CN101054448A - Nucleater, composition and preparation method thereof - Google Patents
Nucleater, composition and preparation method thereof Download PDFInfo
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- CN101054448A CN101054448A CN 200710110426 CN200710110426A CN101054448A CN 101054448 A CN101054448 A CN 101054448A CN 200710110426 CN200710110426 CN 200710110426 CN 200710110426 A CN200710110426 A CN 200710110426A CN 101054448 A CN101054448 A CN 101054448A
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Abstract
The invention provides an organic carboxylic acid rare earth complex compound, combination containing the above nucleator and method for preparing same. The organic carboxylic acid rare earth complex compound and combination containing the above nucleator can improve the crystallization behaviors and mechanical properties of the semi-crystallized polymers, especially PP.
Description
Technical field
The present invention relates to a class nucleator and composition and preparation method.More particularly, relate to organic carboxyl acid rare earth compounding that is used for polypropylene nucleater and the composition and method of making the same that contains aforementioned nucleator, described nucleator and composition can improve crystalling propylene behavior and mechanical property.
Background technology
Semi-crystalline resins is polyethylene, polypropylene etc. for example, and its crystallization behavior, crystal habit, spherulite size directly influence the processing and the application performance of goods.Therefore utilizing nucleator improvement hypocrystalline polymeric crystallization behavior, crystal habit, spherulite size to improve polymer properties is simple and easy to do method.
Nucleator is realized by the heterogeneous nucleation mode the crystalline modified effect of semi-crystalline polymer.Certainly dissimilar nucleators can induce semi-crystalline polymer with different crystal habit crystallizations, finally demonstrates different physical and mechanical properties.For example, generally nucleator is divided into alpha-crystal form nucleator and beta crystal-type nucleater according to the different crystal habits of inducing acrylic resin.The alpha-crystal form nucleator induces acrylic resin with the alpha-crystal form crystallization, can improve Tc, degree of crystallinity, crystallization velocity, and makes fine grain sizeization, can improve functions such as polyolefinic rigidity, tensile strength, heat-drawn wire, the transparency and surface luster; Beta crystal-type nucleater then is to induce polyolefin resin with the beta crystal crystallization, gives the nucleator type of the good shock strength of goods, heat-drawn wire and porosity rate.The alpha-crystal form nucleator is often not quite identical by the knot product behavior that changes polymkeric substance is showed the kind of different structure in crystalline modified effect.
With the polypropylene is example, and polypropylene nucleater commonly used can be divided on chemical structure: organic class and mineral-type, mineral-type comprise for example talcum powder etc., and organic class comprises organic phosphate metal salt, metal salt of organic carboxylic acid and glucitol derivative and high molecular type.
Milliken Co. has disclosed the hexahydrophthalic acid metal-salt at Chinese patent 02807376.2 and can be used as polyolefin nucleating agent recently; Chinese patent 02807188.3,02811278.4,02810330.0,02813562.8 etc. has then disclosed saturated [2.2.2] dicarboxylate, two ring [2.2.1] heptane dicarboxylate salts as polyolefin catalyst.This is the nucleator of a class novel texture, and is inhomogeneous but this type of nucleator disperses in polypropylene.Milliken Co. has disclosed improved prescription, dispersing method, preparation polypropylene agglomerate to improve dispersion effect at Chinese patent 02807497.1,200480028900.1,200480037146.8 etc.
Chinese patent CN 1114651C and CN 1473869A have disclosed based on the aliphatic carboxylic acid rare-earth salts as polypropylene beta crystal nucleating agent.
But do not utilize so far, single alicyclic dicarboxylic acid's rare earth compounding, phthalic acid rare earth compounding, two ring [2.2.1] heptane dicarboxylic acid rare earth compoundings, and and two ring [2.2.1] heptane dicarboxylic acid title complex title complexs as the report of polypropylene nucleater.
