CN101268131A - Polymer compositions comprising nucleating or clarifying agents - Google Patents

Abstract

A polymer composition comprises a polyolefin and a nucleating or clarifying agent dispersed or dissolved in the polyolefin. Methods for producing the polymer composition and method for producing articles from the polymer composition are also described. Molded polymer articles and polymer film may be manufactured using the compositions of the invention.

Description

The polymer composition that comprises nucleator or finings

The cross reference of related application

The application requires to be committed on September 16th, 2005 No. the 60/717th, 645, the U.S. Provisional Patent Application of United States Patent (USP) trademark office; Right of priority with No. the 60/731st, 224, the U.S. Provisional Patent Application of submitting on October 28th, 2005.

Technical field

The present invention relates to comprise the polymer composition of nucleator or finings.The present invention further provides the method for manufacture and use thereof of this polymer composition.

Background technology

In industry, need improved polyolefine, especially comprise polyethylene.Polyethylene is used to make various goods, comprises molded products, film and other structures.Improved polymeric object can provide some required optical characteristics, for example mist degree of Jiang Diing (haze) or higher transparency (clarity).The preparation of these goods is to apply nucleator or finings before making goods at the improved polymkeric substance of use in polymkeric substance, and might apply extra additive.The mechanical property of improving these polymkeric substance also is desirable.

Polymer composition can be melted, to manufacture miscellaneous goods.These goods can comprise film, fiber and various types of molded products.The multiple polymers processing technology is known, and it comprises extruding, blowing, molded, compression and injection, wherein with melted polymer cools, and is shaped to entity.Every kind of method has specific physics and the chemical action of himself to polymkeric substance.And each method all customizes, with the performance of using minimum energy and being required by polymkeric substance with the accurate realization of the manufacturing speed of maximum.Usually, a kind of compound or structural formula use in one type polymer processing technology and can not foretell that identical structural formula can be successfully used to the processing technology of another kind of type.Need a large amount of repetition tests and determine with experiment whether concrete preparation is applicable to the polymer processing technology of particular type.

Thermoplastic compounds must show some physical property, to help widespread use.Particularly, in polyolefine, for example, the homogeneity of crystal arrangement is necessary for effective, durable, multi-functional polyolefin articles is provided sometimes during crystallization.In order to realize required physical properties, can use some compound and composition, in molded or manufacturing processed so that the nucleation site of polyolefin crystal growth to be provided.Known nucleator changes the crystalline structure of thermoplastic polymer.

Use nucleator can increase crystalline temperature and speed.Contain these nucleation compound compositions with than the not faster speed crystallization of nucleation polyolefine.Crystallization causes the manufacturing cycle to reduce under higher temperature, and causes for example improvement of rigidity of many kinds of physical propertiess.

Nucleator provides the nucleation site for crystal growth in the process of cooling of thermoplastic melt preparation.Exist these nucleation sites to cause the quantity of small-crystalline bigger.Owing to wherein form littler crystal, can realize the transparence of target thermoplastic material.But, always do not cause excellent transparency.Crystallographic dimension even more (and more little), then scattering of light is few more.Therefore, the transparency of thermoplastic article itself can be improved.Therefore, thermoplastic material nucleator compound is extremely important in industry, because they can be enhanced the transparency, improves physical properties and technology is accelerated.

The extruding of polymkeric substance is a common mode of making extruded plastic product.But also known other is used for the method for processable polymer.Variation between various types of polymer processing technology on processing technology, temperature and similar parameters is very big.Usually, can not predict or definite any particular formulations that is used for one type processing (for example extruding) can be applied to dissimilar polymer processing technology or effective therein that this dissimilar polymer processing technology is used different temperature, machining process, set time and conditions of similarity.And every type polymkeric substance and every kind of nucleator itself provide unique character.Additive or the method that can not predict the polymkeric substance that is used for a type can play a role satisfactorily at another kind of polymkeric substance.

