CN100478365C

CN100478365C - Acid-modified propylene polymer, process for producing the same, film and multilayered article formed thereby

Info

Publication number: CN100478365C
Application number: CNB028210948A
Authority: CN
Inventors: 大西陆夫; 巽富美男; 津乘良一; 神泽贡; 杉田泰久
Original assignee: Prime Polymer Co Ltd
Current assignee: Prime Polymer Co Ltd
Priority date: 2001-10-23
Filing date: 2002-10-23
Publication date: 2009-04-15
Anticipated expiration: 2022-10-23
Also published as: CN1575305A; WO2003035706A1; JPWO2003035706A1; JP4614659B2

Abstract

An acid-modified propylene polymer satisfying the following (1) to (4). (1) The intrinsic viscosity [eta] as measured in decalin at 135 DEG C: 1 dL/g or higher. (2) The ratio of acid content to the number of polymer chains ss value: from 0.5 to 3.0. (3) The content of components having molecular weight Mw of 10,000 or lower LP content: 0.5 wt.% or lower. (4) The content of unreacted acid compound containing ethylenic double bond and polar group in the same molecule: 2 wt.% or lower. The polymer has a high molecular weight and retains properties of the raw propylene polymer. It is hence usable as a film or molding.

Description

Modified propylene homopolymer and production method thereof, by its film that makes and laminate

Technical field

The present invention relates to sour modification propene polymer, produce its method, the multi-layered board that contains the composite composition of described polymkeric substance and other polymkeric substance and contain described polymkeric substance.

Because the propene polymer of described sour modification has high molecular weight and keeps the character of original propene polymer, makes film or molding so the propene polymer of sour modification of the present invention is suitable for.

In addition, the propene polymer of the preferred sour modification of the present invention does not conform to unreacted acid and low-molecular-weight component basically, so there be not oozing out of low-molecular-weight component in it.

So the propene polymer of sour modification of the present invention is applicable to the various application that usually produce problems such as oozing out from film.

In addition, the invention still further relates to multi-layered board, more particularly, relate at vapour lock layer and supporting and fabulous fusible multi-layered board is arranged between the resin layer with high vapour lock.

Background technology

Propene polymer by undersaturated carboxylic acid or acid anhydrides are added to the sour modification for preparing in the propene polymer and preparation method thereof is known.

The propene polymer of many sour modifications is the affixtures that are used for the high acid content of lower molecular weight of modified resin character.

So the propene polymer of sour modification is not directly as molding.

On the other hand, having done some effort produces and still keeps the propylene polymerization properties and the reactive polymkeric substance of good chemical is arranged.

Japanese Patent postpones open application form Sho 63-90511 and discloses the technology of removing the low-molecular-weight component of by-product with unsaturated carboxylic acid or anhydride modified propene polymer the time by the following method, its quantity about 10% also has detrimentally affect to the character that generates polymkeric substance: (1) is dissolved in a kind of solvent with the propene polymer of modification, the deposition or the method for crystallization in a kind of poor solvent then, or (2) are under refluxing, with the polymkeric substance of specific solvent extraction modification.But, in this technology, a large amount of low-molecular-weight component of by-product.

Japanese Patent postpones open application form Hei 2-185505 and discloses the technology of removing unreacted unsaturated carboxylic acid or acid anhydrides under up to 120 ℃ temperature up to the dione compounds of 30 times of the modified propylene polymer quantity that generates of using.

In addition, Japanese Patent postpones open application form Hei 4-202202 and discloses the technology of removing unreacted unsaturated carboxylic acid or acid anhydrides up to the mixed solvent of the diketone of 7 times of the modified propylene polymer quantity that generates and aromatic hydrocarbons under 90-110 ℃ high temperature of using.

But there are some shortcomings in back two kinds of technology, not only comprise and will use a large amount of solvents, but also comprise because high treatment temp makes the modified propylene polymer of generation that fused danger be arranged.

Therefore conventional, produce and do not conform to basically that the character that generates polymkeric substance is had the method for the sour modified propylene polymer of dysgenic low-molecular-weight component by product is unknown, even to its research.

Particularly, with a small amount of solvent the method for removing the compound that in same molecular, contains unreacted second olefinic double bond and polar group under the mitigation condition and the acid amount that extremely long-pending control is added and resin properties for example between molecular weight and the regularity STUDY ON THE EQUILIBRIUM seldom know.

So far, the propene polymer of sour modification has been used as the unmodified resin plate of container, for example bowl that is used for food, beverage, medicine etc. or the dish made from thermoplastic resin board molding.

The container of these hot briquettings needs good vapour lock, particularly to all gases vapour lock of oxygen, water vapor and carbonic acid gas for example, so that prevent material oxidation, moisture absorption wherein and rot, thereby keeps its quality.

Propene polymer is owing to its fabulous intensity, thermotolerance and the transparency etc., and they are widely used in various application, for example container and wrapping material.But propene polymer does not have enough vapour locks.Owing to this reason, usually that propene polymer and other vapour lock film of moulding resin, aluminium foil, al deposition hot in nature etc. are laminated together.

In order to produce the propene polymer sheet material of good vapour lock, the bonding coat that the propene polymer of propene polymer skin by sour modification made be laminated to the vapour lock resin for example two lip-deep methods of the internal layer that makes of ethylene/vinyl alcohol copolymer (EVOH) be known.

But when traditional sour modified propylene polymer was used as bonding coat between the gentle resistive layer of skin, described bonding coat had only low bond strength.If when the container that is made by such laminated plate material is subjected to being out of shape, usually between layer, occur peeling off or separating, make its vapour lock variation.

In order to address the above problem, use the propene polymer of sour modification traditionally.

For example, postpone among open application form Sho 64-38232 and 64-38233 and the Japanese Patent Sho 60-34461 at Japanese Patent, the polyolefine that has proposed to use special modification as the laminate adhesive resin, is a laminate that the resin on basis and polymeric amide or EVOH make by polyolefine as the resin on basis.

But disclosed modified polyolefin is the modified product of ethylene/alpha olefin polymer for the resin on basis.In addition, because the polyolefine as basal layer is a based copolymers for ethene only for basic resin also is limited to basically, therefore produce such problem, promptly with comparing of being made by propene polymer, the laminate of generation is variation aspect thermotolerance and rigidity usually.

In addition, Japanese Patent postpones open application form Hei 9-111069 and discloses the method for using modified propylene polymer to combine with other modified propylene polymer as the bonding coat resin.But because modified propylene polymer has low molecular weight, bonding coat does not have sufficiently high bond strength; And owing to use the modified propylene polymer of two or more kind, thereby further improved cost.

The film of lamination aluminium foil or al deposition with the method that obtains vapour lock in, produce some problems like this, for example, be not suitable for electric furnace and be difficult to reclaim resin because the opaque material that makes be cannot see.

And Japanese Patent postpones open application form Hei 8-238711 and discloses a kind of vapour lock laminate that is coated to the film that forms on the product surface of polymer molding by the aqueous solution with alkali metal silicate solutions and coupler composition that comprises.

Though can the described vapour lock laminate of low cost production, and do not need for example vapor deposition of special steps, the laminate that makes is usually in vapour lock and still can not be satisfactory aspect strength of coating and the water tolerance.

In view of these problems, finished the present invention.An object of the present invention is to provide a kind of propene polymer that high-molecular weight acid modification is arranged, it is substantially free of has dysgenic low-molecular-weight component by product to its character, and do not conform to unreacted unsaturated acid or acid anhydrides basically, and a kind of method of the propene polymer of producing described sour modification is provided and contains the propene polymer of described sour modification and the composite composition of other polymkeric substance.

Another object of the present invention is to provide a kind of like this use that the vapour lock multi-layered board of the sour modified propylene polymer production of high bond strength is arranged between vapour lock layer and substrate resin layer, the vapour lock layer can or not peel off from the base material separation basically, or do not have basically defective for example crackle occur therein, even be out of shape or be placed on for a long time heating and super-humid conditions following time by the container that its is produced, so still keep high vapour lock.

Detailed Description Of The Invention

Because to addressing the above problem the broad research of carrying out, the inventor finds, above-mentioned purpose reaches by the propene polymer with high-molecular weight acid modification, the acid content of its binding to one polymer chain is limited to a specified range, does not conform to basically that its character is had dysgenic molecular weight is 100000 or lower low-molecular-weight component.

In addition, the inventor finds that also described sour modified propylene polymer should be produced by the following method: mutually blend and melt-kneaded are produced the propene polymer of the specific ortho acid modification of specific fusing point with propene polymer (A), radical initiator (B) and the compound (C) that contains second olefinic double bond and polar group in same molecular; Then with the propene polymer and the C of the ortho acid modification that generates ₆-C ₂₀Aliphatic series and/or clicyclic hydrocarbon (D) contact with the mixed solvent of dialkyl ketone (E), then with C ₁-C ₈The mixture of alcohol (F), dialkyl ketone (E) or component (E) and (F) contacts.On the basis of above-mentioned discovery, finished the present invention.

And the inventor finds that also above-mentioned purpose also reaches by the multi-layered board with such laminar structure, is about to the bonding coat that layer that the vapour lock resin the makes propene polymer by above-mentioned specific sour modification make and is adhered on the propylene polymer.On the basis of these discoveries, finish the present invention.

Therefore, the invention provides:

1. one kind is satisfied the following propene polymer that requires the sour modification of (1)-(4):

(1) limiting viscosity [η] (in perhydronaphthalene 135 ℃ of measurements): 1 deciliter/gram or higher;

(2) ratio (β value) of acid content and polymer chain number: 0.5-3.0;

(3) molecular weight is 10000 or lower component concentration (LP content): 0.5% (quality) or lower; And

The content of (4) unreacted acid (compound that in same molecular, contains second olefinic double bond and polar group): 2% (quality) or lower.

