CN1966563B - Beta crystal form polypropylene nucleating agent and polypropylene resin composition containing same - Google Patents
Beta crystal form polypropylene nucleating agent and polypropylene resin composition containing same Download PDFInfo
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- CN1966563B CN1966563B CN2006101180736A CN200610118073A CN1966563B CN 1966563 B CN1966563 B CN 1966563B CN 2006101180736 A CN2006101180736 A CN 2006101180736A CN 200610118073 A CN200610118073 A CN 200610118073A CN 1966563 B CN1966563 B CN 1966563B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/06—Vinyl chloride
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
Abstract
The invention discloses a nucleating agent for beta crystalline polypropylene (PP) and a crystallized polypropylene resin combination containing the nucleating agent. The nucleating agent can be added directly into PP or added into PP in the form of concentrated masterbatch with the dosage of 005-10 wt.% PP. Higher levels of beta-crystal PP can be induced and the beta-crystal content can reach to90% through calculation of WAXD. Compared with pure PP, the prepared beta-crystalline PP has improved toughness and impact strength, which are increased by more than 3 times. The structure of the beta crystalline polypropylene is shown by formula (I), wherein M is selected from IIB group metal cation, and X is selected from substituted or nonsubstituted C5-C8 single ring or multi-ring alkanes, olefins, aromatics, and so on.
Description
Technical field
The present invention relates to a kind of Beta-crystalline polyacrylic, specifically, the present invention relates to a kind of crystalline polypropylene compsn that is used for improving the nucleator of Vestolen PP 7052, polypropylene blend or polypropylene copolymer Beta-crystalline polyacrylic ratio and contains this nucleator.
Background technology
The crystalline structure of known isotatic polypropylene can form five kinds of α, β, γ, δ and plan six side's attitudes etc.Wherein, alpha-crystal form is an oblique system, and is the most stable, be mainly this type of crystal formation in the present commercial Vestolen PP 7052, but its toughness is relatively poor, and this also is the reason of common PP shock resistance difference.Beta crystal belongs to hexagonal system, and the Vestolen PP 7052 of this crystal formation has good impelling strength.Improve the content of beta crystal in the Vestolen PP 7052, the performance of improving PP is of great importance.
Beta crystal is to be to be unfavorable for a kind of crystal formation of generating on thermodynamics metastable state, the kinetics, under common condition, is difficult to obtain.Research shows, is quenched into 120 ℃ of left and right sides isothermal crystals rapidly from molten state, can obtain the Beta-crystalline polyacrylic of high level; It is main sample that strict temperature control can access beta crystal, and thermograde is big more, helps generating beta crystal more; Induce down at high shear rate in addition, also can generate beta crystal in the isotatic polypropylene.Above-described method of inducing beta crystal, limitation is big in actual production process, is difficult to carry out the productive applied research report of not relevant as yet so far Beta-crystalline polyacrylic.Nucleator is the feasible way that obtains high level beta crystal material at present.At present; Effectively the kind of beta nucleater is divided into organic and inorganic two big types; Organicly type mainly contain condensed-nuclei aromatics class (dye pigment type), organic acid and salt type and acid amide type, and mineral-type mainly contain inorganic salt, inorganic oxide and some low melting point metal powder.
Beta crystal is that triumphant plucked instrument of nineteen fifty-nine (H.D.Keith) and handkerchief red (F.J.Padden) are found when the spherocrystal of research alpha-crystal form.Leugering found the be formed with promoter action of γ crystal formation quinacridone red (Quinacridone) dyestuff (commodity are called E3B) to Beta-crystalline polyacrylic in 1967; Garbarczyk in 1981 and Paukszta find that a series of fused ring compounds such as triphen dithiazine (Triphenodithiazine) etc. also have β nucleating effect preferably; But this type material cost height, synthetic difficulty; And can make product dye dark rose-red color, and this is unallowable in many products.
US-B-6,235,823 have described the purposes of diamide compound as beta nucleater, and good β nucleating effect is arranged, but exist cost higher equally, and problem such as cost an arm and a leg.
CN 1004076B, DE-A-3610644, EP 0682066 etc. disclose a series of salt with di-carboxylic acid and IIA family metallic element (particularly pimelic acid and calcium stearate) mixture and can be used as beta crystal-type nucleater efficiently; But this method is being extruded, is being formed precipitate easily in the moulding process such as blowing and influence service efficiency and quality of item because the part of di-carboxylic acid is decomposed.
EP 0887475 (being CN 1210103,1999) as beta crystal-type nucleater, also has effect preferably with the salt of baroque imido acid and IIA family metallic element, but has synthetic complicated, a problem that cost is high equally.In a word, as in the material of beta crystal-type nucleater, metals ion is IIA family element in the periodic table of elements at present.
