CN1329416C - Modified propylene polymer and polyolefin resin composition - Google Patents
Modified propylene polymer and polyolefin resin composition Download PDFInfo
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- CN1329416C CN1329416C CNB038239256A CN03823925A CN1329416C CN 1329416 C CN1329416 C CN 1329416C CN B038239256 A CNB038239256 A CN B038239256A CN 03823925 A CN03823925 A CN 03823925A CN 1329416 C CN1329416 C CN 1329416C
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Abstract
A polyolefin resin composition including the following (A), (B) and (C), or the following (A), (B), (C) and (D): (A) a polymer synthesized from an alpha-olefin having 3 or more carbon atoms, (B) a modified propylene based polymer satisfying the following (1) to (4): (1) the content of polar group moieties resulting from a compound containing in the same molecule thereof an ethylenic double bond and a polar group is from 0.10 to 0.30 mmol .
Description
Technical field
The present invention relates to be used for requirement low-gravity and high rerum natura (mechanical characteristic, thermal property etc.) automotive material, use modified propylene polymer compound, polyolefine resin composition and their manufacture method in the Industrial materials field of engineering plastics.
Background technology
Propylene resin with rerum natura of being equal to mutually with engineering plastics (high heat-resisting, high strength etc.) is in the past always by with mineral filler such as glass fibre, talcum and acronal is compound makes.In addition, for above-mentioned comprehensive rerum natura is brought up to engineering plastics levels such as nylon, carry out the raising of inorganic filler content always and use special mineral filler etc.The comprehensive rerum natura leap of its result improves, and but then, the low-gravity that polypropylene itself has, the advantage of low price are also lost totally.
Therefore, realize that under the situation of the polyolefinic excellent strong point of not obvious infringement the leap of comprehensive rerum natura improves, the nano-dispersed technological development of mineral filler is constantly being carried out.For example, disclose layered clay mineral is distributed in the acrylic resin, has realized the initial technology (for example, opening flat 6-41346 communique with reference to the spy) that the rerum natura leap improves with nano-scale.The improving technology (for example, open with reference to the spy 2001-240709 communique, spy are opened the 2002-37940 communique, the spy opens the 2002-167484 communique) of this technology is also disclosed in addition.These all be by in the acrylic resin of original no compatibilized performance with clay equably high dispersing (nano-dispersed) realize the technology of rerum natura raising.
But, in these technology, do not reach high comprehensive rerum natura as yet, and, think to have the flexible shortcoming of shortage from the viewpoint of the design of resin as target.
On the other hand, also carried out trial that acronal self is improved.For example, known in acronal the sour modification body and the manufacture method thereof of addition unsaturated carboxylic acid or its acid anhydrides.The majority of this acid modification body is to add adult with the low peracid of the molecular weight that is modified as purpose of resin.Therefore, can't use as formed body so far.
On the other hand, though few in number, also carried out keeping the rerum natura of acronal and the trial that manufacturing has chemically reactive polymkeric substance.
When adopting unsaturated carboxylic acid or its acid anhydrides to carry out MODIFICATION OF POLYPROPYLENE, disclose for 10% left and right sides by-product, rerum natura is produced dysgenic lower molecular weight body, after 1. employing is dissolved into modified polypropene in the solvent, the method that it is separated out, or 2. the technology (for example, opening clear 63-90511 communique with reference to the spy) that method of extraction is removed is carried out with specific solvent refluxing limit in the limit.This many by-products of technology lower molecular weight body.
In addition, a large amount of dione compounds that uses 30 times of amounts for modified polypropene is disclosed, the technology (for example, opening flat 2-185505 communique with reference to the spy) of under 120 ℃ high temperature unreacted unsaturated carboxylic acid or its acid anhydrides being removed.In addition, disclose for modified polypropene and used a large amount of diketone of 7 times of amounts and the mixed solvent of aromatic hydrocarbons, the technology of under 90-110 ℃ high temperature unreacted unsaturated carboxylic acid or its acid anhydrides being removed (for example, open flat 4-202202 communique with reference to the spy), these two technology are except the shortcoming of using a large amount of solvents, owing at high temperature handle, so modified polypropene might the fusion adhesion.
As mentioned above, for by-product hardly to rerum natura produce the sour modified propylene polymer compound of dysgenic lower molecular weight body manufacture method, use the method that a small amount of solvent removes unreacted unsaturated carboxylic acid or its acid anhydrides and want the harmonious actively research of control of sour addition amount and resin properties (molecular weight, systematicness etc.) is not almost carried out as yet under mild conditions.
The present invention In view of the foregoing proposes, and purpose is to be provided at polyolefine resin composition and the manufacture method thereof that has high comprehensive rerum natura under the situation of not damaging polyolefinic characteristic.
In addition, the object of the present invention is to provide the resin properties excellence, by-product produces the modified propylene polymer compound and the manufacture method thereof of dysgenic lower molecular weight body to rerum natura hardly.
Summary of the invention
The invention provides following modified propylene polymer compound, polyolefine resin composition and their manufacture method.
[1], the modified propylene polymer compound, it satisfies following (1)-(4):
(1) the polar group content partly that comes comfortable same intramolecularly to contain the compound of two keys of ethylenic and polar group is 0.10-0.30mmol/g,
The limiting viscosity of measuring in (2) 135 ℃, tetraline ([η]
A) be 0.8-3.0dl/g,
(3) molecular weight distribution (Mw/Mn) surpasses 2.5,
(4) molecular weight (Mw) is below the 5 weight % at the one-tenth component below 10,000.
[2], [1] described modified propylene polymer compound, wherein, the limiting viscosity of described modified propylene polymer compound ([η]
A) and the limiting viscosity ([η] in 135 ℃, tetraline, measured as the acronal of its raw material
S) ratio ([η]
A/ [η]
s) be more than 0.2.
[3], [1] or [2] described modified propylene polymer compound, wherein, the described compound that contains two keys of ethylenic and polar group at same intramolecularly is unsaturated carboxylic acid and/or its derivative.
The manufacture method of each described modified propylene polymer compound of [4], [1]-[3], it comprises: acronal, radical initiator and same intramolecularly are contained the compound of two keys of ethylenic and polar group, more than the fusing point of described acronal, carry out melting mixing under the temperature of 180 ℃ of less thaies.
[5], polyolefine resin composition, it contains following (A), (B) and (C) or following (A), (B), (C) and (D):
(A) polymkeric substance of the alpha-olefin of carbon number more than 3,
The described modified propylene polymer compound of each of (B) [1]-[3],
(C) organise layered inorganic compound,
(D) rubbery polymer.