Description of drawings

Fig. 1-4 is corresponding to the embodiment 8A-8D in this paper embodiment chapters and sections.

Fig. 1 has shown the sample photo of the injection molding high density polyethylene(HDPE) of making according to the method among this paper embodiment 8 (HDPE) (sample 8A);

Fig. 2 has shown the sample photo of the injection molding HDPE (sample 8B) that makes according to the method among this paper embodiment 8;

Fig. 3 has shown the sample photo of the injection molding HDPE (sample 8C) that makes according to the method among this paper embodiment 8; With

Fig. 4 is the sample photo according to the injection molding HDPE (sample 8D) of the manufacturing of the method among this paper embodiment 8.

Summary of the invention

The present invention relates generally to and comprises polyolefin substrate (matrix) and be dispersed or dissolved in nucleator in this matrix or the polymer composition of finings.In some embodiments, the present invention relates to comprise polyethylene and be dispersed in or be dissolved in nucleator in the polyethylene matrix or the polymer composition of finings.In another embodiment, polymer composition also contains at least a additive except that nucleator and/or finings, for example second polyolefine.The method of making polymer composition of the present invention and the goods of making by polymer composition of the present invention have been the present invention further provides.

Embodiment

The present invention relates to comprise polyolefin substrate (for example, polyethylene matrix) and disperse and/or be dissolved in the nucleator in this matrix and/or the polymer composition of finings.The polyethylene that forms the matrix of some embodiment of polymer composition can be any suitable polyethylene.For example, matrix can be made up of new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), medium-density polyethylene (MDPE), high density polyethylene(HDPE) (HDPE) or any combination.Desirable especially is the polyethylene of density in 0.910 to 0.980g/cc scope.And, the invention still further relates to the manufacturing of the molded products, sheet material or the film that use these compositions.Can use these compositions to make blown film (blown film) or cast film (cast film).Can also use composition of the present invention to make the injection molded polymer parts.

Nucleator or finings

The nucleator and/or the finings that are included in the polymer composition can be any suitable nucleator and/or finings.For example, suitable nucleator and/or the finings benzoate, two ring dicarboxylic acid metal salts, hexahydrophthalic acid metal-salt, bisacetal derivative such as the Sorbitol Powder acetal that include but not limited to benzoate, replacement, phosphate ester salt, glycerinate (glycerolate salt), two-, three-and four-acid amides, rosin (pine rosin) derivative, talcum, pigment and combination thereof.The benzoate that is suitable as nucleator and/or finings includes but not limited to Sodium Benzoate, lithium benzoate, p-tert-butyl benzoic acid aluminium and combination thereof.

Operable other nucleators are also arranged.Nucleator can be specified to the material that any effective promotion liquid polymers takes place to change mutually to semi-crystalline polymer (by using poor formula scanning calorimeter to measure faster crystallization rate or being clearly with observation by light microscope to small-crystalline).The example of these nucleators has 2, and 6-aphthalimide, aliphatics be single-and dicarboxylate such as pimelic acid calcium and calcium suberate and polymerization nucleator such as polyvinyl eyclohexane, high-crystallinity polypropylene (HCPP) and branched p 0 lypropylene.

When nucleator was the polymerization nucleator, then the suitable applications level was higher.In these embodiments, the amount of additive is typically about 100 in composition, and 000ppm or littler is about 50, and 000ppm or littler is about 25,000ppm or littler, or about 20,000 or littler.

When enforcement is of the present invention, can use extra additive as further described herein.The extra additive of this class can be selected from: second polyolefine, octadecyldiethanol amine, between alkoxylate-toluidine compound, poly-(ethylene glycol), poly-(ethylene glycol) derivative, the multipolymer that contains the oxyethane segment, polyvalent alcohol and derivative thereof, the segmented copolymer that contains at least one polyvalent alcohol block, polycaprolactone derivative and multipolymer thereof, based on the polyester of the pure and mild aliphatic dicarboxylic acid of binary aliphatic and the multipolymer of these polyester, polycarbonate derivatives and multipolymer thereof.

