.3, the molecular weight distribution of the modified polymer tends to be less than 3.
This ratio represents the degree of cleavage of the molecular chain of the modified polymer, and the larger the ratio, the more the molecular chain of the modified polymer is not cleaved.
The raw material propylene polymer will be described later.
[0011]
The modified propylene polymer of the present invention has a molecular weight distribution (Mw / Mn) of 3 or more, preferably 3.5 or more. If this value is less than 3, the moldability of a film or the like is lowered.
Here, Mw represents a weight average molecular weight, and Mn represents a number average molecular weight.
[0012]
The content [b] of the polar group part derived from the compound (modifier) containing the ethylenic double bond and the polar group in the same molecule contained in the modified propylene polymer of the present invention, and the modified propylene polymer The content [B] of the polar group derived from a compound (modifier) having an ethylenic double bond and a polar group in the same molecule grafted in the coalescence is ([b]-[B]) × The relationship 100 / [b] ≦ 2 is satisfied. If this value exceeds 2, it is likely to cause odor of the product, mold corrosion during molding, and bad odor during molding. This value is preferably 1 or less.
[0013]
Here, the content [b] is specifically the total content of the content [B] and the content of the polar base derived from the unreacted modifier.
That is, the above relational expression indicates the ratio of the polar base portion derived from the unreacted modifier contained in the modified polymer. Therefore, the smaller this value is, the smaller the content of the unreacted modifier.
[0014]
The content [B] is preferably 20 to 400 mmol / kg, more preferably 40 to 350 mmol / kg, and still more preferably 80 to 300 mmol / kg. When this value is less than 20 mmol / kg, the concentration of the polar base is low, and the performance for resin modification may not be sufficiently exhibited. On the other hand, if it exceeds 400 mmol / kg, the intrinsic viscosity of 0.5 dl / g or more ([η]_a) May be difficult to obtain.
The modifier constituting the polar base will be described later.
[0015]
The modified propylene-based polymer of the present invention has (A) intrinsic viscosity ([η]) measured at 135 ° C. in tetralin._r) Is 1 to 4 dl / g, and the component amount having a molecular weight of 1 million or more is 10 to 50% by weight of a propylene polymer, (B) a compound containing an ethylenic double bond and a polar group in the same molecule (modifier) ) And (C) the radical initiator is mixed at a temperature of 40 to (melting point of propylene polymer (A) −50) ° C., preferably 50 to (melting point of propylene polymer (A) −70) ° C. And it can manufacture by melt-kneading at the temperature of melting | fusing point -180 degreeC of a propylene-type polymer (A).
When the mixing temperature is less than 40 ° C., temperature control becomes difficult. On the other hand, when (melting point of propylene-based polymer (A) −50) ° C. is exceeded, torque increases due to partial melting of the resin, and productivity decreases.
When the melt kneading temperature is lower than the melting point of the propylene-based polymer (A), torque is increased due to partial melting of the resin, and productivity is lowered. On the other hand, when it exceeds 180 ° C., the molecular weight of the modified polymer is lowered, and Mw / Mn tends to be less than 3. [Η]_a/ [Η]_rBecomes less than 0.3.
[0016]
The propylene polymer (A) is not particularly limited as long as the above requirements are satisfied. For example, propylene homopolymer, propylene and α-olefin (for example, ethylene, 1-butene, 4-methyl-1-pentene, etc.) ) And random copolymers, block copolymers, graft copolymers, and mixtures thereof. Among these, a propylene homopolymer is preferable.
[0017]
The propylene polymer (A) has an intrinsic viscosity [η] measured in tetralin at 135 ° C._rIs 1 to 4 dl / g, preferably 2 to 3.5 dl / g. When it is less than 1 dl / g, the intrinsic viscosity ([η]) of 0.5 dl / g or more_aIt is difficult to produce a modified polymer having On the other hand, when it exceeds 4 dl / g, temperature control at the time of mixing each component in an extruder will become difficult, and quality will become easy to vary.
[0018]
The amount of the component having a molecular weight of 1 million or more in the propylene polymer (A) is 10 to 50% by weight, preferably 15 to 30% by weight. When the amount of this component is less than 10% by weight, the polar base content ([B]) decreases, and the molecular weight distribution (Mw / Mn) of the modified polymer tends to be less than 3. On the other hand, if it exceeds 50% by weight, it becomes difficult to control the temperature when the components are mixed in the extruder, and the quality tends to vary.
The component amount having a molecular weight of 1 million or more means a component amount having a molecular weight of 1 million or more in the GPC curve.
[0019]
The propylene polymer (A) has a melting point (Tm) of preferably 140 to 170 ° C, more preferably 150 to 165 ° C.