[6], [5] described polyolefine resin composition, wherein, the melt flow rate (MFR) of described alpha-olefinic polymer (A) is the 0.1-200g/10 branch,
Described alpha-olefinic polymer (A) is homopolymer or the multipolymer that contains second alpha-olefin of first alpha-olefin of carbon number more than the 3 carbon number 2-20 different with above-mentioned first alpha-olefin with 0-20 weight %.
[7], the manufacture method of [5] or [6] described polyolefine resin composition, it comprise described (A), (B) and (C) or (A), (B), (C) and (D) mix, carry out melting mixing.
Description of drawings
Fig. 1 is the synoptic diagram of twin screw extruder.
Embodiment
Below polyolefine resin composition of the present invention is described.
Resin combination of the present invention contains following (A), (B) and (C), or following (A), (B), (C) and (D).
(A) polymkeric substance of the alpha-olefin of carbon number more than 3;
(B) satisfy the modified propylene polymer compound of following (1)-(4):
(1) the polar group content partly that comes comfortable same intramolecularly to contain the compound of two keys of ethylenic and polar group is 0.10-0.30mmol/g,
The limiting viscosity of measuring in (2) 135 ℃, tetraline ([η]
A) be 0.8-3.0dl/g,
(3) molecular weight distribution (Mw/Mn) surpasses 2.5,
(4) molecular weight (Mw) is below the 5 weight % at the one-tenth component below 10,000;
(C) layered inorganic compound that organises;
(D) rubbery polymer.
At first, each component to composition of the present invention describes.
As alpha-olefinic polymer (A), can enumerate the homopolymer of the alpha-olefin of carbon number more than 3, preferred carbon number 3-20, and the alpha-olefin of carbon number 3 or more and the carbon number 2-20 different with it, preferably random copolymers, segmented copolymer, the graft copolymer of the alpha-olefin of carbon number 2-10.Here, the copolymerization of the alpha-olefin of carbon number 2-20 is partly measured and is preferably 0-20 weight %, more preferably 0-10 weight %.
As the concrete example of alpha-olefinic polymer (A), can enumerate homopolymer such as propylene, 1-butylene, 4-methyl-1-pentene, the various multipolymers of propylene and ethene, propylene and 1-butylene, 4-methyl-1-pentene.Wherein, be preferably the segmented copolymer of homopolymer, propylene and the ethene of propylene.These can use independent a kind, also can be used in combination.
The melt flow rate (MFR) of alpha-olefinic polymer (A) is preferably the 0.1-200g/10 branch, more preferably the 1-100g/10 branch.If not enough 0.1g/10 branch, the formability of composition reduces sometimes.On the other hand, if surpass the 200g/10 branch, the shock-resistance of composition reduces sometimes.
Alpha-olefinic polymer (A) can use the known method manufacturing.
Modified propylene polymer compound (B) satisfies following (1)-(4).
(1) the polar group content partly that comes comfortable same intramolecularly to contain the compound (properties-correcting agent) of two keys of ethylenic and polar group is 0.10-0.30mmol/g,
The limiting viscosity of measuring in (2) 135 ℃, tetraline ([η]
A) be 0.8-3.0dl/g,
(3) molecular weight distribution surpasses 2.5,
(4) molecular weight is below the 5 weight % at the one-tenth component below 10,000.
In above-mentioned (1), if the not enough 0.10mmol/g of content of polar group part, when with its and other resin, when filler combination is used, in order fully to manifest the effect of polar group, must its combined amount of raising, cause damage economically.On the other hand, if surpass 0.30mmol/g, form and aspect reduce, and production stability, molecular-weight adjusting when the making difficulty that becomes.When particularly in composition of the present invention, using, if not enough 0.10mmol/g, the dispersion of peeling off that can fully not produce the layered inorganic compound that organises (C).On the other hand, if surpass 0.30mmol/g, with the consistency reduction of alpha-olefinic polymer (A).The content of polar group part is preferably 0.15-0.3mmol/g, more preferably 0.2-0.3mmol/g.
Below describe for the properties-correcting agent that constitutes this polar group part.
In above-mentioned (2), limiting viscosity ([η]
AIf) not enough 0.8dl/g, when separately or with other resins, when filler combination is used, cause the reduction of mechanics rerum natura easily.On the other hand, if surpass 3.0dl/g, when separately or with other resins, when filler combination is used, become that formability reduces, the reason of gel in the formed body.Limiting viscosity ([η]
A) be preferably 0.9-2.5dl/g, more preferably 1.0-2.0dl/g.
Above-mentioned limiting viscosity ([η]
A) and as the limiting viscosity ([η] of the acronal of polymer-modified raw material
S) ratio ([η]
A/ [η]
S) be preferably more than 0.2, more preferably more than 0.25.Should be such as fruit less than 0.2, polymer-modified molecular weight distribution becomes below 2.5 easily.
In addition, the cut-out degree of the molecular chain that this is more polymer-modified than expression, this means that than big more polymer-modified molecular chain is not cut off more.
Below the raw material propylene base polymer is described.
In above-mentioned (3), molecular weight distribution (Mw/Mn) is mixed the quite difficulty that becomes if be below 2.5 in composition, and rigidity reduces.Molecular weight distribution preferably surpasses 2.8, more preferably surpasses 3.0.Here, Mw represents weight-average molecular weight, and Mn represents number-average molecular weight.
This molecular weight distribution (Mw/Mn) can adopt example gel permeation chromatography (GPC) method to measure.
In above-mentioned (4), molecular weight (Mw) is if be that one-tenth component below 10,000 surpasses 5 weight %, and the shock-resistance of composition reduces.In addition, become the reason of deterioration of complete adhesion, the surface texture of formed body sometimes.This one-tenth component is preferably below the 3 weight %, more preferably below the 2 weight %.
In addition, so-called molecular weight (Mw) is the one-tenth component below 10,000, means the one-tenth component of molecular weight in the GPC curve (Mw) below 10,000.
Modified propylene polymer compound (B) preferably satisfies following (5)-(6).
(5) content of unreacted properties-correcting agent is for analyzing below the boundary value
(6) fusing point is 145-170 ℃
In above-mentioned (5), the content of unreacted properties-correcting agent can be tried to achieve by following operation.
With polymer-modified be dissolved in the p-Xylol after, it is precipitated in acetone separates out, carry out the operation that unreacted properties-correcting agent is removed fully.Should operate and added up to 5 times repeatedly, carry out quantitatively with the content of aforesaid method to the part of the polar group in polymer-modified.With this quantitative values as the content (solvent refining process) that does not contain the properties-correcting agent in unreacted properties-correcting agent polymer-modified.
The content of so-called unreacted properties-correcting agent is being analyzed below the boundary value, and the content that means the properties-correcting agent in polymer-modified is in the analytical error scope of above-mentioned quantitative values.
In above-mentioned (6), if 145 ℃ of fusing point less thaies when separately or with other resins, when filler combination is used, cause stable on heating reduction sometimes jointly.More preferably 155-170 ℃ of fusing point.