US 6599968, US 6946507 and CN 1498245 have announced the nucleator of some structural similitudies that comprise with this patent, but it does not propose to use as the brilliant nucleator of β in patent.
Summary of the invention
The purpose of this invention is to provide a kind of can the generation high-content beta crystal and can significantly improve polyacrylic shock strength and flexible nucleator by the induced crystallization Vestolen PP 7052, and the crystalline polypropylene compsn that contains this nucleator.
The open ortho position of another object of the present invention di-carboxylic acid IIB metal-salt is as the application of crystalline polypropylene resin beta crystal-type nucleater.
Technical scheme of the present invention:
The present invention provides the compound that contains formula (I) expression as the crystalline polypropylene beta crystal-type nucleater, and the crystalline polypropylene compsn that contains this nucleator or this nucleating agent compositions.
Wherein, M is selected from the IIB metals ion;
X is selected from C
5-C
8Monocycle or multi-ring alkyl;
Be selected from one group of substituted C of group of following composition
5-C
8Naphthenic base:
C
1-C
9Alkyl, hydroxyl, C
1-C
9Alkoxyl group, C
1-C
9Alkene oxygen base, amine, C
1-C
9Alkylamine, halogen, phenyl, alkyl phenyl, the two or C of company
1-C
9Carbocylic radical.
C
5-C
8Monocycle or many cycloalkenyl groups;
Be selected from one group of substituted C of group of following composition
5-C
8Cycloalkenyl group:
C
1-C
9Alkyl, hydroxyl, C
1-C
9Alkoxyl group, C
1-C
9Alkene oxygen base, amine, C
1-C
9Alkylamine, halogen, phenyl, alkyl phenyl, the two or C of company
1-C
9Carbocylic radical.
Phenyl;
Be selected from one group of substituted phenyl of group of following composition:
C
1-C
9Alkyl, C
1-C
9Alkoxyl group, hydroxyl, aldehyde radical, halogen, trihalogenmethyl, three halogen methoxyl groups, benzoyl-, anilino, carboxamido-group;
One 5～6 element heterocycle base;
Hydroxyl, substituted 5～6 yuan of heterocyclic radicals of aldehyde radical.
Nucleator of the present invention comprises the compound of above-mentioned general formula (I) expression, in above-mentioned general formula, as the IIB metals ion that M representes, can enumerate out: zinc, cadmium etc.
X can be selected from C in above-mentioned general formula (I)
5-C
8Monocycle or multi-ring alkyl can be enumerated out: cyclopentyl, cyclohexyl, suberyl, ring octyl group, dicyclo [2.2.1] heptane base, dicyclo [2.2.2] octyl.The compound that can enumerate out is: the adjacent dioctyl phthalate zinc of cyclopentyl, the adjacent dioctyl phthalate cadmium of cyclopentyl, the adjacent dioctyl phthalate zinc of cyclohexyl, the adjacent dioctyl phthalate cadmium of cyclohexyl, the adjacent dioctyl phthalate zinc of suberyl, the adjacent dioctyl phthalate cadmium of suberyl, the adjacent dioctyl phthalate zinc of ring octyl group, the adjacent dioctyl phthalate cadmium of ring octyl group, dicyclo [2.2.1] heptane-2; 3-zinc carboxylate, dicyclo [2.2.1] heptane-2; 3-carboxylic acid cadmium, dicyclo [2.2.2] octane-2; 3-zinc carboxylate, dicyclo [2.2.2] octane-2,3-carboxylic acid cadmium.Wherein preferred compound is: dicyclo [2.2.1] heptane-2; 3-zinc carboxylate, dicyclo [2.2.1] heptane-2,3-carboxylic acid cadmium, dicyclo [2.2.2] octane-2,3-zinc carboxylate, dicyclo [2.2.2] octane-2; 3-carboxylic acid cadmium; Preferred especially compound is: dicyclo [2.2.1] heptane-2,3-zinc carboxylate, dicyclo [2.2.2] octane-2,3-zinc carboxylate.
X is optional from substituted C in above-mentioned general formula (I)
5-C
8Monocycle or multi-ring alkyl, substituting group can be selected from: C
1-C
9Alkyl, hydroxyl, C
1-C
9Alkoxyl group, C
1-C
9Alkene oxygen base, amine, C
1-C
9Alkylamine, halogen, phenyl, alkyl phenyl, the two or C of company
1-C
9Carbocylic radical.