[0020]
Such a propylene polymer (A) is a known highly stereoregular catalyst such as magnesium atom, titanium atom, halogen atom, polyvalent carboxylic acid, as described in JP-A-63-234004. Propylene, propylene and other α-olefins using a highly stereoregular catalyst obtained from a solid catalyst component containing an acid ester, an organoaluminum compound such as triethylaluminum, and an electron donating compound such as t-butyltriethoxysilane Can be produced by (co) polymerization. At that time, the amount of hydrogen supplied at the time of polymerization may be reduced.
[0021]
Examples of polar groups contained in the modifier (B) include carboxylic acid groups, carboxylic anhydride groups, carboxylic acid ester groups, carboxylic acid halide groups, carboxylic acid amide groups, carboxylic acid imide groups, carboxylic acid groups, and sulfones. Examples thereof include an acid group, a sulfonic acid ester group, a sulfonic acid chloride group, a sulfonic acid amide group, a sulfonic acid group, an epoxy group, an amino group, and an oxazoline group. Of these, a carboxylic acid group and a carboxylic anhydride group are preferable.
[0022]
The modifying agent (B) used in the present invention is not particularly limited, but is preferably an unsaturated carboxylic acid containing the above polar group and / or a derivative thereof.
As unsaturated carboxylic acid or its derivative (s), unsaturated mono- or dicarboxylic acid, or these derivatives are mentioned, for example. Specific examples of these derivatives include anhydrides, esters, halides, amides, imides, and salts of carboxylic acids. Among these, unsaturated dicarboxylic acid or its anhydride is preferable.
[0023]
Specific examples of unsaturated mono- or dicarboxylic acids include acrylic acid, methacrylic acid, maleic acid, endo-bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid (endic acid), fumaric acid Tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid and the like.
[0024]
Specific examples of the unsaturated carboxylic acid derivative include maleenyl chloride, maleimide, maleic anhydride, endic acid anhydride, methyl acrylate, acrylic acid amide, methyl methacrylate, glycidyl methacrylate, methacrylic acid amide, citraconic anhydride, Itaconic anhydride, nadic anhydride, monomethyl maleate, dimethyl maleate, monomethyl fumarate, dimethyl fumarate and the like can be mentioned.
[0025]
Of these unsaturated carboxylic acids or derivatives thereof, acrylic acid, methacrylic acid and maleic anhydride are preferred, and maleic anhydride is more preferred. These may be used individually by 1 type, and may be used in combination of 2 or more types.
[0026]
As radical initiator (C), butyl peroxide, α, α-bis (t-butylperoxy) diisopropylbenzene, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, t-butylperacetate, t-butylperdiethylacetate T-butyl perisobutyrate, t-butyl per-sec-octoate, t-butyl perpivalate, cumyl perpivalate, t-butyl perbenzoate, t-butyl perphenyl acetate, t-butyl cumyl peroxide, Di-t-butyl peroxide, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, 2,2-di- (t-butylperoxy ) Butane, lauroyl peroxy 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,4-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,4,4-trimethylpentyl- 2-hydroperoxide, diisopropylbenzene hydroperoxide, cumene hydroperoxide, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydrophthalate, di-t-butylperoxyase Rate, t-butylperoxy-3,3,5-trimethylhexoate, t- Chiruperuokishi - isopropyl monocarbonate, succinate Nick acid peroxide, and vinyltris - (t-butylperoxy) silane, t- butyl peroxycarboxylic benzoate and the like. Of these, preferably, benzoyl peroxide, t-butyl peroxybenzoate, 1,3-bis (t-butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) Xin-3, dicumyl peroxide, α, α-bis (t-butylperoxy) diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane. These may be used individually by 1 type, and may be used in combination of 2 or more types.
[0027]
At the time of producing the modified polymer of the present invention, additives such as an antioxidant and calcium stearate can be further blended as necessary.
[0028]
The modifier (B) is preferably blended in an amount of 2 to 10 parts by weight, more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the propylene polymer (A).
[0029]
The radical initiator (C) is preferably blended in an amount of 0.2 to 3 parts by weight, more preferably 0.3 to 2 parts by weight with respect to 100 parts by weight of the propylene polymer (A).
[0030]
In the production method of the present invention, each of the above components is mixed at 40 to (Tm-50) ° C., preferably 50 in the mixing zone (M zone) 2 of the cylinder using, for example, a twin screw extruder shown in FIG. It can mix at the temperature of-(Tm-70) degreeC, and can melt-knead in the temperature of Tm-180 degreeC in the reaction zone (R zone) 3 and 4 of a cylinder.