Summary of the invention
The objective of the invention is to propose a class nucleator and composition and preparation method.More particularly, relate to organic RE carboxylate ligand compound that is used for polypropylene nucleater and the composition and method of making the same that contains aforementioned nucleator, described nucleator and composition can improve the crystallization behavior and the mechanical property of semi-crystalline polymer.
More specifically, the present invention proposes single alicyclic dicarboxylic acid's rare earth compounding, two alicyclic dicarboxylic acid's rare earth compounding, phthalic acid rare earth compounding, norbornylene dioctyl phthalate rare earth compounding, methyl norbornylene dioctyl phthalate rare earth compounding and contain the composition and method of making the same of rare earth compounding, described rare earth compounding and composition can improve crystalling propylene behavior and mechanical property.
The organic carboxyl acid rare earth compounding that the present invention relates to comprises single alicyclic dicarboxylic acid's rare earth compounding, two alicyclic dicarboxylic acid's rare earth compounding, phthalic acid rare earth compounding, norbornylene dioctyl phthalate rare earth compounding, methyl norbornylene dioctyl phthalate rare earth compounding.
The organic carboxyl acid rare earth compounding preparation method who the present invention relates to, be that organic carboxyl acid or its an alkali metal salt that adopts is meant single alicyclic dicarboxylic acid, two alicyclic dicarboxylic acid, phthalic acid, norbornylene dioctyl phthalate, methyl norbornylene dioctyl phthalate or its an alkali metal salt, with solvable rare-earth salts reaction, separate the preparation of dry back.
The preparation method of the organic RE carboxylate ligand compound that the present invention proposes is to adopt the double decomposition precipitation method, and wherein the mol ratio of organic carboxylate and solvable rare-earth salts is 1～3: 1～2.
The preparation method of the organic RE carboxylate ligand compound that the present invention proposes, its preparation method can adopt double decomposition precipitation method well known to those skilled in the art:
(1) organic carboxyl acid with etc. mol ratio alkali, sodium hydroxide for example, preparation organic carboxyl acid salt brine solution, perhaps directly adopt the organic carboxyl acid salt brine solution, to wherein dripping soluble rare-earth salt, regulation system pH value 8～10, generate white precipitate, obtain after removing water, drying;
(2) organic carboxyl acid with etc. mol ratio alkali, sodium hydroxide for example, preparation organic carboxyl acid salt brine solution, perhaps directly adopt the organic carboxyl acid salt brine solution, in pre-configured soluble ree salt brine solution, drip regulation system pH value 8～10, generate white precipitate, obtain after removing water, drying;
(3) organic carboxyl acid with etc. mol ratio alkali, sodium hydroxide for example, preparation organic carboxyl acid salt brine solution, perhaps directly adopt the organic carboxyl acid salt brine solution, pre-configured soluble ree salt brine solution, both are added drop-wise in the reactor simultaneously, regulation system pH value 8～10, generate white precipitate, obtain after removing water, drying.
The organic carboxyl acid that the present invention relates to or its an alkali metal salt comprise single alicyclic dicarboxylic acid, for example hexahydrophthalic acid, methylhexahydrophthaacid acid, and an alkali metal salt, two alicyclic dicarboxylic acid, for example two ring [2.2.1] heptane dicarboxylic acid and an alkali metal salts thereof, phthalic acid, norbornylene dioctyl phthalate, methyl norbornylene dioctyl phthalate or its an alkali metal salt, and an alkali metal salt.
The organic carboxyl acid an alkali metal salt that the present invention proposes is meant the salt of lithium, sodium, potassium, rubidium, caesium etc.
It is muriate well known to those skilled in the art, nitrate, vitriol that the present invention proposes solvable rare-earth salts.
The organic RE carboxylate ligand compound that the present invention proposes is lanthanide complex and composition thereof, and lanthanon comprises lanthanum, neodymium, cerium, praseodymium, yttrium, samarium, europium etc.
The organic RE carboxylate ligand compound that the present invention proposes is the lanthanum title complex.