This polymer-modified (B) can mix by the compound (properties-correcting agent) that raw material propylene base polymer, radical initiator and same intramolecularly is contained two keys of ethylenic and polar group, more than the fusing point of raw material propylene base polymer, carry out melting mixing under the temperature of 180 ℃ of less thaies and make.
As the raw material propylene base polymer, can enumerate for example random copolymers, segmented copolymer, graft copolymer and their mixture of alfon, propylene and alpha-olefin (for example ethene, 1-butylene, 4-methyl-1-pentene etc.).Wherein, be preferably alfon.
The limiting viscosity [η] that the raw material propylene base polymer is measured in 135 ℃, tetraline
sBe preferably more than the 3dl/g, more preferably 4-10dl/g.If not enough 3dl/g, polar group part content reduces (below 0.10) or molecular weight reduction (η＜0.8) sometimes.
The raw material propylene base polymer preferably satisfies following (1)-(3).
(1) the solvable one-tenth component of boiling heptane is for analyzing below the boundary value
(2) molecular weight distribution (Mw/Mn) is below 5
(3) molecular weight (Mw) is more than the 25 weight % at the one-tenth component more than 1,000,000
In above-mentioned (1), the solvable one-tenth component of so-called boiling heptane means below the boundary value that for analyzing stock polymer 10.000g Soxhlet is extracted the extraction residual polyalcohol amount that obtains for 5 times (to be essentially and to analyze below the boundary value) in the scope of 10 ± 0.002g.
In above-mentioned (2), if molecular weight distribution (Mw/Mn) surpasses 5, the molecular weight (Mw) in polymer-modified is that the one-tenth component 10,000 below is big above the possibility of 5 weight % by-products.As long as molecular weight distribution is that then there is no particular restriction below 5, more preferably 3-5.
In addition, this molecular weight distribution can similarly be calculated with polymer-modified molecular weight distribution.
In above-mentioned (3), if molecular weight (Mw) is a one-tenth more than the 1000000 25 weight % that give short measure, the content of polar group part reduces sometimes.As long as this one-tenth component is that then there is no particular restriction more than the 25 weight %, more preferably 25-50 weight %.
In addition, so-called molecular weight (Mw) is the one-tenth component more than 1,000,000, means that molecular weight in the GPC curve (Mw) is the one-tenth component more than 1,000,000.
As radical initiator, can enumerate the peroxidation butyl, α, α-two (t-butyl peroxy) diisopropylbenzene(DIPB), benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, t-butyl peroxy-acetate, t-butyl peroxy diethylacetic acid ester, t-butylperoxy isobutylate, cross the Zhong Xin tert-butyl acrylate, cross the PIVALIC ACID CRUDE (25) tert-butyl ester, cross the withered ester of PIVALIC ACID CRUDE (25), t-butylperoxyl benzoate, t-butyl peroxy phenylacetic acid ester, tertiary butyl cumyl peroxide, ditertiary butyl peroxide, 1,1-di-t-butyl peroxide-3,3, the 5-trimethyl-cyclohexane, 1,1-di-t-butyl peroxy cyclohexane, 2,2-two-(t-butyl peroxy) butane, lauroyl peroxide, 2,5-dimethyl-2,5-two (peroxy benzoate) hexin-3,1,3-two (t-butyl peroxy sec.-propyl) benzene, 1,4-two (t-butyl peroxy sec.-propyl) benzene, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexin-3,2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 2,4,4-trimethyl benzyl-2-hydroperoxide, the diisopropylbenzene(DIPB) hydroperoxide, cumene hydroperoxide, 4,4-di-t-butyl peroxide n-butyl pentanoate, di-t-butyl peroxide hexahydrophthalic acid ester, di-t-butyl peroxide azelate, t-butyl peroxy-3,3,5-tri-methyl hexanoic acid ester, t-butyl peroxy-sec.-propyl carbonic ether, succinic acid peroxide and vinyl three-(t-butyl peroxy) silane etc.Wherein, be preferably 1,3-two (t-butyl peroxy sec.-propyl) benzene, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexin-3, dicumyl peroxide, α, α-two (t-butyl peroxy) diisopropylbenzene(DIPB), 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane.These can use a kind separately, also can be used in combination.
As the polar group that properties-correcting agent contained, can enumerate for example carboxylic acid group, acid anhydride, carboxylic acid ester groups, acid halide base, carboxamide groups, carboxylic imide, carboxylate group, sulfonic group, sulfonate group, sulfuryl chlorio, sulfoamido, sulphonate-base, epoxy group(ing), amino, azoles quinoline base etc.Wherein, optimization acid's base and acid anhydride.
There is no particular restriction for the properties-correcting agent that uses among the present invention, is preferably the unsaturated carboxylic acid and/or its derivative that contain above-mentioned polar group.
As the unsaturated carboxylic acid or derivatives thereof, can enumerate for example unsaturated monobasic or di-carboxylic acid or their derivative.As these derivative, be specially acid anhydrides, ester, halogenide, acid amides, imide and the salt etc. of carboxylic acid.Wherein, be preferably unsaturated dicarboxylic acid or its acid anhydrides.
Concrete example as unsaturated monobasic or di-carboxylic acid, can enumerate vinylformic acid, methacrylic acid, toxilic acid, interior dicyclo [2.2.1]-5-heptene-2,3-dioctyl phthalate (acid of エ Application デ イ Star Network), fumaric acid, tetrahydrophthalic acid, methylene-succinic acid, citraconic acid, Ba Dousuan, iso-crotonic acid, the acid of Na ジ Star Network etc.
As the concrete example of the derivative of unsaturated carboxylic acid, can enumerate Malaysia acyl chlorides, maleimide, maleic anhydride, エ Application デ イ Star Network acid anhydrides, methyl acrylate, acrylamide, methyl methacrylate, glycidyl methacrylate, Methacrylamide, citraconic anhydride, itaconic anhydride, Na ジ Star Network acid anhydrides, monomethyl maleate, dimethyl maleate, monomethyl fumarate, dimethyl fumarate etc.
In these unsaturated carboxylic acid or derivatives thereofs, preferred vinylformic acid, methacrylic acid and maleic anhydride, more preferably maleic anhydride.These can use a kind separately, also can be used in combination more than 2 kinds.
During polymer-modified manufacturing, radical initiator preferably mixes the 0.1-5 weight part with respect to stock polymer 100 weight parts, more preferably mixes the 0.5-2 weight part.If combined amount less than 0.1 weight part, polar group content reduces sometimes.On the other hand, if surpass 5 weight parts, molecular weight reduction sometimes and molecular weight distribution (Mw/Mn) are below 2.5.