X can be selected from C in above-mentioned general formula (I)
5-C
8Monocycle or many cycloalkenyl groups can be enumerated out: 1-cyclopentenyl, 1-cyclohexenyl, dicyclo [2.2.1]-5-heptenyl, dicyclo [2.2.2]-5-octenyl etc.Wherein preferred compound is: 1-cyclopentenes-2,3-zinc carboxylate, 1-cyclopentenes-2,3-carboxylic acid cadmium, 1-tetrahydrobenzene-2; 3-zinc carboxylate, 1-tetrahydrobenzene-2; 3-carboxylic acid cadmium, dicyclo [2.2.1]-5-heptene-2,3-zinc carboxylate, dicyclo [2.2.1]-5-heptene-2,3-carboxylic acid cadmium, dicyclo [2.2.2]-5-octene-2; 3-zinc carboxylate, dicyclo [2.2.2]-5-octene-2,3-carboxylic acid cadmium.Wherein preferred especially compound is: dicyclo [2.2.1]-5-heptene-2,3-zinc carboxylate, dicyclo [2.2.2]-5-octene-2,3-zinc carboxylate.
X is optional from substituted C in above-mentioned general formula (I)
5-C
8Monocycle or many cycloalkenyl groups, substituting group can be selected from: C
1-C
9Alkyl, hydroxyl, C
1-C
9Alkoxyl group, C
1-C
9Alkene oxygen base, amine, C
1-C
9Alkylamine, halogen, phenyl, alkyl phenyl, the two or C of company
1-C
9Carbocylic radical.
X can be selected from phenyl in above-mentioned general formula (I), and specifiable compound is: phthalic acid zinc salt, phthalic acid cadmium salt.
X is optional from substituted phenyl in above-mentioned general formula (I), and substituting group can be selected from: C
1-C
9Alkyl, C
1-C
9Alkoxyl group, hydroxyl, aldehyde radical, halogen, trihalogenmethyl, three halogen methoxyl groups, benzoyl-, anilino, carboxamido-group.
X can be selected from one 5～7 element heterocycle base in above-mentioned general formula (I); Specifiable compound is: oxo bridge-dicyclo [2.2.1] in the 7--5-heptene-2; Oxo bridge-dicyclo [2.2.1] in 3-dicarboxylicacid zinc salt, the 7--5-heptene-2; Oxo bridge-dicyclo [2.2.1] in 3-dicarboxylicacid cadmium salt, the 7--5-heptane-2, oxo bridge-dicyclo [2.2.1] in 3-dicarboxylicacid zinc salt, the 7--5-heptane-2,3-dicarboxylicacid cadmium salt.
X can be selected from hydroxyl, substituted one 5～7 element heterocycle base of aldehyde radical in above-mentioned general formula (I); Specifiable compound is: oxo bridge-dicyclo [2.2.1] in 1-hydroxyl-7--5-heptene-2; Oxo bridge-dicyclo [2.2.1] in 3-dicarboxylicacid zinc salt, the 1-hydroxyl-7--5-heptene-2; Oxo bridge-dicyclo [2.2.1] heptane-2 in 3-dicarboxylicacid cadmium salt, the 1-hydroxyl-7-, oxo bridge-dicyclo [2.2.1] heptane-2 in 3-dicarboxylicacid zinc salt, the 1-hydroxyl-7-, 3-dicarboxylicacid cadmium salt.Wherein preferred compound is: oxo bridge-dicyclo [2.2.1] in 1-hydroxyl-7--5-heptene-2, oxo bridge-dicyclo [2.2.1] heptane-2 in 3-dicarboxylicacid zinc salt, the 1-hydroxyl-7-, 3-dicarboxylicacid zinc salt; Oxo bridge-dicyclo [2.2.1] in 1-aldehyde radical-7--5-heptene-2; Oxo bridge-dicyclo [2.2.1] in 3-dicarboxylicacid zinc salt, the 1-aldehyde radical-7--5-heptene-2; Oxo bridge-dicyclo [2.2.1] heptane-2 in 3-dicarboxylicacid cadmium salt, the 1-aldehyde radical-7-; Oxo bridge-dicyclo [2.2.1] heptane-2 in 3-dicarboxylicacid zinc salt, the 1-aldehyde radical-7-, 3-dicarboxylicacid cadmium salt.Wherein preferred compound is: oxo bridge-dicyclo [2.2.1] in 1-aldehyde radical-7--5-heptene-2, oxo bridge-dicyclo [2.2.1] heptane-2 in 3-dicarboxylicacid zinc salt, the 1-aldehyde radical-7-, 3-dicarboxylicacid zinc salt.
The method of manufacture of the compound of above-mentioned general formula (I) expression, not restriction especially, the replacement(metathesis)reaction of for example carrying out neutralization reaction or adopting embodiment to provide with corresponding bronsted lowry acids and bases bronsted lowry obtains this compound.Through the compound that filters, drying obtains, can obtain the raw material powder of nucleator of the present invention.Up to now, the raw material powder of nucleator, the dispersiveness when infiltrating resin in order to make improves, mostly with below its powderised to 10 μ m.Nucleator of the present invention is also identical with always, can be through the above-mentioned raw materials powderization is obtained.