2. according to the propene polymer of the sour modification of heading, it is 2.5 or lower that the propene polymer of wherein said sour modification satisfies (5) molecular weight distribution (Mw/Mn);

3. according to the propene polymer of the sour modification of heading, the content that the propene polymer of wherein said sour modification satisfies (6) unreacted acid (compound that contains second olefinic double bond and polar group in same molecular) is analysis limit or lower;

4. method of producing the propene polymer of sour modification, described method comprises:

With propene polymer (A), radical initiator (B) and the compound (C) that contains second olefinic double bond and polar group in same molecular mutually blend and melt-kneaded, producing fusing point is the propene polymer of 145-170 ℃ ortho acid modification; Then with the propene polymer and the C of the ortho acid modification that generates ₆-C ₂0 aliphatic series and/or clicyclic hydrocarbon (D) contact under 40-90 ℃ with the mixed solvent of dialkyl ketone (E), then with C ₁-C ₈The mixture of alcohol (F), dialkyl ketone (E) or component (E) and (F) contacts.

5. according to the method for above-mentioned the 4th aspect, wherein with the propene polymer (A) and the radical initiator (B) of 0.01-1 part quality and the compound that in same molecular, contains second olefinic double bond and polar group (C) blend of 0.1-10 part quality of 100 parts of quality;

6. according to the method for above-mentioned the 4th aspect, wherein dialkyl ketone (E) is 0.5 or lower with the mass ratio of the propene polymer of ortho acid modification;

7. according to the method for above-mentioned the 4th aspect, wherein dialkyl ketone (E) is an acetone;

8. according to the method for above-mentioned the 4th aspect, wherein propene polymer (A) satisfies following (7)-(10) that require:

(7) limiting viscosity [η] (in perhydronaphthalene 135 ℃ of measurements): 2.8 deciliter/gram or higher;

(8) the soluble component concentration of boiling heptane: 2% (quality) or lower;

(9) molecular weight distribution (Mw/Mn): 5 or lower; With

(10) molecular weight Mn is 1000000 or higher component concentration: 25% (quality) or higher;

9. according to the method for above-mentioned the 4th aspect, wherein propene polymer (A) satisfies following (11)-(13) that require:

(11) ¹³The pentad[mmmm that CNMR measures] cut (9 peak area method): 80% (quality) or higher;

(12) ¹³The δ value of CNMR (interior mark: TMS): 17.2,17.6,30.6,31.6,35.9,36.0,38.6 and the 42.3ppm place signal is arranged; And

(13) mean particle size of propene polymer (A): 200-3000 micron;

10. the propene polymer of a method of describing with above-mentioned the 4th aspect sour modification of producing;

11. film that makes with the propene polymer molding of the sour modification of the method production of the above-mentioned the 1st or 4 aspects description;

12. laminate that contains the macromolecule membrane of the film above-mentioned the 11st aspect described and the superincumbent polar functionalities of lamination;

13. according to the laminate of above-mentioned the 12nd aspect, wherein the macromolecule membrane of polar functionalities is a polyamide layer;

14. multi-layered board that contains with lower floor:

The bonding coat (a) that the propene polymer of the sour modification that the method for describing with the above-mentioned the 1st or 4 aspects is produced makes;

By vapour lock resin (G) make the layer (b); And

The layer (c) that makes by propene polymer (A '),

Described layer (b) and (c) bonding mutually by bonding coat (a);

15. the propene polymer according to above-mentioned the 14th aspect is the multi-layered board on basis, it contains:

The bonding coat (a1, a2) that the propene polymer of the sour modification that the method for describing with the above-mentioned the 1st or 4 aspects is produced makes;

The internal layer (b) that makes by vapour lock resin (G); And

Two skins (c1, c2) that make by propene polymer (A '),

Described skin (c1, c2) is adhered to the both sides of internal layer (b) respectively by bonding coat (a1, a2); And

16. the propene polymer according to above-mentioned the 15th aspect is the multi-layered board on basis, wherein said multi-layered board is by producing skin (c1), bonding coat (a1), internal layer (b), bonding coat (a2) and skin (c2) by the mutual successively lamination of this order.

Implement the preferred embodiments of the invention

The propene polymer of sour modification of the present invention satisfies following (1)-(4) that require, also further preferred following require (5) and/or (6) of satisfying:

(1) limiting viscosity [η] (in perhydronaphthalene 135 ℃ of measurements): 1.0 deciliter/gram or higher, preferred 1.2 deciliter/gram or higher;

(2) ratio (β value) of acid content and polymer chain number: 0.5-3.0;

(3) molecular weight of measuring with gel permeation chromatography (GPC) is 10000 or lower component concentration: 0.5% (quality) or lower, preferred 0.2% (quality) or lower;

The content of (4) unreacted acid (compound that in same molecular, contains second olefinic double bond and polar group): 2% (quality) or lower;

(5) molecular weight distribution (Mw/Mn): 5 lower, preferred 2.8 or lower, more preferably 2.3 or lower; And

(6) content of above-mentioned unreacted acid: analysis limit or lower.

When the limiting viscosities [η] of measurement were less than 1.0 deciliter/gram under 135 ℃ in perhydronaphthalene, the polymkeric substance of generation was having variation considerably aspect the mechanical properties that is fit to the propene polymer requirement.

In addition, when propene polymer and the kneading of other polymer melt, owing between the molecular weight huge difference is arranged, polymkeric substance may not have good consistency mutually.

In addition, propene polymer may not be molded as film.Even such propene polymer is made film and be used as bonding coat in multi-layered board, but the multi-layered board that generates usually has sizable variation aspect the bond strength between each layer.

When being used for injection moulding-moulded parts, the limiting viscosity of the propene polymer of sour modification [η] is preferably the 1-1.8 deciliter/gram, and when being used for film, its limiting viscosity [η] is preferably the 1.5-3 deciliter/gram.

Acid content in the propene polymer of acid modification is calculated as follows.That is to say, the propene polymer of the sour modification that makes is made film, then its fourier transform infrared absorption spectrum of the measured thin film that will so make.

For example, carboxylic acid for example the content of maleic anhydride obtain in order to following method.

Just, the propene polymer bead of just sour modification is hot pressed into the about 0.2 millimeter film of thickness under 220 ℃, so that measure the infrared absorption peak intensity that belongs to carbonyl in 1700-1800 centimetre-1 scope with fourier transform infrared spectroscopy view (FT-IR).

The calibration curve that is used for calculating from the infrared absorption peak intensity of measuring acid content makes in order to the below method: the blended mixts that will be used for the unsaturated carboxylic acid of modified-reaction or acid anhydrides and Powdered unmodified propylene polymer carries out similar FT-IR and measures.

The ratio (hereinafter referred to as " β value ") of acid content and polymer chain number refers to acid content (moles per gram) and ratio by the polymer chain number (moles per gram) of number-average molecular weight Mn (with gel permeation chromatography described below (GPC) method measurement) calculating.The β value is that 1 finger, 1 molecule unsaturated carboxylic acid is added on 1 polymer chain.

When the β value less than 0.5 the time, have the polymer molecule that is not adhered in a large number on the vapour lock resin (G).So,, need the quantity of the modified propylene polymer of raising blend, thereby cause method uneconomical in order to obtain to the enough bond strengths of resin.

The β value needs contain in a large number the compounds (C) of second olefinic double bond and polar group in same molecular greater than the production of 3.0 modified propylene polymer, not only make method uneconomical, and, also make the serious variation of character of the propene polymer of generation owing to the existence that is helpless in a large number vapour lock resin (G) adherent grafting molecule.

The β value is 0.8-2.5,0.9-2.0 most preferably more preferably.

Calculate from weight-average molecular weight Mw and the number-average molecular weight Mn that the molecular weight of measuring propene polymer with the GPC method under following equipment and condition obtains respectively with molecular weight and molecular weight distribution (Mw/Mn) that gel permeation chromatography (hereinafter referred to as " GPC ") is measured:

Gpc measurement equipment

Chromatographic column: TOSOGMHHR-H (S) HT

Detector: the RI detector of liquid chromatograph " WATERS 150C "

Measuring condition

Solvent: 1,2, the 4-trichlorobenzene

Temperature: 145 ℃

Flow velocity: 1.0 ml/min

Sample concentration: 2.2 mg/ml

The sample size of using: 160 microlitres

Calibration curve: general calibration curve

Routine analyzer: HT-GPC (Ver.1.0)

When the molecular weight with gpc measurement is 10000 or lower component concentration when surpassing 0.5% (quality), the modified propylene polymer of generation usually character, outward appearance and practicality for example the binding property on molded article surface and ooze out aspect variation.

Molecular weight be 10000 or lower component concentration be preferably 0.2% (quality) or lower, more preferably 0.1% (quality) or lower.

When molecular weight distribution (Mw/Mn) surpassed 5, because a large amount of low-molecular-weight components are wherein arranged, the propene polymer of the sour modification of generation had been used for the multi-layered board variation aspect for example exudative or binding property of various character of being everlasting often.

Molecular weight distribution (Mw/Mn) be preferably 3.0 or lower, more preferably 2.8 or lower.

When molecular weight distribution (Mw/Mn) becomes too hour, the β value usually surpasses 3.0.For fear of this problem, molecular weight distribution (Mw/Mn) most preferably is 1.9-2.5.

Unreacted acid content refers in the propene polymer of sour modification the quantity of unreacted still (promptly not binding to the propylene) unsaturated carboxylic acid or acid anhydrides, and it is measured with above-mentioned acid content measuring method.

The content of above-mentioned unreacted acid calculates by following formula to the acid content (B) on the propylene with acid content (A) and binding in the propene polymer bead of the sour modification of identical acid content measuring method mensuration:

Unreacted acid content (%)=[100x (A-B)]/A

For example, [100x (A-B)]/A≤unreacted acid content of 2 expressions is 2% or lower.

Acid content (B) on the propylene of binding in the propene polymer bead of sour modification obtains in order to method down.

Under agitation, propene polymer bead and 0.25 2,6 di tert butyl 4 methyl phenol (BHT) that restrains as antioxidant with the sour modification of about 5 grams in 0.5 liter of p-Xylol are heated to 130 ℃, and are dissolved in wherein fully.