In addition, properties-correcting agent preferably mixes the 1.5-10 weight part with respect to stock polymer 100 weight parts, more preferably mixes the 2-6 weight part.If combined amount less than 1.5 weight parts, polar group content reduces sometimes.On the other hand, if surpass 10 weight parts, the residual quantity of unreacted properties-correcting agent might increase and production stability might reduce.And then the form and aspect of goods also worsen sometimes significantly.
Blending means as each component is not particularly limited, and can enumerate for example dry mix.Can use twin screw extruder for example shown in Figure 1 after the mixing, at melting mixing more than the fusing point of stock polymer, under the temperature of 180 ℃ of less thaies.During melting mixing, preferably making from the hopper bottom 1 of twin screw extruder barrel the resin temperature of plasticizing zone front portion 2 is temperature below 150 ℃, makes more than the fusing point that is stock polymer from the plasticizing zone 3 and 4 resin temperatures to die head 5 of barrel, the temperature of 180 ℃ of less thaies.At this moment, in order to prevent dispersing of properties-correcting agent, the resin temperature of hopper bottom 1 is preferred below 130 ℃, more preferably below 100 ℃, is preferably normal temperature-60 ℃ especially.
If making the melting mixing temperature is more than 180 ℃, when making the stock polymer modification make the content of polymer-modified polar group part reach above-mentioned scope, molecular weight distribution narrows down easily, is below 2.5.In addition, so-called melting mixing temperature means highest temperature temperature partly in the barrel of twin screw extruder, in Fig. 1, means the temperature the plasticizing zone 3 and 4 from die head 5 to barrel.
Melting mixing (delay) time is preferably 10-120 second.
During melting mixing preferably under inert atmosphere.At this moment, can add steam, perhaps under reduced pressure volatile component be removed.
As shaper, use single screw extrusion machine, twin screw extruder etc.
As twin screw extruder, can enumerate 20mm ラ ボ プ ラ ス ト ミ Le, 35mmTEM (toshiba machine system twin screw extruder) etc.
If adopt this method to make modified propylene polymer compound (B), make the polymkeric substance that needn't use ultra-high molecular weight in the raw material.In addition, because the decomposition multiplying power of manufacturing raw material etc. is little, the production stability in the time of can realizing making, cost reduce.In addition, owing to can reduce the usage quantity of radical initiator (superoxide), therefore also can expect polymer-modified form and aspect improvement.
Modified propylene polymer compound of the present invention has kept the characteristic of stock polymer owing to the molecular weight height, therefore can be used as film, formed body use.In addition, owing to contain unreacted properties-correcting agent hardly, the content of lower molecular weight body is also few, so separating out of lower molecular weight body lacked.Therefore, also can separate out in the purposes that becomes problem and use at film etc.
Modified propylene polymer compound of the present invention is except these characteristics, owing to also have the characteristic that content is many, molecular weight distribution is wide of polar group part, therefore suitable manufactured materials as the polyolefins nano-complex.If be of the present invention polymer-modified, though when the manufacturing of nano-complex macro-mixing, also can significantly suppress the reduction of rerum natura.
That is, modified propylene polymer compound (B) has the characteristic of high polar group part content, high molecular, wide molecular weight distribution and the poor characteristic of low molecular weight compositions.Use has the polymer-modified of this characteristic, is effective for the raising of the comprehensive rerum natura of composition of the present invention.
As the layered inorganic compound that organises (C), can enumerate the material that the interlayer cation of layered silicate is for example replaced by alkylammonium.As layered silicate, can enumerate layered clay mineral, specifically can enumerate the layered clay mineral of smectitess such as montmorillonite, wilkinite, saponite, hectorite, beidellite, ス テ イ Block Application サ イ ト, nontronite; Vermiculite; Halloysite; Mica; These fluorochemical etc.These can be natural goodses, also can be syntheticss.
The swelling property material that the preferred interlayer cation of layered silicate is replaced by alkylammonium easily.The cation exchange capacity of layered silicate is preferably 70 milliequivalents/more than the 100g, more preferably 85-250 milliequivalent/100g.
As the concrete example of the layered silicate of preferred use, can enumerate montmorillonite, wilkinite, swelling property mica, swelling property fluorine mica etc., preferred especially montmorillonite and swelling property fluorine mica.
Interlayer cation is that layered silicate remains on the layer and the positively charged ion of interlayer, can enumerate potassium ion, sodium ion, calcium ion, barium ion etc.
As alkylammonium, can enumerate hexyl ammonium ion, octyl ammonium ion, 2-ethylhexyl ammonium ion, dodecyl ammonium ion, octadecyl ammonium ion, dioctyl Dimethyl Ammonium ion, trioctylammonium ion, stearyl ammonium ion, distearyl ammonium ion etc.Wherein, preferred octadecyl ammonium ion, dioctyl Dimethyl Ammonium ion, trioctylammonium ion, stearyl ammonium ion, distearyl ammonium ion.
The part of interlayer cation can be replaced, and also can all be replaced.Replacement amount is preferably more than 50% of interlayer cation, more preferably 80-100%.
The layered inorganic compound (C) that organises can adopt the known method manufacturing.For example, above-mentioned layered silicate is distributed to the aqueous solution of the suspension liquid that obtains in the water and above-mentioned alkylammonium salt, react 30 minutes-5 hours while stirring at normal temperatures after, from reaction solution,, wash, dry and obtain the solids component solid-liquid separation.When layered silicate and alkylammonium salt are mixed,, preferably mix 0.5-1.5 times of equivalent, more preferably mix the doubly normal alkylammonium salt of 0.8-1.2 with respect to the cation exchange capacity of layered silicate.
The interlayer cation of layered inorganic compound (C) is replaced by alkylammonium owing to organise, and therefore compares with the layered silicate before the displacement, and interfloor distance increases.If the layered inorganic compound that organises (C) of this state is mixed with modified propylene polymer compound (B), the chain of the part of modified propylene polymer compound (B) combines with the layered inorganic compound that organises (C), or invades its interlayer.Its result is in composition, and the interfloor distance of the layered inorganic compound that organises (C) further enlarges.The shear-stress that is subjected to when in the present invention, this layered inorganic compound that organises (C) is by melting mixing and equably, be distributed in the composition imperceptibly.
The layered inorganic compound (C) that organises can a kind uses separately, also can be used in combination more than 2 kinds.
As rubbery polymer (D), can enumerate olefin type elastomer, ethene/olefin type elastomers such as 1-octene copolymer, hydrogenation styrene/butadiene block copolymer styrenics such as (SEBS) elastomericss etc. such as ethylene/propylene rubber.Wherein, optimization styrene class elastomerics, more preferably hydrogenation styrene/butadiene block copolymer.These can a kind use separately, also can be used in combination more than 2 kinds.