The median size of nucleator of the present invention is below the 10 μ m, is preferably below the 5 μ m, more preferably below the 0.5 μ m.In addition, the lower limit of the median size of nucleator of the present invention does not limit especially, but is generally 0.01 μ m.So-called median size among the present invention is expressed as D50 (is the particle diameter of quality criteria aggregate-value 50% corresponding to average quality).
The consumption of nucleator of the present invention is the 0.005-10% of Vestolen PP 7052 weight, is preferably the 0.01-3% of Vestolen PP 7052 weight.Certainly, the consumption of nucleator also can surpass 10% of Vestolen PP 7052 weight, but this will improve production cost significantly.
In application, can above-mentioned nucleator directly be added, also can be made into the form that concentrates master batch, join then in Vestolen PP 7052, polypropylene blend or the polypropylene copolymer.
Polypropylene beta crystal nucleating agent of the present invention; Be applicable to the blend product for preparing polypropylene articles or Vestolen PP 7052 and other material with ordinary method; Said here Vestolen PP 7052 can be the homopolymer of propylene; Also can be the multipolymer of propylene and ethene, wherein can also contain other material such as oxidation inhibitor, processing aid, filler etc.
But resin material instead of part copolymerized type propene polymer of the present invention and be used to make Vestolen PP 7052 extruding pipe material and injection-molded item.
Comprise and in this acrylic resin, mix beta-nucleated dose that defines in one or more claims 1, promptly obtain a kind of acrylic resin that beta crystal-type nucleater is arranged;
The said crystalline polypropylene resin compsn that contains beta crystal-type nucleater also contains in oxidation inhibitor, processing aid or the filler one or more;
The invention still further relates to a kind of formed article, contain above-mentioned compsn, said composition is the molded article of realizing through injection moulding, blowing, compression moulding, rotational moulding or slush moulding or extrusion molding.
The polypropylene beta crystal nucleating agent that the present invention adopts, this nucleator can induce Vestolen PP 7052 to produce the beta crystal of high level effectively, significantly improve polyacrylic resistance to impact shock, but do not have the problem that makes PP goods form and aspect deterioration, and production cost is relatively low.
Compare with existing polypropylene beta crystal nucleating agent, the outstanding advantage of beta crystal-type nucleater of the present invention is: synthesis technique is simple, and cost is relatively low; The goods form and aspect are not had deterioration, and contamination-free produces; Can induce PP to produce the beta crystal of high level, through the data of wide-angle x-ray diffraction analysis, the beta crystal relative content of trying to achieve according to the Turner-Jones formula can reach 75-90%.
Description of drawings
Fig. 1 is the ir spectra of embodiment 1.
Fig. 2 is the ir spectra of embodiment 3.
Fig. 3 is the WAXD spectrogram of HOPP of 130 ℃ of isothermal crystals of embodiment 10.
Fig. 4 is the polyacrylic WAXD spectrogram with 10 ℃/min cooling nonisothermal crystallization of embodiment 10.
Embodiment
Below through embodiment the synthetic of nucleator of the present invention further described.
The preparation of salt of the present invention
Embodiment 1
Dicyclo [2.2.1]-5-heptene-2, the preparation of 3-zinc carboxylate:
The aqueous solution of 80.0g norbornylene acid anhydrides (164.2g/mol) is heated to 80 ℃ of reactions 1 hour, adds 66.4gZnCl then
2Reacted 1 hour, suction filtration, washing obtains white precipitate, dries 2 hours for 103 ℃, gets the 108.0g product.Fig. 1 dicyclo [2.2.1]-5-heptene-2, the 3-zinc carboxylate.
Ir spectra is seen Fig. 1, because the ir spectra of naphthenic hydrocarbon is very complicated, many sharp-pointed absorption bands occur in the fingerprint region, and these bands of a spectrum are difficult to make clear and definite ownership.Ring strain has remarkable influence to the C-H stretching vibration frequency.The ownership of each absorption peak is following in the top infrared spectrogram: 3644cm
-1And 3466cm
-1Be the stretching vibration peak δ (OH) of hydroxyl, 3078cm
-1Be the stretching vibration δ (C=C-H) of (C=C-H), the 2952nd, methylene radical stretching vibration absorption peak δ (CH
2), 1598cm
-1Be C=C stretching vibration absorption peak δ (C=C), 1536cm
-1, 1442cm
-1Be respectively the unsymmetrically v (CO of carboxylate radical negative ion
2 -, as) with symmetrical stretching vibration v (CO
2 -, s) absorption peak, 738cm
-1Be methylene radical rocking vibration r (CH
2).