Here, the mixing zone is a region in which the raw materials for producing the modified propylene polymer are mixed, but the modification reaction does not occur so much. The reaction zone is the active agent for the unmodified propylene polymer. This is a region where a denaturation reaction is occurring.
Even when one extruder is used, the site of the mixing zone and reaction zone may change depending on the modification conditions, but in general terms used in the screw design in the cylinder, Usually, a zone containing a part of the compression zone is a mixing zone and a metering zone or a zone containing a part of the metering zone and the compression zone is a reaction zone.
In the present invention, each component may be mixed in advance by a method such as dry blending before mixing and melt-kneading with a molding machine such as a twin screw extruder.
At the time of mixing and melt-kneading, the resin temperature from the hopper lower part 1 of the twin-screw extruder cylinder to the mixing zone 2 is preferably set to a temperature of 40 to (Tm-50) ° C., and from the reaction zones 3 and 4 of the cylinder to the die 5 The resin temperature up to is Tm to 180 ° C. At this time, the resin temperature of the hopper lower part 1 is preferably 130 ° C. or lower, more preferably 100 ° C. or lower, and particularly preferably room temperature to 60 ° C. in order to prevent scattering of the modifier.
The melt kneading temperature means the temperature of the highest temperature part in the cylinder of the twin screw extruder, and in FIG. 1, it means the temperature between the die 5 and the reaction zones 3 and 4 of the cylinder.
[0031]
The melt kneading (residence) time is preferably 10 to 120 seconds.
At the time of melt-kneading, it is preferable to keep in an inert gas atmosphere. At this time, steam may be added or volatile components may be removed under reduced pressure.
As the molding machine, a single screw extruder, a twin screw extruder or the like is used.
Examples of the twin screw extruder include a 20 mm lab plast mill, 35 mm TEM (Toshiba Machine twin screw extruder), and the like.
[0032]
In the production method of the present invention, preferably, the modified polymer obtained by the above operation is further subjected to (D) an aliphatic hydrocarbon having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and (E) a dialkyl ketone. In the mixed solvent, a treatment is performed at a temperature of 40 to 90 ° C, and a vacuum heat treatment is performed at a temperature of 100 ° C or more. Here, the vacuum heat treatment refers to performing heat treatment in a state where the pressure is reduced to 0 to 100 Torr. The decompression method is not particularly limited.
When the processing temperature of the mixed solvent is lower than 40 ° C., the removal efficiency of the unreacted modifier (B) may be reduced due to insufficient swelling of the pellets. On the other hand, when it exceeds 90 ° C., it becomes difficult to carry out with a water or steam heating system, and the pellet properties may change (such as fusion).
When the temperature of the vacuum heat treatment is less than 100 ° C., the residual monomer in the pellet may not be sufficiently removed.
[0033]
Specific examples of the aliphatic hydrocarbon (D) include linear hydrocarbons such as hexane, heptane, octane and decane, and alicyclic hydrocarbons such as cyclohexane and decalin. Of these, hexane, heptane, and octane are preferable.
[0034]
The alkyl groups of the dialkyl ketone (E) may be the same or different. Carbon number of an alkyl group becomes like this. Preferably it is 3-20, More preferably, it is 3-6. Specific examples of the dialkyl ketone (E) include acetone, methyl ethyl ketone, methyl isobutyl ketone and the like. Of these, acetone and methyl ethyl ketone are preferable.
[0035]
In the present invention, the aliphatic hydrocarbon (D) is preferably 50 to 300 parts by weight, more preferably 80 to 150 parts by weight, and the dialkyl ketone (F) is preferably 100 parts by weight of the modified polymer. Is 50 to 300 parts by weight, more preferably 80 to 150 parts by weight.
[0036]
If a modified propylene polymer is produced by such a method, a general propylene resin can be used as a production raw material, and it is not necessary to use an ultrahigh molecular weight polymer or the like. In addition, since the decomposition rate of manufacturing raw materials is small and the amount of processing solvent used is reduced, production stability and cost reduction during manufacturing can be achieved, which is economical.
[0037]
Since the modified propylene polymer of the present invention has a high molecular weight and retains the properties of the raw material polymer, it can be used as a film or a molded product. Further, since it contains almost no unreacted modifier and the content of the low molecular weight substance is small, the bleed out of the low molecular weight substance is small. Therefore, it can be used for applications where bleeding out of a film or the like becomes a problem.
In addition to these properties, the modified propylene polymer of the present invention is suitable as a polyolefin nanocomposite production material because it has the properties of a large polar base content and a wide molecular weight distribution. If it is a modified polymer of this invention, even if it mix | blends abundantly at the time of manufacture of a nanocomposite, the fall of a physical property can be suppressed remarkably.