Can in composition of the present invention, suitably mix other additives such as nucleator, oxidation inhibitor, UV light absorber, exterior lubricant, softening agent, static inhibitor, tinting material, fire retardant, flame retardant as required.As nucleator, can enumerate the metal-salt, talcum, phthalocyanine derivates etc. of phosphoric acid of the metal-salt, methylene-bis (2, the 4-DI-tert-butylphenol compounds) sodium acid phosphate etc. of the carboxylic acid of aluminium two (p-tert-butyl benzoic acid salt) etc. for example.As softening agent, can enumerate for example polyoxyethylene glycol, polyamide oligomer as well as, ethylenebisstearamide, phthalic ester, polystyrene oligopolymer, polyethylene wax, mineral oil, silicone oil etc.As fire retardant, can enumerate for example brominated Polystyrene, bromination syndiotactic polystyrene, brominated polyphenylether etc.As flame retardant, can enumerate for example antimony compounds such as ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.As oxidation inhibitor, for example can enumerate (2,6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate phosphorus such as (ア デ カ ア one ガ ス society system, PEP-36) is oxidation inhibitor, four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl)] propionic ester Hinered phenols antioxidants such as (ア デ カ ア one ガ ス society system, MARK A060) etc.These additives can use a kind separately, also can be used in combination more than 2 kinds.
Below the manufacture method of composition of the present invention is described.
Composition of the present invention can be by mixing above-mentioned each component, carrying out melting mixing and make.In addition, the temperature during for the blending means of each component, melting mixing, time etc. create conditions that there is no particular restriction, can suitably regulate.
The combined amount of each component, in the composition that contains alpha-olefinic polymer (A), modified propylene polymer compound (B) and the layered inorganic compound that organises (C), (A) component is preferably 50-95 weight part, 50-85 weight part more preferably, (B) component is preferably 4-50 weight part, 10-50 weight part more preferably, and (C) component is preferably 1-30 weight part, 5-20 weight part more preferably.
In addition, in the composition that contains alpha-olefinic polymer (A), modified propylene polymer compound (B), the layered inorganic compound that organises (C) and rubbery polymer (D), (A) component is preferably 30-95 weight part, 40-75 weight part more preferably, (B) component is preferably 4-50 weight part, 10-50 weight part more preferably, (C) component is preferably 1-30 weight part, 5-20 weight part more preferably, and (D) component is preferably 5-40 weight part, 10-30 weight part more preferably.
(A) if combined amount less than 50 weight parts or 30 weight parts of component, cost raises sometimes, the harmony of rigidity and shock-resistance reduces simultaneously.On the other hand, if surpass 95 weight parts, the effect of (C) component is difficult to embody and the harmony of rigidity and shock-resistance reduces sometimes.
(B) if combined amount less than 4 weight parts of component, (C) component peel off become when being dispersed with the difficulty.On the other hand, if surpass 50 weight parts, when raising, cost causes sometimes that the rerum natura of shock-resistance etc. reduces.
(C) if combined amount less than 1 weight part of component, the rigidity of composition improves effect and diminishes sometimes.On the other hand, if surpass 30 weight parts, when peeling off of (C) component disperseed to become difficulty, the lightweight effect of composition reduced sometimes.
(D) if combined amount less than 5 weight parts of component, the shock-resistance of goods reduces sometimes.On the other hand, if surpass 40 weight parts, rigidity reduces sometimes.
In composition of the present invention, by mixed and modified acronal (B), the combined amount of the layered inorganic compound that organises (C) gets final product on a small quantity, therefore can not damage low-gravity characteristic of alpha-olefinic polymer (A).In addition, because can organifying layered inorganic compound (C) high dispersing, therefore can keep rerum naturas such as rigidity, shock-resistance, thermotolerance well with high level, harmony.Composition of the present invention is not only low-gravity, and demonstrates the equal above performance of high specific gravity polypropylene-base matrix material (for example filling steatitic polypropylene etc.) in the past.
The suitable Industrial materials of composition of the present invention as automotive materials such as collision bumper, panel board, use engineering plastics.
Embodiment
Below embodiments of the invention are described, but the present invention is not limited to these embodiment.
In addition, content, the limiting viscosity [η] of the polar group of modified propylene polymer part
A, molecular weight distribution (Mw/Mn), molecular weight (Mw) the one-tenth component (LP amount) below 10,000 and the limiting viscosity [η] of the raw material propylene polymkeric substance of modified propylene polymer
S, fusing point adopts following method to measure.
(1) content of polar group part
With polymer-modified film forming, use it to measure the fourier-transform infrared absorption spectrum and calculate.
(2) limiting viscosity [η]
A, [η]
S
In 135 ℃, tetraline, measure.
(3) Mw/Mn, LP amount
The Mw and the Mn that are converted by the polypropylene of measuring under following apparatus and condition calculate.The LP amount is obtained as the one-tenth component of molecular weight (Mw) below 10,000 in the GPC curve.
(GPC determinator)
Post: TOSOGMHHR-H (S) HT
Detector: phase chromatography-use RI detector WATERS 150C
(condition determination)
Solvent: 1,2, the 4-trichlorobenzene
Temperature: 145 ℃
Flow velocity: 1.0mL
Test portion concentration: 2.2mg/mL
Injection rate: 160 μ L
Detection line: Universal Calibration
Analysis program: HT-GPC (1.0 editions)
(4) fusing point
Use differential scanning calorimetry (DSC), under nitrogen gas stream, under 220 ℃, with the test portion fusion after 3 minutes, cool to 25 ℃ with 10 ℃/minute, 25 ℃ keep 3 minutes after, with 10 ℃ of/minute intensifications, obtain fusing the summit of endothermic curve and obtain.
In addition, the melt flow rate (MFR) (M.I.) of acronal (A-1 and A-2) is according to JIS-K7210, at resin temperature: 230 ℃, load: measure under the 2.16kg.
Production Example 1
[synthesizing of raw material propylene polymkeric substance]
(1) modulation of prepolymerization catalyst composition
After the there-necked flask displacement that have stirrer of nitrogen, add heptane 400ml, the diethyl aluminum chloride 18g of processed, commercially available Sol dimension type titanium trichloride catalyst (eastern beautiful fine chemicals company make) 2g with internal volume 0.5L.Temperature is 20 ℃ in keeping, and imports propylene while stirring.After 80 minutes, stop to stir the prepolymerization catalyst composition of 0.8g propylene that obtained the polymerization of every 1g solid catalyst.