Productive rate: 90.2%; Fusing point:＞300 ℃.
IR(KBr，cm
-1)：3078；2952；1598；1536；1442
Embodiment 2
Dicyclo [2.2.1] heptane-2, the preparation of 3-zinc carboxylate
The aqueous solution of 80.0g norbornylene acid anhydrides (164.2g/mol) is heated to 80 ℃ of reactions 1 hour, this mixture is transferred to carries out hydrogenation (50psi, room temperature) 8 hours in the autoclave then.Filter out gac.Remove in the vacuum under 75 ℃ and anhydrate, the IR spectroscopic analysis shows consistent with desired structure, and GS-MS shows two key saturation ratios of＞99%.Again the product that obtains is joined and contain 66.4gZnCl
2The aqueous solution in the reaction 1 hour, suction filtration, the washing, obtain white precipitate, 103 ℃ the oven dry 2 hours, the 107.7g product.
Productive rate: 89.3%; Fusing point:＞300 ℃.
Embodiment 3
The preparation of maleic acid zinc
The aqueous solution of 80.0g MALEIC ANHYDRIDE (98.06g/mol) is heated to 80 ℃ of reactions 1 hour, adds 111.2gZnCl then
2Reacted 1 hour, suction filtration, washing obtains white precipitate, dries 2 hours for 103 ℃, gets the 127.7g product.
Productive rate: 87.2%; Fusing point:＞300 ℃.
IR(KBr，cm
-1)：1570；1440；1310
Embodiment 4
The preparation of zinc phthalate
The aqueous solution of 80.0g phthalic acid (166.1g/mol) is heated to 80 ℃ of reactions 1 hour, adds 65.6gZnCl then
2Reacted 1 hour, suction filtration, washing obtains white precipitate, dries 2 hours for 103 ℃, gets the 81.5g product.
Productive rate: 73.7%; Fusing point:＞300 ℃.
IR(KBr，cm
-1)：1614；1404；1558；1446
Pyromellitic Acid two zinc
The aqueous solution of 80.0g pyromellitic acid anhydride (218.7g/mol) is heated to 80 ℃ of reactions 1 hour, adds 99.7gZnCl then
2Reacted 1 hour, suction filtration, washing obtains white precipitate, dries 2 hours for 103 ℃, gets the 91.3g product.
Productive rate: 65.4%; Fusing point:＞300 ℃.
IR(KBr，cm
-1)：1608；1398；1537；1441
Embodiment 6
Dicyclo [2.2.1]-5-heptene-2, the preparation of 3-carboxylic acid cadmium:
The aqueous solution of norbornylene acid anhydrides (164.2g/mol) is heated to 80 ℃ of reactions 1 hour, adds 89.3gCdCl then
2Reacted 1 hour, suction filtration, washing obtains white precipitate, dries 2 hours for 103 ℃, gets the 120.7g product.
Productive rate: 84.7%; Fusing point:＞300 ℃.
Embodiment 7
Oxo bridge-dicyclo [2.2.1] in the 7--5-heptene-2,3-dicarboxylicacid zinc salt
The MALEIC ANHYDRIDE of 10g porphyrize is joined in the 100ml ether, and stirring is suspended in the ether MALEIC ANHYDRIDE, adds the 7.5ml furans then, loads onto reflux condensing tube, vibration, reaction beginning and heat release.Room temperature reaction 3 hours, reaction gradually fully and have crystal to separate out.Suction filtration, filtrating evaporate to dryness ether in hot water bath obtains portioned product.50 ℃ of vacuum-dryings, obtain oxo bridge-dicyclo [2.2.1] in the 16.0g 7--5-heptene-2 then, the 3-dicarboxylic acid anhydride (yield: 94.5%, fusing point: 118 ℃).
Take by weighing oxo bridge-dicyclo [2.2.1] in 6.0g (0.03614mol) 7--5-heptene-2; The 3-dicarboxylic acid anhydride adds the 37ml deionized water, at 60 ℃ of reaction 2h; Add zinc chloride 4.9g (0.03614mol) then, continue to stir this mixture down at 60 ℃ and obtained white precipitate in 2 hours.Filtration washing obtains oxo bridge-dicyclo in the 7.3g 7-[2.2.1]-5-heptene-2 102 ℃ of dryings, 3-dicarboxylicacid zinc salt.