The p-Xylol solution of the propene polymer of the sour modification that so makes is poured in 4 liters of acetone, so that make solid crystallization and deposition, subsequent filtration.

With the solid air drying that makes, then 130 ℃ of following vacuum-dryings 6 hours.

With above-mentioned method, can remove unreacted unsaturated carboxylic acid (not binding to the propylene) and/or acid anhydrides fully.

Acid content in the purified product that so makes (B) is measured with the identical FT-IR method of as above using.

For analysis limit or lower unreacted acid content refer to that (A) value is in the analytical error scope of (B) value.

In the present invention, unreacted acid content preferably is not more than analysis limit.

The fusing point of sour modified propylene polymer of the present invention is preferably 145-170 ℃, more preferably 155-170 ℃.

When the fusing point of the propene polymer of sour modification was lower than 145 ℃, the polymkeric substance of generation is variation aspect thermotolerance or rigidity usually.

When the fusing point of the propene polymer of sour modification surpassed 170 ℃, it is too little that the acid content in the polymkeric substance of generation usually becomes, and makes consistency variation with other polymkeric substance.In addition, may not improve stripping strength between each layer with the propene polymer of described sour modification as the multi-layered board of bonding coat.

The fusing point of representing the propene polymer of sour modification with the summit that observes in the fusion endothermic curve, the following sequential steps of described curve negotiating makes: with sample fusion 3 minutes in nitrogen gas stream under 220 ℃, sample is cooled to 25 ℃ with 10 ℃/minute rate of temperature fall, sample was kept 3 minutes down at 25 ℃, and then, measure with differential scanning calorimeter (DSC) with the heating of 10 ℃/minute temperature rise rate.

The preferred method of the propene polymer of the above-mentioned sour modification of production the present invention is described subsequently.

Just, the method of the propene polymer of the above-mentioned sour modification of production the present invention may further comprise the steps: with propene polymer (A), radical initiator (B) and the compound (C) that contains second olefinic double bond and polar group in same molecular mutually blend and melt-kneaded, producing fusing point is the propene polymer of 145-170 ℃ ortho acid modification; Then with the propene polymer and the C of the ortho acid modification that generates ₆-C ₂₀Aliphatic series and/or clicyclic hydrocarbon (D) contact under 40-90 ℃ with the mixed solvent of dialkyl ketone (E), then with C ₁-C ₈The mixture of alcohol (F), dialkyl ketone (E) or component (E) and (F) contacts.

Propene polymer (A) can be alfon or propylene and a small amount of other monomeric multipolymer.

In addition, multipolymer can be random copolymers or segmented copolymer.

In propene polymer (A), can comprise C with other monomeric example of copolymerization of propylene ₂-C ₂₀, preferred C ₂-C ₁₀Alpha-olefin, for example ethene, 1-butylene, 4-methyl-1-pentene and 1-laurylene; Vinyl compound, for example vinylbenzene, vinyl cyclopentenes, vinyl cyclohexane and vinyl norbornene; Ester class, for example vinyl acetate; Unsaturated organic acid or derivative, for example maleic anhydride; Conjugated diolefine; Unconjugated polyenoid, Dicyclopentadiene (DCPD), 1 for example, 4-hexadiene, two cyclooctadiene, methene norbornene and 5-ethylidene-2-norbornene etc.

Two or more can while and copolymerization of propylene in these monomers.

Be generally 10% (quality) or lower, preferred 5% (quality) or lower with other monomeric content of copolymerization of propylene.

Propene polymer (A) can be produced in the presence of known catalysts, for example the Ziegler-Natta catalyst of being made up of titanous chloride and alkylaluminium cpd that makes with currently known methods and by the composite catalyst of magnesium-containing compound and titanium-containing compound.

Propene polymer (A) is for example preferred with such method production, and wherein in the presence of the catalyzer of the high taxis propene polymer of production, propylene is pressed the two-step reaction polymerization by homopolymerization or propylene and other monomer.

The limiting viscosity [η] of propene polymer (A) is preferably 2.8 deciliter/gram or higher, as (the requiring (6)) of measuring under 135 ℃ in the naphthane solvent.

When limiting viscosity [η] less than the propene polymer (A) of 2.8 deciliter/gram during as raw material, the β value of the propene polymer of the sour modification that generates is usually less than 0.8, molecular weight distribution (Mw/Mn) is greater than 2.5, molecular weight be 10000 or lower component concentration greater than 0.5% (quality).

In addition, when the propene polymer of so sour modification during as bonding coat, the multi-layered board that makes is variation aspect the plunger bond strength between each layer usually.

The limiting viscosity [η] of propene polymer (A) is preferably 4.0 deciliter/gram or higher, more preferably 6.0 deciliter/gram or higher.

To the restriction particularly of the upper limit of the limiting viscosity [η] of propene polymer (A), as long as when producing the propene polymer of sour modification, propene polymer (A) can with other main ingredient melt-kneaded.Consider to be easy to the melt-kneaded step preferred 20 deciliter/gram of the upper limit of the limiting viscosity [η] of propene polymer (A) or lower, more preferably 10 deciliter/gram or lower.

Propene polymer (A) contains (7) so soluble component of boiling heptane of quantity, preferred 2% (quality) or lower, more preferably 0.5% (quality) or lower, analysis limit or lower most preferably.

This just means, the quantity (it is essentially analysis limit or lower) in 10 ± 0.002 gram scopes of the residual propene polymer that obtains later on for 5 times with the extractor extraction 10.000 gram propene polymers of Soxhlet.

Under the boiling analyzable situation of content of the soluble component of heptane in propene polymer (A), the propene polymer of the sour modification that makes with such propene polymer (A) is usually in variation aspect rigidity and the thermotolerance; And the film that the propene polymer molding by described sour modification makes etc. usually produce some problems that for example resemble oozing out.

It is 5 or lower that propene polymer (A) preferably satisfies (8) molecular weight distribution (Mw/Mn).

When the molecular weight distribution (Mw/Mn) of propene polymer (A) surpassed 5, it was 10000 or lower component greater than the molecular weight (Mw) of 0.5% (quality) that the propene polymer of the sour modification of generation usually contains its quantity.

It is 1000000 or higher component that propene polymer (A) contains (9) molecular weight (Mw), preferred 25% (quality) of its quantity or higher, more preferably 25-50% (quality).

When molecular weight (Mw) is 1000000 or higher components contents during less than 25% (quality), it is 10000 or lower component that the propene polymer of the sour modification of generation usually contains molecular weight (Mw) that its quantity surpasses 0.5% (quality).

The molecular weight (Mw) and the molecular weight distribution (Mw/Mn) of propene polymer (A) are measured with the same procedure of above-mentioned use.

(A) do not have concrete restriction to propene polymer, as long as its pentad[mmmm] cut is 80% (quality) or higher (requiring (10)).

The pentad[mmmm of propene polymer (A)] cut is preferably 90% (quality) or higher, more preferably 94% (quality) or higher.

Because the taxis of propylene chain becomes higher, propene polymer has more crystalline.So, have high taxis, be that the use of the propene polymer of high crystalline can be produced for example propene polymer of rigidity and intensity and stable on heating sour modification of fabulous mechanical properties.

The pentad[mmmm of Shi Yonging in the present invention] cut refers to that propene polymer carries out ¹³The ratio that belongs to area that the signal of the unitary meso cut of pentad occupies and the total area of 9 signals that in the 19.0-22.5ppm scope, observe when C-NMR measures at the 21.8ppm place.

Measure above-mentioned pentad[mmmm under the following conditions in order to following equipment] cut.

Equipment: Nippon Denshi Co., JNM-EX 400 types that Ltd. provides ¹³The C-NMR instrument;

Method: the proton method of uncoupling fully;

Sample concentration: 220 milligrams/3 milliliters;

Solvent: 1,2, the mixed solvent of 4-trichlorobenzene and heavy benzol (volume ratio: 90: 10);

Measure temperature: 130 ℃;

Pulse width: 45 °;

Pulse repetition time: 4 seconds; And

Cumulative frequency: 1000 times

Propene polymer (A) preferably satisfy (11) 17.2,17.6,30.6,31.6,35.9,36.0,38.6 and the 42.3ppm place have as the δ value ¹³C-NMR signal (interior mark: TMS).

When signal did not exist, above-mentioned β value usually reduced, and the quantity that adds acid usually descends.

Propene polymer (A) preferably has the mean particle size of (12) 200-3000 micron.

When the mean particle size of propene polymer (A) surpasses above-mentioned scope, the propene polymer of the sour modification of generation usually at melt index, add the aspect instabilities such as quantity of acid.

Propene polymer (A) preferably satisfies all requirements (4)-(9), more preferably further meet the demands (10)-(12).

The example of radical initiator (B) comprises the peroxidation butane, α, α-two (tert-butyl hydroperoxide) diisopropyl benzene, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, the peracetic acid tertiary butyl ester, the diethyl peroxide ra-butyl acetate, peroxidation isopropylformic acid tertiary butyl ester, the secondary sad tertiary butyl ester of peroxidation, peroxidation valeric acid tertiary butyl ester, peroxidation valeric acid cumyl ester, peroxidation phenylformic acid tertiary butyl ester, peroxidation phenylacetic acid tertiary butyl ester, the tert-butyl peroxide isopropyl benzene, peroxidation two uncle's butane, 1,1-di-tert-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 1, the 1-cyclohexane di-tert-butyl peroxide, 2,2-two (tert-butyl hydroperoxide) butane, lauroyl peroxide, 2,5-dimethyl-2,5-two (peroxide benzoate) hexin-3,1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 3-, 1, two (tert-butyl hydroperoxide sec.-propyl) benzene of 4-, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexin-3,2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, 2,4,4-tri-methyl-amyl-2-hydroperoxide, the hydroperoxidation diisopropyl benzene, Cumene Hydroperoxide 80,4,4-di-tert-butyl peroxide valeric acid tertiary butyl ester, peroxidation hexahydrophthalic acid di-t-butyl ester, peroxidation nonane diacid di-t-butyl ester, peroxidation 3,3,5-tri-methyl hexanoic acid tertiary butyl ester, peroxidation sec.-propyl formic acid tertiary butyl ester, succinic acid peroxide, vinyl three (tert-butyl hydroperoxide) silane etc.