The organic RE carboxylic acid complex composition that the present invention proposes is to adopt above-mentioned organic carboxyl acid rare earth compounding and other nucleators are composite obtains, and other nucleators comprise inorganic nucleator, for example talcum powder; Organic nucleating agent comprises machine phosphate metal salt, metal salt of organic carboxylic acid and glucitol derivative, particularly hexahydrophthalic acid metal-salt, saturated [2.2.2] dicarboxylate, two ring [2.2.1] heptane dicarboxylate salts.
The organic RE carboxylic acid complex composition that the present invention proposes is to adopt above-mentioned organic carboxyl acid rare earth compounding and two to encircle [2.2.1] heptane dicarboxylate salts to be mixed with, and wherein to account for be 1～50% (mass percent) to the organic carboxyl acid rare earth compounding.
Organic RE carboxylate ligand compound and composition thereof that the present invention proposes use its consumption to be 0.05～5% of polymer quality as nucleator.
Nucleator that the present invention proposes and composition be applicable to various semicrystalline polymerics well known to those skilled in the art, polypropylene for example, nylon 66 etc.The thermotolerance of resulting product or matrix material, crystal property, mechanical property be improved significantly.
Embodiment
Embodiment 1
Commercially available LaCl
3Be dissolved in and form solution in the deionized water, according to LaCl
3: sodium phthalate is that 2: 1 (mole number) carries out replacement(metathesis)reaction, regulates the pH value to neutrality, can obtain phthalic acid lanthanum title complex through washing, separation, drying treatment.
Adopt the homo-polypropylene powder, melting index 8, antioxidant 1010,168, calcium stearate, above-mentioned phthalic acid lanthanum complex nucleating agent, utilize Dynisco LME-230 laboratory mixing forcing machine mixing granulation, wherein antioxidant 1010,168, calcium stearate quality percentage composition are respectively 0.1%, 0.08%, 0.01%, remain unchanged, phthalic acid lanthanum complex nucleating agent content is respectively 0,0.05%, 0.3%, 1%, 3%, 5%.
Utilize laboratory mixed injection molding machine Dynisco PMM-4-230 to carry out sample preparation, mix after the resin fusion and annotated sample in 2 minutes, sample after room temperature was placed 24 hours, test tensile strength, testing standard ASTM1708, tensile strength is respectively 28.8MPa, 29.1MPa, 29.4MPa, 30.1MPa, 29.2MPa, 29.7MPa.The obtained sample tensile strength of nucleator that contains is than all improves with nucleator.
Utilize MSAL XD2 type diffractometer to carry out XRD to the print that obtains, find its crystalline form, contain a small amount of β crystalline substance based on the α crystalline substance.The DSC test shows adding phthalic acid lanthanum title complex as nucleator, and degree of crystallinity is improved.
Embodiment 2
Identical with embodiment 1, be LaCl
3: sodium phthalate is that 1: 1 (mole number) carries out replacement(metathesis)reaction, preparation phthalic acid lanthanum title complex.
Identical with embodiment 1, as just to adopt embodiment 2 to prepare phthalic acid lanthanum title complex, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 1.4% than the polypropylene with nucleator.
Embodiment 3
Identical with embodiment 2, be LaCl
3: sodium phthalate is that 3: 2 (mole number) carries out replacement(metathesis)reaction, preparation phthalic acid lanthanum title complex.
Identical with embodiment 2, as just to adopt embodiment 3 to prepare phthalic acid lanthanum title complex, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 1.5% than the polypropylene with nucleator.
Embodiment 4
Identical with embodiment 1, just rare-earth salts is LaCl
3With NdCl
3Mixture, be that 2: 1 (mole number) carries out replacement(metathesis)reaction according to the ratio of metal ion and sodium phthalate, preparation phthalic acid lanthanum title complex.
Identical with embodiment 1, just adopt the mixture of the phthalic acid lanthanum/neodymium title complex of embodiment 4 preparation, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 2.2% than the polypropylene with nucleator.