Yield: 94.0%, fusing point:＞300 ℃
Embodiment 8
Oxo bridge-dicyclo [2.2.1] in the 7--5-heptane-2,3-dicarboxylicacid zinc salt
Take by weighing oxo bridge-dicyclo [2.2.1] in 6.0g (0.03614mol) 7--5-heptene-2, the 3-dicarboxylic acid anhydride adds the 60ml deionized water, and at 60 ℃ of reaction 2h, the palladium (5wt%) that then 0.5g is loaded on the gac adds in the solution.This mixture is transferred to the autoclave pressure reactor drum and carries out hydrogenation (50psi, room temperature) 8 hours.Filter out gac.Add zinc chloride 4.9g (0.03614mol) then, continue to stir this mixture down at 60 ℃ and obtained white precipitate in 2 hours.Filtration washing obtains oxo bridge-dicyclo in the 7.2g 7-[2.2.1]-5-heptane-2 102 ℃ of dryings, 3-dicarboxylicacid zinc salt, and the IR spectroscopic analysis shows consistent with desired structure, GS-MS shows two key saturation ratios of＞99%.
Yield: 91.8%, fusing point:＞300 ℃.
Nucleation is renderd a service test
Through following examples use of the present invention is further specified, wherein form umber, content all by weight.
Embodiment 9
Take by weighing 0.025 part, 0.05 part, 0.1 part, 0.2 part, 0.3 part, 1 part, 5 parts, 7 portions embodiment 1 synthetic nucleators respectively with 100 parts of Vestolen PP 7052 (trade mark F401, melt flow rate(MFR) 2.5g/10min, density 0.91g/cm
3), in mixing machine, mix 5min, carry out extruding pelletization through the SJSH twin screw extruder then.Open wide to place and removed moisture in 48 hours, come manufacturing objective Vestolen PP 7052 batten through the CJ-80E injector then.This batten after at room temperature aging 24 hours, is carried out Mechanics Performance Testing, and impact property is pressed ASTM D-256 test.Correlated results is seen table 1
Pure PP F401 also processes batten with same process, and example is carried out above-mentioned test as a comparison.
Table 1 shock strength (J/m)
| The brilliant nucleator concentration of β | Shock strength (J/m) | The per-cent (%) that shock strength improves |
| Comparative Examples | 36.5 | -- |
| Embodiment 1 (0.025%) | 137.5 | 277 |
| Embodiment 1 (0.05%) | 142.3 | 290 |
| Embodiment 1 (0.1%) | 151.9 | 316 |
| Embodiment 1 (0.2%) | 162.2 | 344 |
| Embodiment 1 (0.3%) | 162.4 | 345 |
| Embodiment 1 (1%) | 159.7 | 338 |
| Embodiment 1 (5%) | 139.6 | 282 |
| Embodiment 1 (7%) | 138.3 | 279 |
Weigh 100 parts of Vestolen PP 7052 (trade mark F401, melt flow rate(MFR) 2.5g/10min, density 0.91g/cm
3) and 0.2 part of the foregoing description in the brilliant nucleator of synthetic β, in mixing machine, mix 5min, carry out extruding pelletization through the SJSH twin screw extruder then.Open wide to place and removed moisture in 48 hours, come manufacturing objective Vestolen PP 7052 batten through the CJ-80E injector then.This batten after at room temperature aging 24 hours, is carried out Mechanics Performance Testing, and impact property is pressed the ASTMD-256 test.Correlated results is seen table 2.
The nucleation Vestolen PP 7052 that forcing machine is extruded (nucleator is embodiment 1 a synthetic compound); 200 ℃ of fusion compactings in flakes on the hot platform of polarizing microscope; At 130 ℃ of isothermal crystals with 10 ℃/min decrease temperature crystalline, (Ni filters sample, CuK ray (40KV at Rigaku D/max-2500 type wide-angle X ray diffractor then respectively; 100mA), λ=1.54056 * 10
-10M) record the WAXD spectrogram on.See Fig. 2 and Fig. 3.
Pure PP F401 also processes batten with same process, and example is carried out above-mentioned test as a comparison.
Table 2 shock strength (J/m)
| The brilliant nucleator of the β that adds | Shock strength (J/m) | The per-cent (%) that shock strength improves |
| Comparative Examples | 36.5 | -- |
| Embodiment 1 | 162.2 | 344 |
| Embodiment 2 | 165.3 | 353 |
| Embodiment 3 | 161.7 | 343 |
| Embodiment 4 | 167.5 | 359 |
| | 152.1 | 317 |
| Embodiment 6 | 159.1 | 336 |
| Embodiment 7 | 158.9 | 335 |
| Embodiment 8 | 161.3 | 342 |
Embodiment 11
To batten, utilize Perkin-Elmer Diamond DSC thermal analyzer, N by embodiment 10 mades
2Protection behind 130 ℃ of following isothermal crystals, is heated to 200 ℃ with the scanning speed of 10 ℃/min from 50 ℃, writes down various sample melting process, near T 154 ℃
1The melting peak that the place occurs is the brilliant melting peak of β, and heat content is Δ H
β, near T 167 ℃
2The melting peak that the place occurs is the brilliant melting peak of α, and heat content is Δ H
α, the relative content of beta crystal is by computes,
k
DSC＝ΔH
β/(ΔH
α+ΔH
β)
Pure PP F401 processes batten example as a comparison, carries out above-mentioned test equally.