(2) the raw material propylene polymkeric substance is synthetic
With the stainless steel autoclave thorough drying that has stirrer of internal volume 10L, after with nitrogen replacement, add the heptane 6L of processed, with propylene with the nitrogen replacement in the system.Then, add hydrogen 0.06MPaG, import propylene while stirring.Behind 65 ℃ of temperature, the propylene pressure 0.75MPaG, convert with solid catalyst in being stabilized in system, add the heptane slurry 50ml that contains synthetic prepolymerization catalyst composition among the 0.5g above-mentioned (1), the limit is supplied with the propylene limit continuously and carry out polymerization in 1.5 hours under 65 ℃.
Then, temperature is 50 ℃ in making, and weakens stirring, takes off pressure.Add hydrogen 0.04MPaG then, import propylene while stirring.Under 50 ℃, carry out polymerization in 6 hours on 50 ℃ of interior temperature, the following propylene limit of supplying with continuously of propylene pressure 0.75MPaG.After polymerization finishes, add the methyl alcohol of 50ml, lower the temperature, take off pressure.Content is all transferred in the filter vat that has strainer, be warmed up to 85 ℃, carry out solid-liquid separation.Then, with solid part washing 2 times, carry out vacuum-drying, obtain propene polymer 2.1kg with 85 ℃ 6L heptane.The limiting viscosity of this polymkeric substance [η]
SBe 4.02dl/g, fusing point is 162.In addition, the catalytic activity of every 1g solid catalyst was 4.2kg/g-cat.7.5hr at polymerase 17 .5 hour.With its for carrying out propylene polymerization repeatedly under the identical conditions, with the polymkeric substance that obtains as the raw material propylene polymkeric substance.
Production Example 2
[synthesizing of raw material propylene polymkeric substance]
In Production Example 1 (2), except respectively the hydrogen-pressure of the 1st section and the 2nd section being become 0.03MPaG and the 0.025MPaG, with Production Example 1 synthesis material acronal similarly.The limiting viscosity of this polymkeric substance [η]
SBe 6.05dl/g, fusing point is 161 ℃.
Production Example 3
[synthesizing of raw material propylene polymkeric substance]
(1) modulation of solid catalyst component
After the there-necked flask displacement that have stirrer of nitrogen, add octane 60ml, the diethoxy magnesium 16g of processed with internal volume 0.5L.Be heated to 40 ℃, add silicon tetrachloride 2.4ml, stir after 20 minutes, add dibutyl phthalate 1.6ml.This solution is warmed up to 80 ℃, then splashes into the 77ml titanium tetrachloride, stirred 2 hours down for 125 ℃, carry out operating of contacts in interior temperature.Then, stop stirring and make solid precipitation, clarification part above taking out.The dehydration octane that adds 100ml, warming while stirring to 125 ℃ kept after 1 minute, stopped to stir making solid precipitation, clarified part above taking out.This washing operation is carried out 7 times repeatedly.Then, add the 122ml titanium tetrachloride, stirred 2 hours down for 125 ℃, carry out operating of contacts the 2nd time in interior temperature.Then, carry out 6 washings of carrying out with the dehydration octane under above-mentioned 125 ℃ repeatedly, obtain solid catalyst component.
(2) modulation of prepolymerization catalyst composition
After the there-necked flask displacement that have stirrer of nitrogen with internal volume 0.5L, synthetic solid catalyst component 4g in heptane 400ml, the triisobutyl aluminium 25mmol of adding processed, dicyclopentyl dimethoxyl silane 2.5mmol, above-mentioned (1).At room temperature, import propylene while stirring.After 1 hour, stop to stir the result has obtained the polymerization of the every 1g solid catalyst prepolymerization catalyst composition of 4g propylene.
(3) the raw material propylene polymkeric substance is synthetic
With the stainless steel autoclave thorough drying that has stirrer of internal volume 10L, after with nitrogen replacement, add heptane 6L, triethyl aluminum 12.5mmol, the dicyclopentyl dimethoxyl silane 0.3mmol of processed.With propylene with the nitrogen replacement in the system after, import propylene to it while stirring.Behind 80 ℃ of temperature, the total head 0.8MPa, convert with the Ti atom in being stabilized in system, add the heptane slurry 50ml that contains synthetic prepolymerization catalyst composition among the 0.08mmol above-mentioned (2), the limit is supplied with the propylene limit continuously and carry out polymerization in 3 hours under 80 ℃.
After polymerization finishes, add the methyl alcohol of 50ml, lower the temperature, take off pressure.Content is all transferred in the filter vat that has strainer, be warmed up to 85 ℃, carry out solid-liquid separation.Then, with solid part washing 2 times, carry out vacuum-drying, obtain propene polymer 2.5kg with 85 ℃ 6L heptane.The limiting viscosity of this polymkeric substance [η]
SBe 7.65dl/g, fusing point is 164 ℃.In addition, the catalytic activity of every 1g solid catalyst hour is 9.8kg/g-cat.3hr at polyase 13.With its for carrying out propylene polymerization repeatedly under the identical conditions, with the polymkeric substance that obtains as the raw material propylene polymkeric substance.
Embodiment 1
[synthesizing of maleic anhydride modified propene polymer]
In Production Example 1, add maleic anhydride 5 weight parts and パ one カ De Star Network ス 14-40C (trade(brand)name, 1 in synthetic raw material propylene polymkeric substance 100 weight parts, 3-two-(t-butyl peroxy sec.-propyl) benzene/lime carbonate: 40/60 (weight ratio), chemical drug ア Network ゾ society system) 2.5 weight parts, do and mix, use the twin screw extruder of 35mm to carry out melting mixing.The temperature of twin screw extruder is during melting mixing: 40 ℃ of hopper bottoms, anterior 120 ℃ of plasticizing zone, 170 ℃ of plasticizing zones, 180 ℃ of die heads.In addition, it is corresponding to have the part of reference number among these each several parts and Fig. 1.
In granulated samples 100 weight parts of preparation, add acetone 50 weight parts, heptane 50 weight parts, in 85 ℃ of following heated and stirred 2 hours (in pressure vessel, implementing).Behind this EO, with wire netting particle is reclaimed, it was flooded 15 hours in the acetone of 100 weight parts.Then, reclaim particle with wire netting, air-dry back carry out under 80 ℃ 6 hours, under 130 ℃, carry out vacuum-drying in 6 hours, obtain maleic anhydride modified propene polymer.Physics value is shown in table 1.
Embodiment 2
[synthesizing of maleic anhydride modified propene polymer]
In embodiment 1, except the combined amount with パ one カ De Star Network ス 14-40C becomes 1.5 weight parts, synthesis of maleic anhydride modified propylene polymer similarly to Example 1.Physics value is shown in table 1.
Embodiment 3
[synthesizing of maleic anhydride modified propene polymer]
In embodiment 1, synthetic raw material propylene polymkeric substance in replacing Production Example 1 and using in the Production Example 2 the synthetic raw material propylene base polymer, synthesis of maleic anhydride modified propylene polymer similarly to Example 1.Physics value is shown in table 1.