[0038]
【Example】
Examples of the present invention will be described below, but the present invention is not limited to these examples.
In addition, the measuring method of the various parameters in a present Example is as follows.
(1) Intrinsic viscosity of modified propylene polymer ([η]_a)
Measurements were made at 135 ° C. in tetralin.
(2) Molecular weight distribution of modified propylene polymer (Mw / Mn)
The measurement was performed with the following apparatus and conditions.
(GPC measuring device)
Column: TOSOGMMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
(Measurement condition)
Solvent: 1,2,4-trichlorobenzene
Temperature: 145 ° C
Flow rate: 1.0 ml
Sample concentration: 2.2 mg / ml
Injection volume: 160 microliters
Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver.1.0)
(3) Content of polar base contained in modified propylene polymer ([b])
The modified polymer is formed into a film having a thickness of 0.1 mm using a 5 t press molding machine (manufactured by Kodaira Seisakusho), the Fourier transform infrared absorption spectrum is measured using the film, and 1,700 to 1,800 cm.^-1It was determined by measuring the intensity of the infrared absorption peak due to the carbonyl group generated in
(4) Content of polar base part grafted in modified propylene polymer ([B])
5 g of the modified polymer was dissolved in 500 ml of paraxylene, and then precipitated in 5,000 ml of acetone to completely remove the unreacted modifier. This modified polymer was formed into a film in the same manner as in the case of the content [b], and obtained from a Fourier transform infrared absorption spectrum (solvent purification method).
(5) Intrinsic viscosity of raw material propylene polymer ([η]_r)
Measurements were made at 135 ° C. in tetralin.
(6) Melting point (Tm) of raw material propylene polymer
Using a differential scanning calorimeter (DSC) (Perkin Elmer, DSC7 (trade name)), 0.01 g of a sample was melted at 220 ° C. for 3 minutes in a nitrogen stream, and then cooled to 25 ° C. at 10 ° C./min. The peak top of the melting endothermic curve obtained by holding at 25 ° C. for 3 minutes and then raising the temperature at 10 ° C./min was determined as the melting point.
(7) Amount of components having a molecular weight of 1 million or more in the raw material propylene polymer (MW ≧ 1 million)
It calculated | required from the GPC curve obtained from the apparatus and conditions used by said (2).
(8) Melt index (M.I.) of the propylene homopolymer (a) used in the test examples
Based on JIS-K7210, it measured by resin temperature: 230 degreeC and load: 2.16kg.
[0039]
Production Example 1
[Synthesis of raw material propylene polymer]
(1) Preparation of prepolymerization catalyst component
After replacing the three-neck flask with a stirrer with an internal volume of 0.5 liters with nitrogen gas, dehydrated heptane: 400 ml, diethylaluminum chloride: 18 g, a commercially available sorbet-type titanium trichloride catalyst (Tosoh Finechem) 2 g) was added. The internal temperature was kept at 20 ° C., and propylene was introduced while stirring. After 80 minutes, stirring was stopped to obtain a prepolymerized catalyst component in which 0.8 g of propylene was polymerized per 1 g of the solid catalyst.
[0040]
(2) Synthesis of raw material propylene polymer
A stainless steel autoclave with a stirrer with an internal volume of 10 liters was sufficiently dried, and after nitrogen substitution, 6 liters of dehydrated heptane was added, and nitrogen in the system was substituted with propylene. Thereafter, hydrogen: 0.06 MPaG was added, and propylene was introduced while stirring. After the system was stabilized at an internal temperature of 65 ° C. and a propylene pressure of 0.75 MPaG, a heptane slurry containing 50 g of the prepolymerized catalyst component prepared in the above (1) in terms of solid catalyst was added: 50 ml, While continuously supplying propylene, polymerization was carried out at 65 ° C. for 2 hours.
[0041]
Next, the internal temperature was set to 50 ° C., the stirring was weakened, and depressurization was performed. Thereafter, hydrogen: 0.04 MPaG was added, and propylene was introduced while stirring. While propylene was continuously supplied at an internal temperature of 50 ° C. and a propylene pressure of 0.75 MPaG, polymerization was performed at 50 ° C. for 6 hours. After completion of the polymerization, 50 ml of methanol was added, and the temperature was lowered and the pressure was released. The entire contents were transferred to a filtration tank with a filter, heated to 85 ° C., separated into solid and liquid, and depressurized. Further, the solid part was washed twice with 6 liters of heptane at 85 ° C. and vacuum-dried to obtain 2.4 kg of a propylene polymer. Intrinsic viscosity of this polymer [η]_rWas 3.91 dl / g, the amount of the component having a molecular weight of 1 million or more was 29.8% by weight, and the melting point was 162 ° C. The catalytic activity per 1 g of the solid catalyst was 4.8 kg / g-cat.・ It was 8 hours. Propylene polymerization was repeated under the same conditions as this, and the obtained polymer was used as a raw material propylene polymer (PP-1).