Correlated results is seen table 3
Brilliant nucleator nucleation Vestolen PP 7052 crystal formation content of table 3 different beta and crystallization rate (DSC method)
| The brilliant nucleator of β | T 1(℃)? | ΔH β(J/g)? | T 2(℃)? | ΔH α(J/g)? | k DSC(％)? | t 1/2(min)? |
| Comparative Examples | Do not have | 0 | 168.0 | 99.68 | 0 | 11.8 |
| Embodiment 1 | 154.1 | 50.68 | 167.2 | 49.28 | 50.7 | 6.24 |
| Embodiment 2 | 154.3 | 51.49 | 167.5 | 46.72 | 52.4 | 5.96 |
| Embodiment 3 | 154.1 | 45.21 | 167.7 | 51.32 | 46.8 | 6.56 |
| Embodiment 4 | 154.5 | 47.58 | 167.2 | 48.47 | 49.5 | 5.72 |
| | 154.1 | 39.72 | 167.3 | 51.21 | 43.7 | 5.49 |
| Embodiment 6 | 154.3 | 41.47 | 167.8 | 51.86 | 44.4 | 5.33 |
| Embodiment 7 | 154.5 | 48.33 | 167.2 | 50.38 | 49.0 | 7.34 |
| Embodiment 8 | 154.2 | 49.26 | 167.8 | 50.29 | 49.5 | 7.11 |
Embodiment 12
To the nucleation Vestolen PP 7052 of extruding by forcing machine among the embodiment 10; 200 ℃ of fusion compactings in flakes on the hot platform of polarizing microscope; At 130 ℃ of isothermal crystals with 10 ℃/min decrease temperature crystalline, (Ni filters sample, CuK ray (40KV at Rigaku D/max-2500 type wide-angle X ray diffractor then respectively; 100mA), λ=1.54056 * 10
-10M) record the WAXD spectrogram on, sweep limit is 0～50 °, and sweep velocity is 8 °/min, and the relative content k of beta crystal can try to achieve according to following Turner-Jones formula:
k
x＝H(300)/[H(300)+H(110)+H(040)+H(130)]
Wherein, H (300) is the height of (300) diffraction peak in the beta crystal that occurs on the WAXD diffraction spectra, and H (110), H (040), H (130) are respectively the height of three stronger α diffraction peaks (110), (040) and (130).
Through the relative content of its beta crystal of wide-angle x-ray diffraction (WAXD) method survey, with same process compacting in flakes, example is carried out above-mentioned test as a comparison after the pure PP F401 extruding pelletization.The result sees table 4
The brilliant nucleator nucleation Vestolen PP 7052 crystal formation content (WAXD method) of table 4 different beta
| The brilliant nucleator of β | 130 ℃ of isothermal crystal PP beta crystal contents (%) | 10 ℃/min PP the beta crystal content (%) of lowering the temperature |
| Comparative Examples | 0 | 0 |
| Embodiment 1 | 78.5 | 67.2 |
Claims (10)
1. crystalline polypropylene resin compsn that contains beta crystal-type nucleater comprises:
(1) a kind of crystalline polypropylene resin;
(2) one or more have the beta crystal-type nucleater of ortho position di-carboxylic acid metal-salt structure, and said beta crystal-type nucleater is as shown in the formula shown in (I) compound:
Wherein, M is selected from IIB family metallic cation;
X is selected from:
C
5-C
8Monocycle or multi-ring alkyl;
Be selected from one group of substituted C of group of following composition
5-C
8Naphthenic base:
C
1-C
9Alkyl, hydroxyl, C
1-C
9Alkoxyl group, C
1-C
9Alkene oxygen base, amine, C
1-C
9Alkylamine, halogen, phenyl, alkyl phenyl, the two or C of company
1-C
9Carbocylic radical;
C
5-C
8Monocycle or many cycloalkenyl groups;
Be selected from one group of substituted C of group of following composition
5-C
8Monocycle or many cycloalkenyl groups:
C
1-C
9Alkyl, hydroxyl, C
1-C
9Alkoxyl group, C
1-C
9Alkene oxygen base, amine, C
1-C
9Alkylamine, halogen, phenyl, alkyl phenyl, the two or C of company
1-C
9Carbocylic radical;
Phenyl;
Be selected from one group of substituted phenyl of group of following composition:
C
1-C
9Alkyl, C
1-C
9Alkoxyl group, hydroxyl, aldehyde radical, halogen, trihalogenmethyl, three halogen methoxyl groups, benzoyl-, anilino, carboxamido-group;
5～6 yuan of heterocyclic radicals;
Hydroxyl, substituted 5～6 yuan of heterocyclic radicals of aldehyde radical.