In these radical initiators (B), 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexin-3, peroxidation diisopropyl benzene, α, α-two (tert-butyl hydroperoxide) diisopropyl benzene, 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane, peroxidation phenylformic acid tertiary butyl ester and peroxidation-2 ethyl hexanoic acid tertiary butyl ester are preferred.

By 100 parts of quality propene polymers (A), the quantity of the radical initiator that uses (B) is 0.01-1 part quality, preferred 0.05-0.25 part quality.

When the quantity of the radical initiator (B) that uses surpassed 1 part of quality, the limiting viscosity of the propene polymer of the sour modification of generation [η] was usually less than 1 deciliter/gram, and molecular weight be 10000 or the quantity of lower component usually surpass 0.5% (quality).

When the quantity of the radical initiator (B) that uses during less than 0.01 part of quality, owing to add the unsaturated carboxylic acid or the acid anhydrides of lesser amt, the molecular weight distribution of the propene polymer of the sour modification of generation (Mw/Mn) usually surpasses 2.5.

The example that contains the compound (C) of second olefinic double bond and polar group in same molecular comprises maleic anhydride, toxilic acid, maleic acid ester, the compound that maleinamide and N-thereof replace, maleic acid derivatives is maleate for example, fumaric acid, fumarate, fumaric acid derivatives is fumarate for example, itaconic anhydride, methylene-succinic acid, derivatives from itaconic acid is itaconate for example, vinylformic acid, acrylate, acrylamide, acrylic acid derivative is acrylate for example, methacrylic acid, methacrylic ester, Methacrylamide, methacrylic acid derivative is methacrylate and glycidyl methacrylate for example, α-Yi Jibingxisuan, tetrahydrophthalic acid, the methyl tetrahydrophthalic acid, citraconic acid, citraconic anhydride, Ba Dousuan, iso-crotonic acid, nadic acid, nadic acid anhydrides etc.

In these acid and acid anhydrides, maleic anhydride, vinylformic acid, methacrylic acid etc. are preferred.

By 100 parts of quality propene polymers (A), the consumption that contains the compound (C) of second olefinic double bond and polar group in same molecular can be 0.1-10 part quality, preferred 0.2-2 part quality usually.

When the consumption of compound (C) surpassed 10 parts of quality, the quantity of unreacted compound (C) usually increased.When the consumption of compound (C) during less than 0.1 part of quality, owing to add the compound (C) of lesser amt, the β value is usually less than 0.8.

Simultaneously, propene polymer in sour modification is laminated on other polymeric film, promptly in the multi-layered board that comprises the vapour lock layer, be used as under the situation of bonding coat, by 100 parts of quality propene polymers (A), the consumption of the compound of adding (C) is preferably 0.05-1 part quality, more preferably 0.1-0.5 part quality.

When the consumption of compound (C) too hour, the quantity of the grafting group of introducing by graft reaction usually descends, and when being used for multi-layered board, the polymkeric substance of generation is variation aspect plunger bond strength usually, so that the multi-layered board that makes variation aspect physical properties or vapour lock usually.

On the contrary, when the quantity of the compound (C) that adds is too big, because wherein the quantity of contained compound (C) increases, usually bonding between the gentle resistive resin of the propene polymer of hindered acid modification (G).

In addition, when the quantity of the compound (C) that adds was too big, a large amount of compound (C) is unreacted still when graft reaction usually, cause irritating smell etc. to make the Working environment variation, and the compound (C) that adds greater than desired number increased cost.

To propene polymer (A), radical initiator (B), in same molecular, contain the mutually restriction particularly of method of blend of compound (C) of second olefinic double bond and polar group, for example available dried blending method is with these component blend together.

When producing the propene polymer of sour modification, for example can be under the following conditions with above-mentioned blended mixts melt-kneaded.

The temperature of melt-kneaded is generally 160-270 ℃, preferred 170-250 ℃, more preferably 180-220 ℃.

The time of melt-kneaded (residence time) is generally 10 seconds to 10 minutes, preferred 20 seconds to 5 minutes, more preferably 30-120 second.

When the melt-kneaded temperature was lower than 160 ℃, the efficient of free radical reaction can not get enough raisings, therefore can not reach the sour modification quantity of expection.

When the melt-kneaded temperature was higher than 270 ℃, thermolysis and deterioration by oxidation usually took place in propene polymer (A).

When residence time during less than 10 seconds, free radical reaction can not fully be carried out, and therefore can not reach the sour modification quantity of expection.

Surpass 10 timesharing when the residence time, thermolysis and deterioration by oxidation usually take place in propene polymer (A).

Melt-kneaded is preferably carried out in inert atmosphere.

In some cases, water vapor can be added, or volatile constituent can be under reduced pressure removed.

As molding machinery, can use single multiple screw extruder, Bitruder etc.

The example of Bitruder comprises that the experiment of 20 mm dias moulds the TEM of grinding machine, 35 mm dias (Toshiba Kikai Co., Ltd. provides) Bitruder etc.

Be used for the C that contacts with the propene polymer of the ortho acid modification that makes by said components (A)-(C) melt-kneaded ₆-C ₂₀Aliphatic series and/or C ₆-C ₂₀The example of clicyclic hydrocarbon (D) comprises the straight chain hydrocarbon compound, for example hexane, heptane, octane and decane; And alicyclic hydro carbons, for example perhydronaphthalene and naphthane.

In these compounds, for example hexane and heptane are preferred with solvent in the polymerization that is used for polyolefin production.Can use these solvents and can not go wrong, even wherein contain small amount of impurities, as long as the propene polymer of ortho acid modification can be used their swellings.

As the dialkyl ketone (E) that is used for contacting, can preferably use the ketone of three or three above carbon atoms with the propene polymer of ortho acid modification.The object lesson of dialkyl ketone (E) comprises acetone, methylethylketone, isobutyl methyl ketone etc.In these dialkyl ketones, acetone is particularly preferred.

C ₆-C ₂₀The consumption of the mixed solvent that aliphatic series and/or clicyclic hydrocarbon (D) and dialkyl ketone (E) are formed can be not less than the identical volume or the quality quantity of propene polymer of sour modification, preferred such quantity, so that the propene polymer of sour modification can immerse wherein fully, or higher quantity.

Dialkyl ketone (E) and C ₆-C ₂₀The volume ratio of aliphatic series and/or clicyclic hydrocarbon (D) is preferably 0.05-0.6.

When the propene polymer of the volume ratio of component (E) and component (D) ortho acid modification greater than 0.6 time can not be with the abundant swelling of mixed solvent, so that dialkyl ketone (E) can not immerse the propene polymer of ortho acid modification, makes the deterioration of efficiency of removing unsaturated carboxylic acid or acid anhydrides.

For the propene polymer that makes the ortho acid modification contacts with mixed solvent, for example can use a kind of like this method: the propene polymer with the ortho acid modification under heating is stirred in the mixed solvent.

Being used for the temperature that the propene polymer of ortho acid modification contacts with mixed solvent is 40-90 ℃, preferred 70-90 ℃.

When contact temperature when being lower than 40 ℃, the efficient of removing unsaturated carboxylic acid or acid anhydrides is variation usually.

When the contact temperature was higher than 90 ℃, the propene polymer of the sour modification of generation usually was fused together.

The propene polymer of ortho acid modification and the duration of contact of mixed solvent are 30 minutes to 5 hours, preferred 1-5 hour.

Subsequently, with the propene polymer of ortho acid modification from C ₆-C ₂₀Remove in the mixed solvent that aliphatic series and/or clicyclic hydrocarbon (D) and dialkyl ketone (E) are formed, then with C ₁-C ₈The mixture of alcohol (F), dialkyl ketone (E) or component (E) and (F) contacts.

C ₁-C ₈The example of alcohol (F) comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, butanols, 2-Ethylhexyl Alcohol etc.

As dialkyl ketone (E), can use above-mentioned identical compound.

In order to remove unsaturated carboxylic acid residual in the propene polymer of ortho acid modification or acid anhydrides, with C ₁-C ₈Alcohol (F) fully contacts with the propene polymer of ortho acid modification.

For example can use the C of such quantity ₁-C ₈Alcohol (F), dialkyl ketone (E) or component (E) and mixture (F), consequently the propene polymer with sour modification fully immerses wherein.

Propene polymer and C in the ortho acid modification ₁-C ₈When the mixture of alcohol (F), dialkyl ketone (E) or component (E) and (F) contacted, the temperature of processing was 0-90 ℃, preferred 20-40 ℃, and the time of handling is 10 minutes to 20 hours, preferred 30 minutes to 4 hours, more preferably 30 minutes to 2 hours.

Produce in the method for film at the propene polymer with sour modification of the present invention, for example available 20 microns cast film mould machines are produced the cast film of 40 micron thickness.

For example, with the film laminating so produced on the macromolecular compound of the polar functionalities film that for example polymeric amide (nylon 6, nylon 66 etc.) and polyester (PET, the PBT etc.) film that makes or the propene polymer of not sour modification make.

As laminating method, for example can use the extrusion molding laminating for example heat seal with the propene polymer and the coarctate method of nylon layer of sour modification.

The film that the propene polymer of the present invention acid modification makes can be suitable for producing the multi-layered board of such structure, and promptly the bonding coat (a) that makes of the propene polymer of the layer (c) that makes of the layer (b) that makes of vapour lock resin (G) and propene polymer (A ') by sour modification is bonding mutually.

The available known method of bonding coat (a) is made film shape with the propene polymer of sour modification and is produced.So, do not elaborate here.

Vapour lock resin (G) as using in the internal layer (b) of multi-layered board of the present invention can use ethylene/vinyl alcohol copolymer, polyvinylidene dichloride, polyamide resin etc.In these resins, the ethylene/vinyl alcohol copolymer is preferred.