[0042]
Production Example 2
[Synthesis of raw material propylene polymer]
(1) Preparation of solid catalyst component
After replacing the three-necked flask equipped with a stirrer with an internal volume of 0.5 liter with nitrogen gas, dehydrated octane: 60 ml and diethoxymagnesium: 16 g were added. After heating to 40 ° C. and adding 2.4 ml of silicon tetrachloride and stirring for 20 minutes, 1.6 ml of dibutyl phthalate was added. The temperature of the solution was raised to 80 ° C., and subsequently, 77 ml of titanium tetrachloride was added dropwise, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a contact operation. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. Next, 100 ml of dehydrated octane was added, and the temperature was raised to 125 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Further, 122 ml of titanium tetrachloride was added, and the mixture was stirred at an internal temperature of 125 ° C. for 2 hours to perform a second contact operation. Thereafter, the washing with 125 ° C. dehydrated octane was repeated 6 times to obtain a solid catalyst component.
[0043]
(2) Preparation of prepolymerization catalyst component
After replacing the three-necked flask with a stirrer with an internal volume of 0.5 liter with nitrogen gas, dehydrated heptane: 400 ml, triisobutylaluminum: 25 mmol, dicyclopentyldimethoxysilane: 2.5 mmol, (1) 4 g of the solid catalyst component prepared in (1) was added. Propylene was introduced with stirring at room temperature. After 1 hour, stirring was stopped to obtain a prepolymerized catalyst component in which 4 g of propylene was polymerized per 1 g of the solid catalyst.
[0044]
(3) Synthesis of raw material propylene polymer
A stainless steel autoclave with a stirrer having an internal volume of 10 liters was sufficiently dried, and after nitrogen substitution, dehydrated heptane: 6 liters, triethylaluminum: 15 mmoles, and dicyclopentyldimethoxysilane 0.4 mmoles were added. Nitrogen in the system was replaced with propylene. Propylene was introduced while stirring, and after the system was stabilized at an internal temperature of 80 ° C. and a propylene pressure of 0.80 MPaG, the prepolymerized catalyst component prepared in the above (2) was contained in an amount of 0.04 mmol in terms of Ti atom. Heptane slurry: Polymerization was carried out at 80 ° C. for 3 hours while adding 50 ml and continuously supplying propylene.
[0045]
Next, the internal temperature was set to 80 ° C., stirring was weakened, and depressurization was performed. Thereafter, hydrogen: 0.20 MPaG was added, and propylene was introduced while stirring. Polymerization was carried out at 80 ° C. for 2 hours while continuously supplying propylene at an internal temperature of 80 ° C. and a propylene pressure of 0.60 MPaG. After completion of the polymerization, 50 ml of methanol was added, and the temperature was lowered and the pressure was released. The entire contents were transferred to a filtration tank equipped with a filter, and the temperature was raised to 85 ° C. for solid-liquid separation. Furthermore, the solid part was washed twice with 6 liters of heptane at 85 ° C. and vacuum-dried to obtain 2.3 kg of a propylene polymer. Intrinsic viscosity [η] of this polymer_rWas 3.97 dl / g, the amount of the component having a molecular weight of 1 million or more was 19.4% by weight, and the melting point was 166 ° C. The catalytic activity per 1 g of the solid catalyst was 23.9 kg / g-cat.・ It was 5 hours. Propylene polymerization was repeated under the same conditions as this, and the resulting polymer was used as a raw material propylene polymer (PP-2).
[0046]
Production Example 3
[Synthesis of raw material propylene polymer]
In Production Example 2 (3), the pre-polymerization catalyst component prepared in Production Example 2 (2) was used in a heptane slurry containing 50 milliliters of 0.08 mmol in terms of Ti atoms, and the second stage polymerization was performed. Except not having carried out, it carried out similarly to manufacture example 2 (3), and obtained 2.5 kg of propylene polymers. Intrinsic viscosity of this polymer [η]_rWas 7.61 dl / g, the amount of the component having a molecular weight of 1 million or more was 41% by weight, and the melting point was 164 ° C. The catalytic activity per 1 g of the solid catalyst was 10.5 kg / g-cat.・ It was 3 hours. Propylene polymerization was repeated under the same conditions as this, and the resulting polymer was used as a raw material propylene polymer (PP-3).