The phosphoric acid ester that is suitable as nucleator and/or finings includes but not limited to 2,2 '-methylene radical-two-(4, the 6-di-tert-butyl-phenyl) sodium phosphate (available from Asahi Denka Kogyo K.K., is called " NA-11 ^TM"), hydroxyl two [2,2 '-methylene radical-two-(4, the 6-di-tert-butyl-phenyl) phosphoric acid] aluminium (available from Asahi Denka Kogyo K.K., is called " NA-21 ^TM") with for example at United States Patent (USP) the 5th, 342, No. 868 and the 4th, 463, disclosed other these kind phosphate esters in No. 113.

The two ring dicarboxylic acid metal salts that are suitable as nucleator and/or finings include but not limited to United States Patent (USP) the 6th, 465, No. 551 and the 6th, 534, and disclosed those salt in No. 574.The dicyclo salt of structure shown in below having:

M wherein ₁And M ₂Be independently selected from: sodium, calcium, strontium, lithium, zinc, magnesium and an alkali valency aluminium;

R wherein ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉And R ₁₀Be independently selected from: hydrogen and C ₁-C ₉Alkyl; And further, wherein any two R that the position is adjacent ₃-R ₁₀Alkyl group can randomly merge the formation carbocyclic ring.Especially, two suitable ring dicarboxylic acid metal salts comprise two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium, two ring [2.2.1] heptane-2,3-dicarboxylic acid calcium and combination thereof.Can adopt ﹠amp available from Milliken; Company, Spartanburg, South Carolina's

HPN-68 or HPN-68L.HPN-68L is commercially available, comprises two ring [2.2.1] heptane-2, and 3-dicarboxylic acid disodium is as follows:

This compound can be used for embodiments of the invention, as the following examples 3.

Usually can adopt the compound and the composition of the special metal salt that comprises hexahydrophthalic acid (HHPA), so that required characteristic to be provided in thermoplastic article.HHPA derivative of the present invention is with the nucleator and/or the finings that act on these thermoplastic materials, and is practical and be easy to handle.These compounds can provide good (and being excellent sometimes) Tc, rigidity and acid scavenger consistency in being added to thermoplastic material the time.Herein disclosed is the film or the injection molded article of polyethylene and cyclic aliphatic metal-salt.These compounds can be shown as:

M wherein ₁And M ₂Identical or different, and can merge into a positively charged ion, and be selected from the metallic cation of at least a calcium, strontium, lithium and an alkali valency aluminium; And

R wherein ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉And R ₁₀Identical or different, and be selected from hydrogen, C individually ₁-C ₉Alkyl, hydroxyl, C ₁-C ₉Alkoxyl group, C ₁-C ₉Alkene oxygen base, amine and C ₁-C ₉Alkylamine, halogen and phenyl.One preferred embodiment in, M ₁And M ₂Be merged into calcium ion.The Ca HHPA that mentions herein is meant following compounds:

The bisacetal derivative that is suitable as nucleator and/or finings includes but not limited to sugar alcohol (alditol) acetal, as United States Patent (USP) the 5th, 049, and the Sorbitol Powder acetal described in No. 605.Suitable bisacetal derivative preferably meets following structural formula:

In formula (I), n is generally and is selected from 0,1 or 2 value.R is selected from the aromatic group of hydrogen, thiazolinyl (as allyl group), alkyl, alkoxyl group, hydroxyalkyl, haloalkyl, aromatic group and replacement usually.R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉And R ₁₀Usually be independently selected from hydrogen, fluorocarbon, thiazolinyl, alkyl, alkynyl, alkoxyl group, carboxyl, halogen, amino, thioether (thioether) and aromatic group.In some embodiments, be selected from R ₁, R ₂, R ₃, R ₄, R ₅, R ₆, R ₇, R ₈, R ₉And R ₁₀Any two adjacent groups can merge the formation cyclic group, this cyclic group is selected from methylene radical dioxy base, cyclopentyl, cyclohexyl or other similar cyclic groups.In some embodiments, nucleator or finings preferably 1,3:2, two (3, the 4-dimethyl benzylidene) Sorbitol Powders (being called DMDBS later on) of 4-, it is available from MiliikenChemical, and commodity are by name

3988.