The ethylene/vinyl alcohol copolymer can be produced by make the saponification of ethylene/vinyl acetate multipolymer with known method.

The copolymerization ratio of ethene and vinyl acetate between to for plastic is generally 20-80% (mole), preferred 25-75% (mole) in the ethylene/vinyl alcohol copolymer.

When the copolymerization ratio in the ethylene/vinyl alcohol copolymer during less than 20% (mole), the multipolymer of generation is variation aspect mouldability usually.When the copolymerization ratio in the ethylene/vinyl alcohol copolymer during greater than 80% (mole), the multi-layered board of generation is variation aspect vapour lock usually.

Polyvinylidene dichloride can be the vinylidene chloride homopolymer or contains for example vinylidene chloride copolymer of vinylchlorid, acrylate, vinyl cyanide, vinyl acetate between to for plastic etc. of other comonomer, and the quantity of comonomer is 5-20%.

As polyamide resin, for example applicable nylon 6, nylon 66, NYLON610, nylon 12, MXD nylon, amorphous nylon, terephthalic acid/hexanodioic acid/hexamethylene diamine copolymer etc.

The propene polymer that uses in the layer (c) of multi-layered board of the present invention (A ') can be original unmodified propene polymer, its form be alfon or with the multipolymer of other comonomer on a small quantity.

The propene polymer of multipolymer form (A ') can be random copolymers or segmented copolymer.

In addition, the composition of multiple propene polymer also can be used as propene polymer (A ').

For example, with the kind and the content of other comonomer of propene polymer (A ') copolymerization and produce identical that the method for propene polymer (A ') can be with propene polymer (A).

Multi-layered board of the present invention has such structure, and wherein the bonding coat (a) that makes of the propene polymer of the layer (c) that makes of the layer (b) that makes of vapour lock resin (G) and propene polymer (A ') by above-mentioned sour modification is bonding mutually.

So multi-layered board of the present invention has and comprises layer (c), bonding coat (a) and layer (b) by this mutual laminated laminate structure in proper order.Except these layers of pressing the said sequence arrangement, in multi-layered board, also can there be other middle layer for example to reclaim resin layer.

In addition, layer (c) or (b) protective layer or the embossed decorative layer that improves scuff resistance and decoration can be arranged.

In addition, multi-layered board of the present invention also is fit to form by at least five layers, such structure is more particularly arranged, and wherein the bonding coat (a1, a2) that makes of the propene polymer of the skin (c1, c2) that makes of propene polymer (A ') by above-mentioned sour modification is adhered to the both sides of the internal layer (b) that vapour lock resin (G) makes.

So the multi-layered board of producing has skin (c1), bonding coat (a1), internal layer (b), bonding coat (a2) and the skin (c2) by this order.Have again, the outside of binder layer (a1 or a2) or inboard on optional layer can be provided.

For example, the middle layer that can have in bonding coat (a1 or a2) the recovery resin of the similar type of using make.In addition, can there be thermal synthesis layer in bonding coat (a1 or the a2) outside, or protective layer or embossed decorative layer, so that improve the intensity or the outward appearance of the multi-layered board that generates.

In addition, in multi-layered board of the present invention, preferably press this order with skin (c1), bonding coat (a1), internal layer (b), bonding coat (a2) and outer (c2) mutual continuous laminating.

In multi-layered board of the present invention, the thickness of bonding coat (a) is not specifically limited, respectively be 10-50 micron, preferred 20-30 micron usually.

When the thickness of bonding coat during less than 10 microns, vapour lock resin layer (b) is usually peeled off mutually with propylene polymer resin layer (c) and is separated.When the thickness of bonding coat surpassed 50 microns, generally speaking, the multi-layered board of generation is variation aspect rigidity usually, and production cost increases.

Thickness as the vapour lock resin layer of internal layer (b) is not specifically limited, is generally 100-1000 micron, preferred 150-700 micron.

When the thickness of vapour lock resin layer (b) during, may be difficult to make thin like this thin film layer less than 100 microns.When the thickness of vapour lock resin layer (b) surpassed 1000 microns, the multi-layered board of generation usually had relatively poor processibility, for example is difficult to rolling.

The layer (c) that layer (b) and the propene polymer (A ') that multi-layered board of the present invention can make by bonding coat (a), the vapour lock resin (G) that modified propylene polymer is made makes is produced by the mutual lamination of this order.

The example of producing the laminating of multi-layered board comprises the co-extrusion method, for example co-extrusion curtain coating moulding method and co-extrusion blow moulding method, heat seal, laminating etc.

In these methods, co-extrusion curtain coating moulding method is preferred.

Multi-layered board of the present invention can be controlled the number of the modification group of each molecular chain introducing and produce simultaneously by the propene polymer of simple process as raw material.

In addition, because with the modified propylene polymer of comparing high molecular and containing less modification quantity and for example unreacted monomer of lesser amt impurity and low-molecular-weight component arranged that makes with traditional method as the tackiness agent between vapour lock resin and the propene polymer, so the multi-layered board that generates can have fabulous bond strength between each layer, so keep its high vapour lock, and further can low cost production.

Describe the present invention in more detail with reference to following examples, but should be pointed out that and do not plan to limit the scope of the invention with these embodiment.

(1) limiting viscosity [η]

Limiting viscosity [η] is used Rigosha Co., and " VNR-053 type " automatic viscometer that Ltd. provides is measured.

To measure concentration in as the naphthane solvent of antioxidant be the limiting viscosity of the sample of 0.8-1.4 grams per liter containing 1 grams per liter 2,6 di tert butyl 4 methyl phenol (hereinafter referred to as " BHT ") under 135 ℃ with the Ubbelohde capillary viscosimeter.

(2) acid content in the propene polymer of sour modification

Under agitation, about 1 propene polymer and 0.1 BHT that restrains as antioxidant that restrains sour modification is heated to 130 ℃ in 0.1 liter of p-Xylol, and is dissolved in wherein fully.

The propene polymer solution of the sour modification that so makes is added in 1: 1 mixed solvent of 0.5 liter of acetone and methyl alcohol, and pre-deposition filters then.With the filter cake that obtains 130 ℃ of following vacuum-dryings 6 hours, so that therefrom remove unreacted maleic anhydride fully.

The propene polymer of the sour modification of purifying like this 220 ℃ of following hot pressing, is obtained the about 0.2 millimeter film of thickness.Test the film that so makes with fourier transform infrared absorption spectrometer (FT-IR), so that measure at 1700-1800 centimetre ^-1The infrared absorption peak intensity that belongs to carbonyl in the scope.

In order to make the calibration curve that is used for calculating acid content from the infrared absorption peak intensity of measurement like this, to be used for the maleic anhydride and the unmodified propene polymer blend of powdered of above-mentioned modified-reaction, and then the blended mixts that obtains be carried out above-mentioned identical FT-IR and measure.

(3) ratio (β value) of acid content and polymer chain number

Calculate the β value by the acid content in the propene polymer of sour modification (moles per gram) divided by the polymer chain number that calculates by number-average molecular weight (Mn).

When the compound (C) that contains second olefinic double bond and polar group when-molecule in same molecular was added on the polymer chain, the β value equaled 1.

(4) molecular weight is 10000 or lower component concentration, molecular weight distribution (Mw/Mn) and to contain molecular weight be 1000000 or higher component concentration

Measure with aforesaid method.

Simultaneously, with containing 0.33 grams per liter as 1,2 of the BHT of antioxidant, the 4-trichlorobenzene is measured.

(5) taxis (mmmm)

Measure with above-mentioned method.

Simultaneously, with identical 1,2 in above-mentioned (4), the 4-trichlorobenzene is as solvent.

(6) fusing point (Tm)

Measure with above-mentioned method.

Embodiment 1

(1) preparation of solid catalyst

With 0.5 liter of three-necked flask that agitator is housed of nitrogen purging, octane and the 16 gram diethoxy magnesium of dewatering of packing into then 60 milliliters.

The material of flask is heated to after 40 ℃, 2.4 milliliters of silicon tetrachlorides are added.The mixture that generates was stirred 20 minutes, add 1.6 milliliters of phthalic acid dibutyl esters then.

The solution that makes is heated to 80 ℃, splashes into 77 milliliters of titanium tetrachlorides then gradually.The mixture that generates was stirred 2 hours under 125 ℃ of inboard temperature, each component is in contact with one another.

Then, stop to stir the mixture, make deposition of solids, therefrom remove supernatant liquid then.

The solid that so obtains is mixed with 100 milliliters of dehydration octanes, and under agitation with the mixture heating up to 125 that obtains ℃, maintenance is 1 minute under this temperature then.Stop to stir the mixture,, therefrom remove supernatant liquid then so that make deposition of solids.This washing step is repeated 7 times.

In addition, 122 milliliters of titanium tetrachlorides are added in the solid that obtains, then the mixture that generates were stirred 2 hours under 125 ℃ of inboard temperature, make each component carry out the secondary contact.

After this, the mixture that obtains is carried out above-mentioned washing step 6 times with 125 ℃ of dehydration octanes, thereby make ingredient of solid catalyst.

(2) prepolymerization

With 0.5 liter of three-necked flask that agitator is housed of nitrogen purging, the ingredient of solid catalyst of the 400 milliliters of heptane that dewater of packing into then, 25 mmole triisobutyl aluminiums, 2.5 mmole dicyclopentyl dimethoxyl silanes and the above-mentioned preparation of 4 grams.

The inboard temperature of flask is heated to 50 ℃, under agitation propylene is sent into then.

After 1 hour, stop to stir, make pre-polymerized catalyst components, wherein every gram ingredient of solid catalyst makes 4 gram propylene polymerizations.

(3) polymerization of production propene polymer (A)

With the nitrogen complete drying with purge 6 liters of stainless steel autoclaves that agitator is housed, the 6 liters of heptane that dewater of packing into then, 12.5 mmole triethyl aluminums and 0.3 mmole dicyclopentyl dimethoxyl silane.