Embodiment 5
Identical with embodiment 2, be LaCl
3: hexahydrophthalic acid sodium is that 1: 2 (mole number) carries out replacement(metathesis)reaction, preparation hexahydrophthalic acid lanthanum title complex.
Identical with embodiment 2, as just to adopt embodiment 5 to prepare hexahydrophthalic acid lanthanum title complex, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 1.6% than the polypropylene with nucleator.
Embodiment 6
Identical with embodiment 2, be LaCl
3: methylhexahydrophthaacid acid sodium is that 1: 2 (mole number) carries out replacement(metathesis)reaction, preparation methylhexahydrophthaacid acid lanthanum title complex.
Identical with embodiment 2, as just to adopt embodiment 6 to prepare methylhexahydrophthaacid acid lanthanum title complex, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 1.8% than the polypropylene with nucleator
Embodiment 7
Identical with embodiment 2, be LaCl
3: the norbornylene sodium diformate is that 1: 2 (mole number) carries out replacement(metathesis)reaction, preparation norbornylene dioctyl phthalate lanthanum title complex.
Identical with embodiment 2, as just to adopt embodiment 7 to prepare norbornylene dioctyl phthalate lanthanum title complex, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 1.3% than the polypropylene with nucleator
Embodiment 8
Identical with embodiment 2, be LaCl
3: methyl norbornylene sodium diformate is that 1: 2 (mole number) carries out replacement(metathesis)reaction, preparation methyl norbornylene dioctyl phthalate lanthanum title complex.
Identical with embodiment 2, as just to adopt embodiment 8 to prepare methyl norbornylene dioctyl phthalate lanthanum title complex, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 1.8% than the polypropylene with nucleator.
Embodiment 9
Identical with embodiment 2, be LaCl
3: two ring [2.2.1] heptane sodium diformates are that 1: 2 (mole number) carries out replacement(metathesis)reaction, and two ring [2.2.1] heptane dioctyl phthalate lanthanum title complexs fall in preparation.
Identical with embodiment 2, just adopt two of embodiment 9 preparations to encircle [2.2.1] heptane dioctyl phthalate lanthanum title complexs, its consumption is 0 and 0.3%, preparation nucleation polypropylene.The tensile strength of obtained sample improves 3.1% than the polypropylene with nucleator.
Embodiment 10
Identical with embodiment 2, the mass ratio that just adopts two ring [2.2.1] heptane dioctyl phthalate lanthanum title complexs and two ring [2.2.1] heptane sodium diformates is that 1: 1 mixture is a nucleator, its consumption is 0 and 0.2%, and preparation nucleation polypropylene mixes after the resin fusion and annotated sample in 5 minutes.The tensile strength of obtained sample improves 6.1% than the polypropylene with nucleator.
Claims (7)
1, the present invention proposes single alicyclic dicarboxylic acid's rare earth compounding, two alicyclic dicarboxylic acid's rare earth compounding, phthalic acid rare earth compounding, norbornylene dioctyl phthalate rare earth compounding, methyl norbornylene dioctyl phthalate rare earth compounding and contain the composition and method of making the same of rare earth compounding, described rare earth compounding and composition can improve crystalling propylene behavior and mechanical property.
2, organic carboxyl acid rare earth compounding according to claim 1, comprise hexahydrophthalic acid rare earth compounding, methylhexahydrophthaacid acid rare earth compounding, two ring [2.2.1] heptane dicarboxylic acid rare earth compoundings, phthalic acid rare earth compounding, norbornylene dioctyl phthalate rare earth compounding, methyl norbornylene dioctyl phthalate rare earth compounding, and composition.
3, the preparation method of organic carboxyl acid rare earth compounding according to claim 1 is to adopt the double decomposition precipitation method, and the mol ratio that it is characterized in that organic carboxylate and solvable rare-earth salts is 1～3: 1～2.
4, according to the described organic carboxyl acid rare earth compounding of claim 1, it is characterized in that lanthanide complex and composition thereof.
5, according to the described organic carboxyl acid rare earth compounding of claim 1, it is characterized in that organic carboxyl acid lanthanum title complex.