[0047]
Example 1
Raw material propylene polymer (H100M (trade name), manufactured by Idemitsu Petrochemical Co., Ltd., intrinsic viscosity [η]_r: 2.94 dl / g, amount of component having a molecular weight of 1 million or more: 18.5 wt%, melting point: 162 ° C., PP-4): 100 parts by weight, maleic anhydride: 6 parts by weight, perbutyl Z (trade name, t-butyl peroxybenzoate, purity 98%, manufactured by NOF Corporation): 1.2 parts by weight, Irganox 1010 (trade name, manufactured by Ciba Specialty Chemicals): 0.06 parts by weight, Irgaphos 168 (trade name, Ciba) (Specialty Chemicals): 0.14 parts by weight, calcium stearate: 0.04 parts by weight were dry blended, further mixed and melt kneaded using a vented 32 mm twin screw extruder. The temperature of the twin-screw extruder at the time of mixing and melt-kneading was set to a hopper lower part: 40 ° C., a mixing zone (M zone): 80 ° C., a reaction zone (R zone): 170 ° C., and a die: 180 ° C. Each of these parts corresponds to the part given the reference number in FIG.
To the obtained pellet-like sample: 100 parts by weight, acetone: 85 parts by weight and heptane: 85 parts by weight were added, and the mixture was heated and stirred at 85 ° C. for 2 hours (implemented in a pressure resistant reactor). After the operation was completed, the pellets were collected with a wire mesh and vacuum-dried at 140 ° C. and 0.1 Torr for 20 hours to obtain a maleic anhydride-modified propylene polymer (pellet treatment method A). Table 1 and Table 2 show the blending conditions, production conditions, and analysis results.
[0048]
Example 2
A maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the blending amount of perbutyl Z was 1.8 parts by weight in Example 1. The results are shown in Tables 1 and 2.
[0049]
Example 3
In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the amount of perbutyl Z was 0.6 parts by weight. The results are shown in Tables 1 and 2.
[0050]
Example 4
In Example 1, instead of perbutyl Z, perbutyl I (trade name, t-butyl peroxyisopropyl monocarbonate, purity 98%, manufactured by NOF Corporation) was used, and the blending amount was 1 part by weight. In the same manner as in Example 1, a maleic anhydride-modified propylene polymer was synthesized. The results are shown in Tables 1 and 2.
[0051]
Example 5
In Example 1, Nyper BW (trade name, benzoyl peroxide, purity: 98%, manufactured by NOF Corporation) was used in place of perbutyl Z, and the blending amount was 0.8 parts by weight. Example 1 In the same manner, a maleic anhydride-modified propylene polymer was synthesized. The results are shown in Tables 1 and 2.
[0052]
Example 6
In Example 1, instead of perbutyl Z, Perkadox 14 / 40C (trade name, 1,3-bis- (t-butylperoxyisopropyl) benzene / calcium carbonate: 40/60 (weight ratio), Kayaku Akzo Corporation Manufactured): A maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that 3 parts by weight (actual amount of peroxide: 1.2 parts by weight) was used. The results are shown in Tables 1 and 2.
[0053]
Example 7
In Example 1, a maleic anhydride-modified propylene polymer was prepared in the same manner as in Example 1 except that the amount of maleic anhydride was 4.5 parts by weight and the amount of perbutyl Z was 0.9 parts by weight. Synthesized. The results are shown in Tables 1 and 2.
[0054]
Example 8
In Example 1, a maleic anhydride-modified propylene polymer was prepared in the same manner as in Example 1 except that the amount of maleic anhydride was 4.5 parts by weight and the amount of perbutyl Z was 0.6 parts by weight. Synthesized. The results are shown in Tables 1 and 2.
[0055]
Reference example 1
  In Example 1, a maleic anhydride-modified propylene polymer was prepared in the same manner as in Example 1 except that the amount of maleic anhydride was 4.5 parts by weight and the amount of perbutyl Z was 0.3 parts by weight. Synthesized. The results are shown in Tables 1 and 2.
[0056]
Example9
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the amount of maleic anhydride was 3 parts by weight and the amount of perbutyl Z was 0.5 parts by weight. . The results are shown in Tables 1 and 2.
[0057]
Example10
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the amount of maleic anhydride was 3 parts by weight and the amount of perbutyl Z was 0.8 parts by weight. . The results are shown in Tables 1 and 2.
[0058]
Reference example 2
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the amount of maleic anhydride was 3 parts by weight and the amount of perbutyl Z was 0.2 parts by weight. . The results are shown in Tables 1 and 2.