Behind the nitrogen that exists in the propylene replacement(metathesis)reaction system, under agitation propylene is sent into.

Reaction system adds 50 milliliters of heptane slurries that contain by the above-mentioned pre-polymerized catalyst components that makes of Ti atom 0.08 mmole after stablizing under 80 ℃ of inboard temperature and 0.8 MPa (gauge pressure).In addition, when continuously propylene being sent into reaction system, propylene is at 80 ℃ of following polyase 13s hour.

After polymerization is finished, the reaction mixture that generates is mixed with 50 ml methanol, cool off then and reduce pressure.

The material of all amts in the autoclave is transferred in the filtration vessel that has strainer, be heated to 85 ℃ then, separate thereby carry out solid-liquid.

In addition, with the solids wash that obtains 2 times, vacuum-drying then obtains 2.5 kilograms of propene polymers (A) with 6 liters 85 ℃ heptane.

The result confirms, when polyase 13 hour, the catalytic activity of every gram solid catalyst is 9.8 kilograms/gram catalyzer 3 hours.

The character of the propene polymer that so makes (A) is as follows.

(i) limiting viscosity [η]: 7.65 deciliter/gram;

The soluble component concentration of heptane (ii) seethes with excitement: analysis limit or lower;

(iii) molecular weight distribution (Mw/Mn): 3.99 (Mn:370000);

(iv) molecular weight Mw is 1000000 or higher component concentration: 41% (quality);

(v) use ¹³The Pentad[mmmm that C-NMR measures] cut: 96.3% (mole);

(vi) ¹³The δ value of C-NMR (interior mark: TMS): 17.2,17.6,30.6,31.6,35.9,36.0,38.6 and the 42.3ppm place weak signal is arranged; And

(the vii) mean particle size of polymer powder: 750 microns.

(4) method of the propene polymer of the sour modification of production

With 1.2 kilograms of aforesaid propylene polymkeric substance (component A) and maleic anhydride (component C) and Perhexyne 25B (Nippon Yushi Co., Ltd. provide 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexin-3) it is dried mixed that (B component) presses the ratio of mixture shown in the table 1, do to mix the thing melt-kneaded with what 20 mm dia Bitruders will generate then under 180 ℃ fixed temperature, the residence time is 90 seconds, thereby make the propene polymer [1] of the ortho acid modification of bead shape, its maleic anhydride content is 0.081% (mole), and fusing point is 164.5 ℃.

The propene polymer [1] of 1 kilogram of ortho acid modification that obtains is mixed with 0.7 kilogram of heptane (component D) and 0.4 kilogram of acetone (component E), the mixture that generates is stirred 2 hours (use pressurizing vessel) under 85 ℃ of heating.

Subsequently, reclaim bead, at room temperature it was soaked 15 hours in 1.5 kilograms of methyl alcohol (component F) then with wire netting.

Then, reclaim bead with wire cloth, dry air and 80 ℃ of following vacuum-dryings 6 hours obtains the propene polymer of the sour modification of following character:

(i) unreacted acid (maleic anhydride) content: analysis limit or lower;

The (ii) ratio (β value) of acid content and polymer chain number: 1.11;

(iii) molecular weight distribution (Mw/Mn): 1.99;

(iv) molecular weight Mw is 10000 or lower component concentration (LP content): 0.2% (quality); And

(v) limiting viscosity [η]: 1.34 deciliter/gram.

Simultaneously, the propene polymers [1] of the above-mentioned ortho acid modification of 5 gram bead shapes are dissolved in 500 milliliters 130 ℃ the p-Xylol, deposition and crystallization in 4 liters of acetone are therefrom removed unreacted maleic anhydride fully then.

Above-mentioned purification step is repeated 5 times, obtain 5 purified products altogether.

The maleic anhydride content of 5 purified products that so obtain is 0.047 ± 0.001% (mole), and maleic anhydride content is identical in the propene polymer of the sour modification that it makes with above-mentioned production (purifying) method basically.

This shows with method of the present invention can remove unreacted acid simple and reliablely.

The working condition of above-mentioned use is listed table 1-1 in, and the result lists table 2-1 in.

In table 2-1 and 2-2, in the propene polymer of the sour modification that obtains, unreacted maleic anhydride (MAH) content % is calculated by following formula:

Unreacted MAH content (%)=[(MAH-MAHp)/(MAHi-MAHp)] x100

Wherein MAHp represents the MAH content measured with above-mentioned solvent purification method, the propene polymer that promptly is illustrated in the ortho acid modification be dissolved in the p-Xylol and polymkeric substance deposit in acetone and the propene polymer of the sour modification of purifying that the crystallization repetition obtains later on for 5 times in MAH content; And MAHi is illustrated in the MAH content in the propene polymer of ortho acid modification.

In addition, press JIS-K7210, under 230 ℃ and 2.16 kilograms of loads, measured melt index (MI).

Embodiment 2 and 3

Repeat the identical step of embodiment 1, different is changes the ratio of the ratio of heptane (component D) and the propene polymer [1] of ortho acid modification and acetone (component E) and the propene polymer [1] of ortho acid modification, thereby obtains the propene polymer of sour modification.

Analytical results confirms, the propene polymer of the sour modification that makes among the propene polymer of the sour modification that makes and the embodiment 1 has substantially the same character.

Embodiment 4

Repeat the identical step of embodiment 1, the different hexanes that are to use are as component D and the temperature and time that changed for the 2nd step, thereby obtain the propene polymer of sour modification.

Embodiment 5

Repeat the identical step of embodiment 1, the different perhydronaphthalenes that are to use are as component D and the temperature and time that changed for the 2nd step, thereby obtain the propene polymer of sour modification.

Embodiment 6

Repeat the identical step of embodiment 1, different is to use methylethylketone (hereinafter referred to as " MEK ") as component E, thereby obtains the propene polymer of sour modification.

Embodiment 7

Repeat the identical step of embodiment 1, different is changes the ratio of the propene polymer [ratio 1] of methyl alcohol (component F) and ortho acid modification, thereby obtains the propene polymer of sour modification.

Embodiment 8

Repeat the identical step of embodiment 1, different is to use Virahol (hereinafter referred to as " iPrOH ") as component F, thereby obtains the propene polymer of sour modification.

Embodiment 9

Repeat the identical step of embodiment 1, different is to use acetone as component F, thereby obtains the propene polymer of sour modification.

Embodiment 10 and 11

Repeat the identical step of embodiment 1, different is change used Perhexyne25B (Nippon Yushi Co., Ltd. provide 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexin-3) quantity of (B component), thus the propene polymer of sour modification obtained.

Analytical results confirms, in the analytical value scope of the maleic anhydride content of the maleic anhydride content in the propene polymer of the sour modification that two embodiment make in the purified product that makes with embodiment 1 identical method, promptly polymkeric substance is gone up substantially and is not contained unreacted maleic anhydride.

Simultaneously, the fusing point of the propene polymer of the ortho acid modification that obtains among the embodiment 10 and 11 is respectively 167.7 ℃ and 165.1 ℃.

Embodiment 12 and 13

Repeat the identical step of embodiment 1, different is to change used Perhexyne25B (Nippon Yushi Co., Ltd. provide 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexin-3) quantity of (B component) and maleic anhydride (component C), thus the propene polymer of sour modification obtained.

The working condition of above-mentioned use is listed table 1-2 in, and the result lists table 2-1 in.

Simultaneously, the fusing point of the propene polymer of the ortho acid modification that obtains among the embodiment 12 and 13 is respectively 164.9 ℃ and 164.4 ℃.

Embodiment 14

Repeat the identical step of embodiment 1, different is the polymerization procedure (3) that propene polymer (A) is produced in change as described below, thereby obtains the propene polymer of sour modification.

Analytical results confirms, except that wherein not containing the unreacted maleic anhydride, what make among the propene polymer of the sour modification that makes and the embodiment 1 is different.

The working condition of above-mentioned use is listed table 1-2 in, and the result lists table 2-2 in.

Simultaneously, the fusing point of the propene polymer of ortho acid modification is 162.1 ℃.

(3) polymerization of production propene polymer (A)

With the nitrogen complete drying with purge 6 liters of stainless steel autoclaves that agitator is housed, the 6 liters of heptane that dewater of packing into then, 12.5 mmole triethyl aluminums and 0.3 mmole dicyclopentyl dimethoxyl silane.Behind the nitrogen that exists in the propylene replacement(metathesis)reaction system, under agitation with 0.1 kilograms per centimeter ²(gauge pressure) hydrogen is sent into.

After this, under agitation propylene is sent into autoclave, and wherein inboard temperature and propylene pressure are set in 80 ℃ and 8 kilograms per centimeter respectively ²(gauge pressure).

After reaction system is stable, the heptane slurries of the pre-polymerized catalyst components that makes in 50 milliliters of polymerization procedures (2) that contain by Ti atom 0.04 mmole embodiment 1 are added.In addition, when continuously propylene being sent into reaction system, propylene is at 80 ℃ of following polyase 13s hour.

In addition, with the solids wash that obtains 2 times, vacuum-drying then obtains 2.0 kilograms of propene polymers (A) with 6 liters 85 ℃ heptane.

The result confirms, when polyase 13 hour, the catalytic activity of every gram solid catalyst is 14.4 kilograms/gram catalyzer 3 hours.

The character of the propene polymer that so makes (A) is as follows.

(i) limiting viscosity [η]: 3.26 deciliter/gram;

The soluble component concentration of heptane (ii) seethes with excitement: 0.9% (quality);

(iii) molecular weight distribution (Mw/Mn): 3.93 (Mn:150000);

(iv) molecular weight Mw is 1000000 or higher component concentration: 22% (quality);

(v) use ¹³The Pentad[mmmm that C-NMR measures] cut: 97.3% (mole);

(vi) ¹³The δ value of C-NMR (interior mark: TMS): 17.2,17.6,30.6,31.6,35.9,36.0,38.6 and the 42.3ppm place do not have signal; And

(the vii) mean particle size of polymer powder: 920 microns.