Comparative example 1
[synthesizing of maleic anhydride modified propene polymer]
In Production Example 3, add maleic anhydride 1 weight part and カ ヤ Block チ Le B (trade(brand)name, t-butyl peroxy benzoic ether, chemical drug ア Network ゾ society system) 1 weight part in synthetic raw material propylene polymkeric substance 100 weight parts, do and mix, use the twin screw extruder of 35mm to carry out melting mixing.The temperature of twin screw extruder is during melting mixing: hopper bottom, plasticizing zone front portion, plasticizing zone, die head all are 210 ℃.
In granulated samples 100 weight parts of preparation, add acetone 50 weight parts, heptane 50 weight parts, in 85 ℃ of following heated and stirred 2 hours (in pressure vessel, implementing).Behind this EO, with wire netting particle is reclaimed, it was flooded 15 hours in the acetone of 100 weight parts.Then, reclaim particle with wire netting, air-dry back carry out under 80 ℃ 6 hours, under 130 ℃, carry out vacuum-drying in 6 hours, obtain maleic anhydride modified propene polymer.Physics value is shown in table 1.
Comparative example 2
In Production Example 3, add maleic anhydride 5 weight parts and パ one カ De Star Network ス 14-40C 5 weight parts in synthetic raw material propylene polymkeric substance 100 weight parts, do and mix, use the twin screw extruder of 35mm, with the same temperature condition of comparative example 1 under carry out melting mixing.In granulated samples 100 weight parts of preparation, add acetone 50 weight parts, heptane 50 weight parts, in 85 ℃ of following heated and stirred 2 hours (in pressure vessel, implementing).Behind this EO, with wire netting particle is reclaimed, it was flooded 15 hours in the acetone of 100 weight parts.Then, reclaim particle with wire netting, air-dry back carry out under 80 ℃ 6 hours, under 130 ℃, carry out vacuum-drying in 6 hours, obtain maleic anhydride modified propene polymer.Physics value is shown in table 1.
Table 1
| Project | Unit | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Polymer-modified | The content of polar group part | mmol/g | 0.15 | 0.13 | 0.20 | 0.08 | 0.10 |
| [η] A | dl/g | 0.86 | 1.18 | 1.21 | 0.70 | 0.72 | |
| Mw/Mn | - | 3.2 | 3.4 | 3.5 | 1.9 | 1.9 | |
| The LP amount | Weight % | 2.6 | 1.4 | 2.7 | 2.3 | 2.0 | |
| [η] A/[η] S | - | 0.21 | 0.29 | 0.30 | 0.09 | 0.09 |
Embodiment 4-18 and comparative example 3-9
[modulation of polypropylene resin composite]
By blending ratio shown in table 2 and the table 3 with acronal shown below (A), modified propylene polymer (B), the layered inorganic compound that organises (C), rubbery polymer (D) blend after, use twin screw extruder, under 230 ℃, carry out melting mixing, the modulation polypropylene resin composite.
As acronal (A), use following A-1 and A-2.
A-1: high impact resistance polypropylene (propylene-ethylene block copolymer) (J784H (trade(brand)name), bright dipping petroleum chemistry system, copolymerization part content: 12 weight %, M.I.:10g/10 branch)
A-2: alfon (J3000GP (trade(brand)name), bright dipping petroleum chemistry system, M.I.:30g/10 branch)
As modified propylene polymer (B), use following B-1～B-7.
The maleic anhydride modified propene polymer of synthetic among B-1: the embodiment 1
The maleic anhydride modified propene polymer of synthetic among B-2: the embodiment 2
The maleic anhydride modified propene polymer of synthetic among B-3: the embodiment 3
B-4: the commercially available maleic anhydride modified propene polymer (content of Port リ ボ Application De 3200 (trade(brand)names), Network ロ Application プ ト Application society system, polar group part: 0.048mmol/g, [η]
A: 0.76dl/g, Mw/Mn:2.4, LP amount: 4.0 weight %)
B-5: (ユ one メ Star Network ス 1010 (trade(brand)names), Sanyo change into the content of society's system, polar group part to commercially available maleic anhydride modified propene polymer: 0.43mmol/g, [η]
A: 0.19dl/g, Mw/Mn:4.1, LP amount: 43.5 weight %)
B-6: the maleic anhydride modified propene polymer of synthetic in the comparative example 1
B-7: the maleic anhydride modified propene polymer of synthetic in the comparative example 2
As the layered inorganic compound that organises (C), use following C-1 and C-2.
C-1: montmorillonite (Network ニ ピ ア F (trade(brand)name), Network ニ ミ ネ industry society system, organic ammonium salt: 40 weight %)
C-2: swelling property synthetic mica (ソ マ シ Off (trade(brand)name), コ one プ ケ ミ カ Le society system, swelling property fluorine mica, organic ammonium salt: 30 weight %)
As rubbery polymer (D), use following D-1 and D-2.
D-1: ethylene-propylene copolymer rubber (EP02P (trade(brand)name), Japanese synthetic rubber society system)
D-2:SEBS (Network レ イ Application ト Application G1652 (trade(brand)name), shell chemistry society system)
[evaluation of physical property]
For the polypropylene resin composite of preparation, estimate the rerum natura (, estimating the rerum natura of following (1)-(2)) of following (1)-(3) for the composition of embodiment 11-18 and comparative example 7-9.Evaluation result is shown in table 2 and table 3.