[0059]
Example11
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that PP-1 synthesized in Production Example 1 was used instead of PP-4. The results are shown in Tables 1 and 2.
[0060]
Example12
  In Example 1, maleic anhydride was used in the same manner as in Example 1 except that PP-2 synthesized in Production Example 2 was used instead of PP-4, and the blending amount of perbutyl Z was 1.5 parts by weight. A modified propylene polymer was synthesized. The results are shown in Tables 1 and 2.
[0061]
Example13
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the temperature of the mixing zone was 50 ° C. and the amount of perbutyl Z was 1.0 part by weight. The results are shown in Tables 1 and 2.
[0062]
Example14
  In Example 1, maleic anhydride modification was performed in the same manner as in Example 1 except that the temperature of the mixing zone was 60 ° C., the temperature of the reaction zone was 180 ° C., and the amount of perbutyl Z was 1.4 parts by weight. A propylene polymer was synthesized. The results are shown in Tables 1 and 2.
[0063]
Example15
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the processing temperature of the pellet sample was 70 ° C. and the vacuum drying temperature was 120 ° C. (pellet processing method B). . The results are shown in Tables 1 and 2.
[0064]
Example16
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that methyl ethyl ketone was used instead of acetone (pellet treatment method C) in the treatment of the pellet-like sample. The results are shown in Tables 1 and 2.
[0065]
Example17
  In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that hexane was used instead of heptane (pellet treatment method D) in the treatment of the pellet sample. The results are shown in Tables 1 and 2.
[0066]
Comparative Example 1
In Example 1, in place of PP-4, PP-5 (raw material propylene polymer, F704NP (trade name), manufactured by Idemitsu Petrochemical Co., Ltd., intrinsic viscosity [η]_rA maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that 1.67 dl / g, the amount of a component having a molecular weight of 1 million or more: 6.4 wt%, melting point: 163 ° C. was used. The results are shown in Tables 1 and 2.
[0067]
Comparative Example 2
In Example 1, a maleic anhydride-modified propylene polymer was synthesized in the same manner as in Example 1 except that the temperature of the mixing zone was 170 ° C and the temperature of the reaction zone was 230 ° C. The results are shown in Tables 1 and 2.
[0068]
Comparative Example 3
PP-3 synthesized in Production Example 3 was dry blended with 100 parts by weight of PP-3: 1 part by weight of maleic anhydride and 1 part by weight of Kayabutyl B, and melt-kneaded using a 35 mm twin screw extruder. The temperature of the twin screw extruder during melt kneading was 210 ° C. for all of the lower part of the hopper, the mixing zone, the reaction zone, and the die.
In this comparative example, a maleic anhydride-modified propylene polymer was obtained without processing the obtained pellet-shaped sample. The results are shown in Tables 1 and 2.
[0069]
[Table 1]
[0070]
Treatment A: Maleic anhydride-modified propylene polymer / heptane / acetone: 100/50/50 (weight ratio), 85 ° C., 2 hr → 140 ° C., 20 hr vacuum drying
Treatment method B: maleic anhydride modified propylene polymer / heptane / acetone: 100/50/50 (weight ratio), 70 ° C., 2 hr → 120 ° C., 20 hr vacuum drying
Treatment C: Maleic anhydride modified propylene polymer / heptane / methyl ethyl ketone: 100/50/50 (weight ratio), 85 ° C., 2 hr → 140 ° C., 20 hr vacuum drying
Treatment method D: maleic anhydride modified propylene polymer / hexane / acetone: 100/50/50 (weight ratio), 85 ° C., 2 hr → 140 ° C., 20 hr vacuum drying
[0071]
[Table 2]
[0072]
Test Examples 1-6 and Comparative Test Examples 1-5
[Preparation of inorganic filler-reinforced propylene polymer composition]
(A) Propylene homopolymer (J3000GP (trade name), manufactured by Idemitsu Petrochemical Co., Ltd., MI: 30 g / 10 min), (b) Modified propylene polymer blended in the blending ratio shown in Table 3 did. This blend was put into a hopper of a 35 mm diameter twin screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM35 (trade name)), and (c) glass fiber (CS03JAFT17 (trade name), manufactured by Asahi Fiber Glass Co., Ltd.). , Strand length: 3 mm, fiber diameter: 10 μm) is supplied by top feed from the middle of the extruder so as to have the blending ratio shown in Table 3, and melt-kneaded at a cylinder temperature of 230 ° C. to produce a composition. The extruded strand was cut to obtain inorganic filler-reinforced propylene polymer composition pellets.