Embodiment 15

Repeat the identical step of embodiment 1, different is the method that propene polymer is produced in change as described below, thereby obtains the propene polymer of sour modification.

Simultaneously, the fusing point of the propene polymer of ortho acid modification is respectively 161.5 ℃.

(1) prepolymerization

With 0.5 liter of three-necked flask that agitator is housed of nitrogen purging, the Solvay type titanium trichloride catalyst (TosoFine-Chem Co., Ltd. provides) that the 400 milliliters of heptane that dewater of packing into then, 18 gram diethyl aluminum chlorides, 2 grams are purchased.

The temperature of the inboard of flask is remained on 20 ℃, under agitation propylene is sent into then.

After 80 minutes, stop to stir, make pre-polymerized catalyst components, wherein every gram ingredient of solid catalyst makes 0.8 gram propylene polymerization.

(2) polymerization of production propene polymer (A)

With the nitrogen complete drying with purge 6 liters of stainless steel autoclaves that agitator is housed, the 6 liters of heptane that dewater of packing into then.Then with the nitrogen that exists in the propylene replacement(metathesis)reaction system.

After this, under agitation with 0.6 kilograms per centimeter ²(gauge pressure) hydrogen is sent into, and then propylene is sent into.

Reaction system is in 65 ℃ of inboard temperature and 7.5 kilograms per centimeter ²After (gauge pressure) is stable down, 50 milliliters of heptane slurries that contain by solid catalyst 0.5 gram pre-polymerized catalyst components are added.In addition, when continuously propylene being sent into reaction system, propylene is at 65 ℃ of following polyase 13s hour.

Then, inboard temperature is reduced to 50 ℃ and weaken stirring, and with the reaction mixture decompression that generates.

After this, under agitation, with 0.4 kilograms per centimeter ²(gauge pressure) hydrogen is sent into autoclave, sends into propylene then.

In addition, in 50 ℃ of inboard temperature and 7.5 kilograms per centimeter ²Under (gauge pressure) propylene pressure propylene is sent into reaction system continuously, propylene is at 50 ℃ of following polyase 13s hour.

In addition, with the solids wash that obtains 2 times, vacuum-drying then obtains 2.4 kilograms of propene polymers (A) with 6 liters 85 ℃ heptane.

The result confirms that when polymerization 6 hours, the catalytic activity of every gram solid catalyst was 4.8 kilograms/gram catalyzer 6 hours.

The character of the propene polymer that so makes is as follows.

(i) limiting viscosity [η] in 1 step of the mat woven of fine bamboo strips: 2.47 deciliter/gram; And the limiting viscosity [η] in the 2nd step: 2.70 deciliter/gram

The soluble component concentration of heptane (ii) seethes with excitement: 1.2% (quality);

(iii) molecular weight distribution (Mw/Mn): 7.42 (Mn:100000);

(iv) molecular weight Mw is 1000000 or higher component concentration: 18% (quality);

(v) use ¹³The Pentad[mmmm that C-NMR measures] cut: 92.0% (mole);

(the vii) mean particle size of polymer powder: 250 microns.

Comparative Examples 1

Repeat the identical step of embodiment 1, different is changes to 25 ℃ and 24 hours respectively with the temperature and time in the 2nd step, thereby obtains the propene polymer of sour modification.

Analytical results confirms that different with embodiment 1, the propene polymer of the sour modification that makes contains quite a large amount of residual unreacted maleic anhydrides.

Comparative Examples 2

Repeat the identical step of embodiment 1, different is not have for the 3rd step, thereby obtains the propene polymer of sour modification.

Comparative Examples 3

Repeat the identical step of embodiment 1, different is in the 2nd step, does not use heptane as component D, but uses acetone as component E, thereby obtains the propene polymer of sour modification.

Comparative Examples 4

Repeat the identical step of embodiment 1, different is in the 2nd step, uses heptane as component D, but uses acetone as component E, thereby obtains the propene polymer of sour modification.

Reference example 1

The analytical results of " POLYBOND 3002 " (propene polymer of sour modification) that Crompton Corp. provides is listed table 2-2 in.

The character that confirms " POLYBOND 3002 " is different with the propene polymer of sour modification of the present invention.

Reference example 2

Propene polymer (acid content: 5% (weight) with sour modification; " the TOYO-TACK H1000P " that Toyo Kasei KogyoCo., Ltd. provide) and propene polymer (melt index: 7; " F704NP " that Idemitsu Petrochemical Co., Ltd. provide) melt-kneaded together so that the preparation sample.The analytical results of sample is listed table 2-2 in.

The character that has confirmed the blended product that so makes is different with the propene polymer of sour modification of the present invention.

Table 1-1

Table 1-1 (continuing)

Table 1-1 (continuing)

Table 1-2

Table 1-2 (continuing)

Table 1-2 (continuing)

Table 2-1

Table 2-1 (continuing)

	Mw/Mn	LP content (%)	[η]
	Mw/Mn	LP content (%)	[η]	Embodiment 1-9	1.99±0.2	0.2±0.05	1.34±0.1
Embodiment 10	2.17	＜0.1	1.82	Embodiment 1-9	1.99±0.2	0.2±0.05	1.34±0.1
Embodiment 10	2.17	＜0.1	1.82	Embodiment 11	2.06	0.3	1.13
Embodiment 12	2.08	0.3	1.10	Embodiment 11	2.06	0.3	1.13
Embodiment 12	2.08	0.3	1.10	Embodiment 13	2.05	0.4	1.05
Embodiment 14	2.58	1.4	1.2	Embodiment 13	2.05	0.4	1.05
Embodiment 14	2.58	1.4	1.2	Embodiment 15	2.82	2.2	1.14

Table 2-1 (continuing)

	MI gram/10 minutes	Tm(℃)
	MI gram/10 minutes	Tm(℃)	Embodiment 1-9	14±1	164.9±0.5
Embodiment 10	4	166.5	Embodiment 1-9	14±1	164.9±0.5
Embodiment 10	4	166.5	Embodiment 11	37	163.7
Embodiment 12	42	163.4	Embodiment 11	37	163.7
Embodiment 12	42	163.4	Embodiment 13	50	162.4
Embodiment 14	40	161.2	Embodiment 13	50	162.4
Embodiment 14	40	161.2	Embodiment 15	46	160.5

Table 2-2

	MAH content (% (mole))	Unreacted MAH content (%)	The β value
	MAH content (% (mole))	Unreacted MAH content (%)	The β value	Comparative Examples 1	0.063	47	1.49
Comparative Examples 2	0.059	35	1.39	Comparative Examples 1	0.063	47	1.49
Comparative Examples 2	0.059	35	1.39	Comparative Examples 3	0.077	87	1.82
Comparative Examples 4	0.080	96	1.89	Comparative Examples 3	0.077	87	1.82
Comparative Examples 4	0.080	96	1.89	Reference example 1	0.043	-	0.75
Reference example 2	0.095	-	1.58	Reference example 1	0.043	-	0.75

Table 2-2 (continuing)

	Mw/Mn	LP content (%)	[η]
	Mw/Mn	LP content (%)	[η]	Comparative Examples 1	1.99±0.2	0.2±0.05	1.34±0.1
Comparative Examples 2	The same	The same	The same	Comparative Examples 1	1.99±0.2	0.2±0.05	1.34±0.1
Comparative Examples 2	The same	The same	The same	Comparative Examples 3	The same	The same	The same
Comparative Examples 4	The same	The same	The same	Comparative Examples 3	The same	The same	The same
Comparative Examples 4	The same	The same	The same	Reference example 1	4.44	1.7	1.67
Reference example 2	4.53	2.5	1.60	Reference example 1	4.44	1.7	1.67

Table 2-2 (continuing)

	MI gram/10 minutes	Tm(℃)
	MI gram/10 minutes	Tm(℃)	Comparative Examples 1	14±1	164.9±0.5
Comparative Examples 2	The same	The same	Comparative Examples 1	14±1	164.9±0.5
Comparative Examples 2	The same	The same	Comparative Examples 3	The same	The same
Comparative Examples 4	The same	The same	Comparative Examples 3	The same	The same
Comparative Examples 4	The same	The same	Reference example 1	7.5	161.5
Reference example 2	6.9	161.3	Reference example 1	7.5	161.5

[evaluation of cast film character]

The propene polymer of the sour modification that makes in embodiment 1 and 9-10 and reference example 1 and 2 is molded as cast film respectively, so that estimate its character.

Make cast film separately, making thickness is 50 microns.The result lists table 3 in.

With the film of molding 23 ± 1 ℃ of temperature with humidity was placed 16 hours for 50 ± 5% times or shock strength (15 kgfs of each film are measured in longer back; 1/2 inch).

In addition, will keep behind the molding 16 hours or longer film was placed 1 hour or longer for 50 ± 5% times in 23 ± 1 ℃ of temperature and humidity, measured its shock strength then.

With Toyo Seiki Seisakusho Co., the film shock-testing machine that Ltd. provides is measured shock strength under following measuring condition: power is 15 kgfs centimetre, and impact head is that 1/2 inch and mold pressure are 4 kilograms per centimeter ²(gauge pressure).

[to the evaluation of the heat sealer of nylon 6]

On the cast film that nylon 6 film laminatings that rubbish is stretched make in embodiment 1 and 9-10 and reference example 1 and 2, and heat seal is together under the following conditions with the twin shaft of 30 micron thickness.

(i) heater temperature: 250 ℃;

(ii) heat sealed time: 1 second; And

(iii) heat seal pressure: 1 kilograms per centimeter ²

The heat-sealing film that so makes is carried out stripping test under 180 ℃, so that measure its heat sealing strength.

Under 180 ℃, estimate the stripping strength of film with stripping test with five redrawing trier (" RTA-T-5M " that Orientec Co., Ltd. provide).

The result lists table 3 in.

Table 3

Table 3 (continuing)

With comparing that reference example 1 and 2 makes, heat-sealing film that makes among embodiment 1 and the 9-10 and nylon 6 powerful heat seals, and fabulous balance is arranged between shock strength and heat sealing strength.