6,, it is characterized in that it being to adopt the described organic carboxyl acid rare earth compounding of claim 1 and other nucleators are composite obtains according to the described composition that contains rare earth compounding of claim 1.
7, organic carboxyl acid rare earth compounding according to claim 1 and contain the rare earth compounding composition as nucleator is characterized in that its consumption is 0.05～5% of a polymer quality.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710110426 CN101054448A (en) | 2007-06-06 | 2007-06-06 | Nucleater, composition and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710110426 CN101054448A (en) | 2007-06-06 | 2007-06-06 | Nucleater, composition and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824101A (en) * | 2010-05-31 | 2010-09-08 | 福州大学 | Beta-cyclodextrin derivative complex nucleating agent and application thereof in polypropylene |
| CN102617619A (en) * | 2012-03-02 | 2012-08-01 | 中国科学院长春应用化学研究所 | Rare earth complex nanobelt and preparation method thereof |
| CN103627087A (en) * | 2013-11-25 | 2014-03-12 | 福建师范大学 | Method for nucleating and modifying polypropylene through rare earth complex |
| CN104327494A (en) * | 2014-09-11 | 2015-02-04 | 苏州大学 | Thermal oxidation stabilizing additive for polyamide |
| CN104974377A (en) * | 2014-04-14 | 2015-10-14 | 中国石油化工股份有限公司 | Nucleating agent composition containing cyclic carboxylic acid metal salt |
| CN106478985A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of nucleating agent compositions and its application |
| CN106810715A (en) * | 2015-11-27 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of nucleating agent compositions and its application |
| CN106810714A (en) * | 2015-11-27 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of nucleating agent compositions and its application |
| CN107722415A (en) * | 2017-11-09 | 2018-02-23 | 山西省化工研究所（有限公司） | A kind of preparation and its application of polyolefin nucleating agent composition |
| CN107828083A (en) * | 2017-11-09 | 2018-03-23 | 山西省化工研究所（有限公司） | A kind of preparation and its application of polyolefin nucleating agent composition |
-
2007
- 2007-06-06 CN CN 200710110426 patent/CN101054448A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101824101A (en) * | 2010-05-31 | 2010-09-08 | 福州大学 | Beta-cyclodextrin derivative complex nucleating agent and application thereof in polypropylene |
| CN102617619A (en) * | 2012-03-02 | 2012-08-01 | 中国科学院长春应用化学研究所 | Rare earth complex nanobelt and preparation method thereof |
| CN102617619B (en) * | 2012-03-02 | 2014-10-22 | 中国科学院长春应用化学研究所 | Rare earth complex nanobelt and preparation method thereof |
| CN103627087A (en) * | 2013-11-25 | 2014-03-12 | 福建师范大学 | Method for nucleating and modifying polypropylene through rare earth complex |
| CN104974377A (en) * | 2014-04-14 | 2015-10-14 | 中国石油化工股份有限公司 | Nucleating agent composition containing cyclic carboxylic acid metal salt |
| CN104327494A (en) * | 2014-09-11 | 2015-02-04 | 苏州大学 | Thermal oxidation stabilizing additive for polyamide |
| CN106478985A (en) * | 2015-08-31 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of nucleating agent compositions and its application |
| CN106810715A (en) * | 2015-11-27 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of nucleating agent compositions and its application |
| CN106810714A (en) * | 2015-11-27 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of nucleating agent compositions and its application |
| CN107722415A (en) * | 2017-11-09 | 2018-02-23 | 山西省化工研究所（有限公司） | A kind of preparation and its application of polyolefin nucleating agent composition |
| CN107828083A (en) * | 2017-11-09 | 2018-03-23 | 山西省化工研究所（有限公司） | A kind of preparation and its application of polyolefin nucleating agent composition |
| CN107828083B (en) * | 2017-11-09 | 2019-06-18 | 山西省化工研究所（有限公司） | A kind of preparation and its application of polyolefin nucleating agent composition |
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