(1) bending elastic modulus: according to JIS K7203
(2) Izod shock strength: according to JIS K7110 (23 ℃, band breach)
(3) heat-drawn wire: according to JIS K7207
Table 2
| Project | Unit | Embodiment 4 | Embodiment | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | ||
| Composition | Component A | Kind | - | A-1 | A-1 | A-1 | A-1 | A-1 | A-2 | A-1 | A-1 | A-1 | A-1 | A-1 |
| Combined amount | Weight part | 65 | 65 | 65 | 50 | 50 | 65 | 65 | 65 | 65 | 65 | 50 | ||
| B component | Kind | - | B-1 | B-2 | B-3 | B-1 | B-1 | B-1 | B-1 | B-4 | B-5 | B-6 | B-7 | |
| Combined amount | Weight part | 30 | 30 | 30 | 50 | 50 | 30 | 30 | 30 | 30 | 30 | 50 | ||
| Component C | Kind | - | C-1 | C-1 | C-1 | C-1 | C-1 | C-1 | C-2 | C-1 | C-1 | C-1 | C-1 | |
| Combined amount | Weight part | 8 | 8 | 8 | 8 | 20 | 8 | 7 | 8 | 8 | 8 | 8 | ||
| Physics value | Bending elastic modulus | MPa | 2710 | 2680 | 2620 | 2960 | 4340 | 3290 | 3450 | 1880 | 2410 | 2240 | 2330 | |
| The Izod shock strength | KJ/m 2 | 5.4 | 6.5 | 7.1 | 4.6 | 3.1 | 2.2 | 4.9 | 5.0 | 1.9 | 4.2 | 2.8 | ||
| Heat-drawn wire | ℃ | 138 | 135 | 132 | 134 | 140 | 142 | 140 | 124 | 109 | 128 | 129 | ||
Table 3
| Project | Unit | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | Embodiment 15 | Embodiment 16 | Embodiment 17 | Embodiment 18 | Comparative example 7 | Comparative example 8 | Comparative example 9 | ||
| Composition | Component A | Kind | - | A-1 | A-1 | A-1 | A-1 | A-1 | A-2 | A-1 | A-1 | A-1 | A-1 | A-1 |
| Combined amount | Weight part | 55 | 55 | 55 | 50 | 40 | 55 | 55 | 55 | 55 | 55 | 50 | ||
| B component | Kind | - | B-1 | B-2 | B-3 | B-1 | B-1 | B-1 | B-1 | B-1 | B-4 | B-5 | B-7 | |
| Combined amount | Weight part | 25 | 25 | 25 | 50 | 40 | 25 | 25 | 25 | 25 | 25 | 50 | ||
| Component C | Kind | - | C-1 | C-1 | C-1 | C-1 | C-1 | C-1 | C-2 | C-1 | C-1 | C-1 | C-1 | |
| Combined amount | Weight part | 8 | 8 | 8 | 8 | 20 | 8 | 8 | 8 | 8 | 8 | 8 | ||
| Component D | Kind | - | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-1 | D-2 | D-1 | D-1 | D-1 | |
| Combined amount | Weight part | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | ||
| Physics value | Bending elastic modulus | MPa | 1820 | 1730 | 1690 | 1910 | 3800 | 2660 | 2010 | 1790 | 1010 | 1610 | 1490 | |
| The Izod shock strength | KJ/m 2 | 54 | 62 | 74 | 40 | 18 | 8.9 | 48 | 68 | 50.0 | 5.6 | 34 | ||
Therefore the composition of comparative example 3-9 is compared with the composition of embodiment 4-18 owing to there is not use to satisfy the polymer-modified of important document of the present invention, and the harmony of physics value is poor.
According to the present invention, can provide resin properties excellence, secondary modified propylene polymer compound and the manufacture method thereof that rerum natura is produced dysgenic lower molecular weight body of giving birth to hardly.
According to the present invention, can be provided in and have balanced polyolefine resin composition of high rerum natura and manufacture method thereof under the condition of not damaging polyolefinic characteristic.
Claims (9)
1. modified propylene polymer compound, it satisfies following (1)-(4):
(1) the polar group content partly from unsaturated carboxylic acid and/or its derivative is 0.10-0.30mmol/g,
The limiting viscosity of measuring in (2) 135 ℃, tetraline [η]
ABe 0.8-3.0dl/g,
(3) molecular weight distribution mw/mn surpasses 2.5,
(4) molecular weight Mw is below the 5 weight % at the one-tenth component below 10,000.
2. the described modified propylene polymer compound of claim 1, wherein, the limiting viscosity of described modified propylene polymer compound [η]
AWith the limiting viscosity of in 135 ℃, tetraline, measuring as the acronal of its raw material [η]
SRatio [η]
A/ [η]
SBe more than 0.2.
3. the manufacture method of the described modified propylene polymer compound of claim 1, it comprises: acronal 100 weight parts, radical initiator 0.1-5 weight part and unsaturated carboxylic acid and/or its derivative 1.5-10 weight part are mixed, more than the fusing point of described acronal, carry out melting mixing under the temperature of 180 ℃ of less thaies.
4. polyolefine resin composition, it contains following (A), (B) and (C):
(A) the polymkeric substance 50-95 weight part of the alpha-olefin of carbon number more than 3,
(B) the described modified propylene polymer compound of claim 1 4-50 weight part,
(C) the layered inorganic compound 1-30 weight part that organises.
5. polyolefine resin composition, it contains following (A), (B), (C) and (D):
(A) the polymkeric substance 30-95 weight part of the alpha-olefin of carbon number more than 3,
(B) the described modified propylene polymer compound of claim 1 4-50 weight part,
(C) organise layered inorganic compound 1-30 weight part,
(D) rubbery polymer 5-40 weight part.
6. claim 4 or 5 described polyolefine resin compositions, the limiting viscosity [η] of wherein said modified propylene polymer compound (B)
AWith the limiting viscosity of in 135 ℃, tetraline, measuring as the acronal of its raw material [η]
SRatio [η]
A/ [η]
SBe more than 0.2.
7. claim 4 or 5 described polyolefine resin compositions, wherein, the melt flow rate (MFR) of the polymkeric substance of described alpha-olefin (A) is the 0.1-200g/10 branch,
The polymkeric substance of described alpha-olefin (A) is homopolymer or the multipolymer that contains second alpha-olefin of first alpha-olefin of carbon number more than the 3 carbon number 2-20 different with above-mentioned first alpha-olefin with 0-20 weight %.
8. the manufacture method of the described polyolefine resin composition of claim 4, it comprises with described (A), (B) with (C) and mixing, carries out melting mixing.
9. the manufacture method of the described polyolefine resin composition of claim 5, it comprises with described (A), (B), (C) with (D) and mixing, carries out melting mixing.
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| JP263094/2002 | 2002-09-09 | ||
| JP2002263087A JP4185739B2 (en) | 2002-09-09 | 2002-09-09 | Modified propylene polymer and process for producing the same |
| JP263087/2002 | 2002-09-09 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862265A (en) * | 1971-04-09 | 1975-01-21 | Exxon Research Engineering Co | Polymers with improved properties and process therefor |
| US5736492A (en) * | 1995-09-08 | 1998-04-07 | Shell Oil Company | Alkenyl-substituted dicarboxylic derivatives |
| CN1189846A (en) * | 1995-06-30 | 1998-08-05 | 埃克森化学专利公司 | Propylene polymer compsns. having improved impact strength |
-
2002
- 2002-09-09 JP JP2002263087A patent/JP4185739B2/en not_active Expired - Lifetime
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2003
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862265A (en) * | 1971-04-09 | 1975-01-21 | Exxon Research Engineering Co | Polymers with improved properties and process therefor |
| CN1189846A (en) * | 1995-06-30 | 1998-08-05 | 埃克森化学专利公司 | Propylene polymer compsns. having improved impact strength |
| US5736492A (en) * | 1995-09-08 | 1998-04-07 | Shell Oil Company | Alkenyl-substituted dicarboxylic derivatives |
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| CN1688616A (en) | 2005-10-26 |
| JP2004099736A (en) | 2004-04-02 |
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