Embodiment 16 (multi-layered board)

Production example 1: the production of propene polymer (A)

(1) preparation of ingredient of solid catalyst

Produce ingredient of solid catalyst with method identical among the embodiment 1.

(2) prepolymerization

Carry out prepolymerization with method identical among the embodiment 1.

(3) polymerization of production propene polymer (A)

With the nitrogen complete drying with purge 6 liters of stainless steel autoclaves that agitator is housed, the 6 liters of heptane that dewater of packing into then, 12.5 mmole triethyl aluminums and 1.2 mmole dicyclopentyl dimethoxyl silanes.

Reaction system is in 80 ℃ of inboard temperature and 0.78 MPa (8 kilograms per centimeter ²(gauge pressure)) down stable after, 50 milliliters of heptane slurries that contain by the above-mentioned pre-polymerized catalyst components that makes of Ti atom 0.10 mmole are added.In addition, when continuously propylene being sent into reaction system, propylene was 80 ℃ of following polymerizations 4 hours.

Confirm that when polymerization 4 hours, the catalytic activity of every gram solid catalyst was 16.5 kilograms/gram catalyzer 4 hours.

The material of all amts in the autoclave transferred to have in the filtering filtration vessel, be heated to 85 ℃ then, separate thereby carry out solid-liquid.

In addition, with the solids wash that obtains 2 times, vacuum-drying then obtains 3.0 kilograms of propene polymers (A) with 6 liters 85 ℃ heptane.

The character of the propene polymer that so makes (A) is as follows.

(i) limiting viscosity [η]: 8.10 deciliter/gram;

(iii) molecular weight distribution (Mw/Mn): 3.99 (Mn:370000);

(v) use ¹³The Pentad[mmmm that C-NMR measures] cut: 97.8% (mole);

(vi) ¹³The δ value of C-NMR (interior mark: TMS): 17.2,17.6,30.6,31.6,35.9,36.0,38.6 and the 42.3ppm place weak signal is arranged;

(the vii) mean particle size of polymer powder: 720 microns; And

(viii) fusing point: 164.8 ℃

Produce the production of the propene polymer of routine 2:(acid modification)

With 12.0 kilograms of propene polymers (A) of in production example 1, producing, 4.8 grams 2,5-dimethyl-2,5-two (tert-butyl hydroperoxide) hexane (B) (" the Perhexyne 25B " that Nippon Yushi Co., Ltd. provide; Purity: 40% (weight); 12 restrain) and dried the mixing of 48 gram maleic anhydrides (C), use 20 mm dia Bitruders 230 ℃ of following melt-kneaded then, thereby make the propene polymer bead of unpurified modified by maleic acid anhydride graft.

With propene polymer, 1.5 kilograms of acetone and 2.5 kilograms of heptane 8 liters of stainless steel pressure containers of packing into of the unpurified modified by maleic acid anhydride graft of 3.5 grams,, and under this temperature, stirred 2 hours the mixture heating up to 80 that generates ℃.

Behind the cool to room temperature,, then it was soaked 12 hours in 5.0 kilograms of acetone with stainless steel metal net filtration bead.

With the bead dry air that reclaims,, obtain the propene polymer of modified by maleic acid anhydride graft then 80 ℃ of following dried making an uproar 6 hours.

[producing the method for multi-layered board]

With following material produce multi-layered board: (i) be used for the propene polymer of the modified by maleic acid anhydride graft that bonding coat (a1, a2) produces as the production example 2 of the propene polymer of sour modification; (ii) be used for ethylene/vinyl alcohol copolymer (" the EVAL J102 " that KrarayCo., Lt d. provide of vapour lock resin layer (b) as vapour lock resin (G); Ethylene content: 32% (mole); Density: 1170 kilograms/meter ²MI value: 2.0 grams/10 minutes); And (iii) be used for alfon (" E-105GM " that Idemitsu Petrochemical Co., Ltd. provide of outer resin layer (c1, c2) as propene polymer (A '); Press the MI value that JIS-K7210 measures under 230 ℃ and 21.2 Ns load: 0.5 restrains/10 fens).

3 classes/5 layer multi-layer sheet materials that such layer structure more particularly, arranged with the production of multilayer T connector curtain coating mould machine: outer resin layer (c1)/bonding coat (a1)/vapour lock resin layer (b)/bonding coat (a2)/outer resin layer (c2).

The thickness that has confirmed to make film is 1.0 millimeters, and the thickness between each layer is than being c1/a1/b/a2/c2=47/2/2/2/47.

The multi-layered board that so makes is cut into 15 mm wides, carry out stripping test then, so that peel off mutually when two-layer along 90 ° direction with 50 millimeters/minute speed, measure the interlaminar strength 5 times between each outer resin layer (c1, c2) gentle resistive resin layer (b) with recommending meter.

The character of the propene polymer of acid modification and mean value, maximum value and the minimum value of interlaminar strength are listed table 4 in.

Comparative Examples 5-7

Repeat identical step among the embodiment 16, the different propene polymers that is to use the modified by maleic acid anhydride graft that is purchased is as the propene polymer of the sour modification of bonding coat (a1, a2).

More particularly, in Comparative Examples 5, " POLYBOND 3002 " that Crompton Corp. provides; In Comparative Examples 6, " the TOYO-TACK E-100 " that Toyo Kasei Kogyo Co., Ltd. provide; In Comparative Examples 7, " the ADMAR QF-500 " that Mitsui Chemical Co., Ltd. provide is as the propene polymer of sour modification.

In the Comparative Examples 5-7 of the propene polymer that uses modified by maleic acid anhydride graft, be 10000 or lower component because all polymkeric substance contain a large amount of molecular weight, so its interlaminar strength is little.

Table 4

Commercial Application

According to the present invention, be easy to produce a kind of like this acrylic polymers of modification, it has high molecular weight, the by-product low molecular compound of less content and be substantially free of unreacted unsaturated carboxylic acid or acid anhydrides.

In addition, the acrylic polymers of sour modification of the present invention has substantially the same character with original acrylic polymers, and with the macromolecular material that contains functional group good compatibility is arranged. In addition, modified propylene polymer of the present invention is more far better than the simple blend mixture of acrylic polymers and low molecular modification product aspect physical property.

With between the multi-layered board vapour lock layer of the acrylic polymers production of sour modification of the present invention and the supporting resin bed high bonding strength being arranged, so avoided some defectives, be out of shape and when being heated or be placed on for a long time high humidity lower time such as the container of being produced by its etc., the vapour lock layer is peeled off or is come off from base material. Therefore, described multi-layered board can keep its high vapour lock, and can low-cost production.

Therefore, multi-layered board of the present invention usually can be used for producing splendid attire because its quality such as oxidation, moisture absorption plastic holding device of the material of variation in time, such as the container that is used for sweet food (such as fruit and jelly), be used for distillation and scalding food containers, be used for the containers for medical use of dress liquid medicine etc.

In addition, multi-layered board of the present invention not only is suitable as container, but also is suitable as bag-shaped packing articles.

Claims

1. one kind is satisfied the following alfon that requires the modification of (1)-(4):

(1) limiting viscosity [η], in naphthane 135 ℃ of mensuration: 0.1 liter/gram or higher;

(2) ratio of acid content and polymer chain number, β value: 0.8-2.5;

(3) molecular weight Mw is 10000 or lower components contents, LP content: 0.5% quality or lower; And

(4) content of the unreacted acid of toxilic acid or maleic anhydride: 2% quality or lower.

2. according to the alfon of the modification of claim 1, it is 2.5 or lower that the alfon of wherein said modification satisfies (5) molecular weight distribution mw/mn.

3. according to the alfon of the modification of claim 1, the content that the alfon of wherein said modification satisfies the unreacted acid of (6) toxilic acid or maleic anhydride is analysis limit or lower.

4. the method for the alfon of a modification of producing claim 1, described method comprises:

With mutual blend of the compound (C) of alfon (A), radical initiator (B) and toxilic acid or maleic anhydride and melt-kneaded, producing fusing point is the alfon of 145-170 ℃ thick modification; With

With the alfon of the thick modification that generates with contain C ₆-C ₂₀Aliphatic series and/or clicyclic hydrocarbon (D) contact under 40-90 ℃ temperature with the mixed solvent of dialkyl ketone (E), then with C ₁-C ₈The mixture of alcohol (F), dialkyl ketone (E) or component (E) and (F) contacts.

5. according to the method for claim 4, wherein with the alfon (A) of 100 parts of quality and radical initiator (B) and the toxilic acid of 0.1-10 part quality or compound (C) blend of maleic anhydride of 0.01-1 part quality.

6. according to the method for claim 4, wherein dialkyl ketone (E) is 0.5 or lower with the mass ratio of the alfon of thick modification.

7. according to the method for claim 4, wherein dialkyl ketone (E) is an acetone.

8. according to the method for claim 4, wherein alfon (A) satisfies following (7)-(10) that require:

(7) limiting viscosity [η], in naphthane at 135 ℃ of mensuration: 2.8dl/g or higher;

(8) the soluble components contents of boiling heptane: 2% quality or lower;

(9) molecular weight distribution, Mw/Mn:5 or lower; With

(10) molecular weight Mw is 1000000 or higher components contents: 25% quality or higher.

9. according to the method for claim 4, wherein alfon (A) satisfies following (11)-(13) that require:

(11) ¹³Five unit group [mmmm] cuts that CNMR measures, 9-peak area method: 80mol% or higher;

(12) ¹³The δ value of CNMR, interior mark: TMS: 17.2,17.6,30.6,31.6,35.9,36.0,38.6 and the 42.3ppm place signal is arranged; And

(13) mean particle size of alfon (A): 200-3000 micron.

10. the film that makes of the alfon of the modification of a molding claim 1.

11. the laminate of the macromolecule membrane of film that contains claim 10 and lamination polar functionalities thereon.

12. according to the laminate of claim 11, wherein the macromolecule membrane of polar functionalities is a polyamide layer.