[0073]
  In addition, as modified propylene polymer (b), the following b-1 to b-8 were used.
b-1: Maleic anhydride-modified propylene polymer synthesized in Example 1
b-2: Maleic anhydride-modified propylene polymer synthesized in Example 2
b-3: Maleic anhydride-modified propylene polymer synthesized in Example 7
b-4: Example12-Modified maleic anhydride-modified propylene polymer
b-5: Maleic anhydride-modified propylene polymer synthesized in Comparative Example 2
b-6: Maleic anhydride-modified propylene polymer synthesized in Comparative Example 3
b-7: Commercially available maleic anhydride-modified propylene polymer (Polybond 3200 (trade name), manufactured by Crompton, content of polar base: 48 mmol / kg,
        [Η]_a: 0.76 dl / g, Mw / Mn: 2.4)
b-8: Commercially available maleic anhydride-modified propylene polymer (Yumex 1010 (trade name), manufactured by Sanyo Chemical Co., Ltd., polar base content: 429 mmol / kg,
        [Η]_a: 0.19 dl / g, Mw / Mn: 4.1)
[0074]
[Evaluation of the physical properties]
This pellet was injection-molded using an injection molding machine at a cylinder temperature of 210 ° C. and a mold temperature of 50 ° C. to produce an ASTM standard test piece, and the following mechanical properties (1) to (4) were evaluated. . The evaluation results are shown in Table 3.
(1) Tensile strength at break: Conforms to ASTM D638
(2) Bending strength: Conforms to ASTM D790
(3) IZOD impact strength: Conforms to ASTM 256 (23 ° C, with notch)
(4) Thermal deformation temperature: Conforms to ASTM D648 (Load: 18.6 kgf)
[0075]
[Table 3]
[0076]
Since the composition of the comparative test example did not use the modified polymer satisfying the requirements of the present invention, the physical property value was lower than that of the composition of the test example.
[0077]
【The invention's effect】
According to the present invention, it is possible to provide a modified propylene polymer having an excellent balance between the molecular weight and the content of the acid component, a wide molecular weight distribution, and a low content of the unreacted acid component, and a method for producing the same.
[Brief description of the drawings]
FIG. 1 is a schematic view of a twin screw extruder.
[Explanation of symbols]
1 Lower hopper
2 Mixing zone (M zone)
3, 4 Reaction zone (R zone)
5 dice

Claims (6)

(A) propylene-based polymer having an intrinsic viscosity [η] _r measured in tetralin of 135 ° C. of 2 to 4 dl / g and a molecular weight of 1,000,000 or more, 10 to 50% by weight,
(B) a compound containing an ethylenic double bond and a polar group in the same molecule, and
(C) a radical initiator,
Mixed at a temperature of 40 to (melting point of the propylene-based polymer (A) −50) ° C.,
Melting and kneading at a temperature of the melting point of the propylene polymer (A) to 180 ° C.,
A method for producing a modified propylene polymer satisfying the following (1) to (4).
(1) Intrinsic viscosity [η] _a measured in tetralin at 135 ° C. is 0.8 to 2.0 dl / g
(2) The molecular weight distribution (Mw / Mn) is 3 or more. (3) The content [B] of the polar group derived from the compound (B) grafted in the modified propylene polymer, and the content [ B] and the total content [b] of the polar base portion derived from the unreacted compound (B) contained in the modified propylene-based polymer,
([B]-[B]) × 100 / [b] ≦ 2
Satisfy the relationship.
(4) The content [B] is 80 to 300 mmol / kg. Wherein the intrinsic viscosity [eta] _a modified propylene-based polymer, the ratio of the intrinsic viscosity [eta] _r of the propylene polymer which is a raw material _{(A) ([η] a} / [η] r) is, The method for producing a modified propylene polymer according to claim 1, which is 0.3 or more. The method for producing a modified propylene polymer according to claim 1 or 2 , wherein the compound (B) is an unsaturated carboxylic acid and / or a derivative thereof. The modification | denaturation as described in any one of Claims 1-3 with which the said content [B] and the said content [b] satisfy | fill the relationship of ([b]-[B]) * 100 / [b] <= 1. A method for producing a propylene-based polymer. Further, (D) in a mixed solvent of an aliphatic hydrocarbon having 6 to 20 carbon atoms and (E) a dialkyl ketone, the treatment is performed at a temperature of 40 to 90 ° C.
The method for producing a modified propylene-based polymer according to any one of claims 1 to 4, which is subjected to vacuum heat treatment at a temperature of 100 ° C or higher. The melting point of the propylene polymer (A) is 140 to 170 ° C. The method for producing a modified propylene polymer according to any one of claims 1 to 5 .