2. according to the compsn of claim 1; It is characterized in that said crystalline polypropylene resin is that a kind of HPP homopolymer polypropylene or a kind of contains the polypropylene random copolymer of one or more comonomers of selecting a group from following composition, alternately or segmented copolymer: ethene, C
4-C
20Terminal olefin, vinyl cyclohexane, VCH, C
4-C
20Alkadiene, C
5-C
12Cyclic diolefine and norbornene derivative.
3. according to the compsn of claim 1, it is characterized in that described beta crystal-type nucleater, IIB metals ion are zinc, cadmium.
4. according to the compsn of claim 1, it is characterized in that described beta crystal-type nucleater, di-carboxylic acid are the ortho position carboxylic acid, the coordinate mode of carboxyl and metal can be the monodentate coordination, can be the chelating coordination, also can be the bridge-type coordination; Di-carboxylic acid can form following several kinds of coordination modes with metal: the coordination of intramolecularly chelating, the coordination of intramolecularly bridge-type, intermolecular chelating coordination, intermolecular bridge-type coordination.
5. the crystalline polypropylene resin compsn that contains beta crystal-type nucleater according to claim 1 is characterized in that the consumption of nucleator is the 0.005-10% of Vestolen PP 7052 weight.
6. a kind of method that the acrylic resin of beta crystal-type nucleater is arranged is provided, comprises the beta crystal-type nucleater that in this acrylic resin, mixes definition in one or more claims 1.
7. the purposes of formula (I) compound that defines in the claim 1 is as the beta crystal-type nucleater of acrylic resin.
8. the crystalline polypropylene resin compsn that contains beta crystal-type nucleater according to claim 1 is characterized in that, also contains in oxidation inhibitor, processing aid or the filler one or more.
9. a formed article contains the compsn according to claim 1.
10. according to the formed article of claim 9, wherein, said composition is the molded article of realizing through injection moulding, blowing, compression moulding, rotational moulding or slush moulding or extrusion molding.
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| EP2441792B1 (en) * | 2010-10-13 | 2014-12-17 | Treofan Germany GmbH & Co.KG | Highly active beta-nucleating agent for polypropylene |
| CN102070829A (en) * | 2010-12-20 | 2011-05-25 | 北京化工大学 | Microsphere polypropylene beta nucleating agent and preparation method thereof |
| US9045615B2 (en) * | 2011-08-24 | 2015-06-02 | Fina Technology, Inc. | Metal carboxylate additives for thermoplastics |
| CN102516656A (en) * | 2011-12-06 | 2012-06-27 | 天津大学 | Improved polypropylene and method for improving yield strength and toughness of polypropylene |
| JP7084729B2 (en) * | 2018-01-23 | 2022-06-15 | 株式会社Adeka | Nucleating agent composition, olefin resin composition containing it and its molded product |
| CN111925559B (en) * | 2019-05-13 | 2022-01-04 | 中国石油天然气股份有限公司 | Amide polyolefin beta-crystal form nucleating agent and preparation method and application thereof |
| CN111718527A (en) * | 2020-07-07 | 2020-09-29 | 山东齐润源新材料科技有限公司 | Polyolefin nucleating agent 20R and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100465A (en) * | 1985-04-01 | 1986-07-09 | 中国科学院上海有机化学研究所 | Beta-crystalline polyacrylic, production method and application |
| CN1863857A (en) * | 2003-10-03 | 2006-11-15 | 美利肯公司 | Improved nucleating additive formulations of bicyclo[2.2.1]heptane dicarboxylate salts |
-
2006
- 2006-11-08 CN CN2006101180736A patent/CN1966563B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100465A (en) * | 1985-04-01 | 1986-07-09 | 中国科学院上海有机化学研究所 | Beta-crystalline polyacrylic, production method and application |
| CN1863857A (en) * | 2003-10-03 | 2006-11-15 | 美利肯公司 | Improved nucleating additive formulations of bicyclo[2.2.1]heptane dicarboxylate salts |
Non-Patent Citations (1)
| Title |
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| 郑实.β型成核剂在聚丙烯中的应用 1. NA 2BW 引导聚丙烯结晶行为及力学性能.《华东理工大学学报(自然科学版)》.2006,第32卷(第1期),第12-15页. * |
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