Be suitable as two of nucleator and/or finings-, three-and four-acid amides include but not limited to: contain by single and condensed 4,5,6 two of the acid amides core that 7-unit's aromatics or cyclic aliphatic ring are formed-and three-acid amides; Contain two of the acid amides core formed by two and three aliphatic carboxylic acids or two and three aliphatic amines-and three-acid amides; Contain by aliphatic series three-and the acid amides core formed of tetracarboxylic acid and aliphatic series or cycloaliphatic amine three-with four-acid amides.These compounds exemplify in some patent disclosure texts, and these open texts comprise WO 2004072168, EP 0940431 and WO 200506387.

Nucleator or finings can exist with any appropriate vol in polymer composition.Usually, the amount of nucleator and/or finings is enough to increase the Tc of the polyolefine (for example polyethylene) that forms matrix with perceiving in the composition, or presents in an amount at least sufficient to change the optical characteristics that polymer composition measures with respect to the original polyolefinic optical characteristics that forms matrix.For example, when the polyolefine that forms matrix is polyethylene, the amount that nucleator and/or finings exist in polymer composition is enough to reduce the mist degree that measures with respect to original polyethylene, increases the glossiness that measures, or increases the transparency that polymer composition measures.Usually, the amount that nucleator and/or finings exist in polymer composition is per 1,000,000 parts about 0.1 part (ppm) or more, about 1ppm or more, about 5ppm or more, or about 10ppm or more (based on the weight of nucleator and/or finings and the gross weights of polymer composition).In these embodiments, the amount that nucleator and/or finings exist in polymer composition is about 10, and 000ppm or still less is about 5,000ppm or still less, or about 1,000ppm or still less.Comprise in those embodiments of two or more nucleators and/or finings at polymer composition, the amount that every kind of nucleator and/or finings exist in composition can be in one of scope mentioned above, or in addition alternatively, the nucleator that comprises in the composition and/or the total amount of finings can be in one of scopes mentioned above.

Second Application of Additives

As mentioned above, polymer composition is except the polyolefine that forms matrix and be dispersed or dissolved in basic intravital nucleator and/or the finings, can also comprise at least a extra additive.This additive can any suitable raising nucleator and/or the additive of caused nucleation of finings and/or clarification; But suitable additive does not need to demonstrate the raising of this nucleation and/or clarification.In some embodiments, this additive can be extra nucleator and/or finings, but in other embodiments, then is not.

When enforcement is of the present invention, can use extra additive.Example includes but not limited to following additive: second polyolefine, octadecyldiethanol amine, between alkoxylate-toluidine compound, poly-(ethylene glycol), poly-(ethylene glycol) derivative, the multipolymer that contains the oxyethane segment, polyvalent alcohol and derivative thereof, the segmented copolymer that contains at least one polyvalent alcohol block, polycaprolactone derivative and multipolymer thereof, based on the polyester of the pure and mild aliphatic dicarboxylic acid of binary aliphatic and the multipolymer of these polyester, polycarbonate derivatives and multipolymer thereof.

The additive that is suitable for polymer composition comprises but (for example is not limited to polyolefine, be the polyolefine except that polyethylene when the polyolefine that forms matrix is polyethylene), between octadecyldiethanol amine, alkoxylate-multipolymer (for example, the segmented copolymer of oxyethane and propylene oxide) of toluidine compound, polyoxyethylene glycol (comprising simple PEG and ether and ester derivative), oxyethane and propylene oxide and making up.

Be suitable as between the alkoxylate of additive-toluidine compound includes but not limited at United States Patent (USP) the 4th, those compounds described in 113, No. 721, and can be according to for example United States Patent (USP) the 4th, between those alkoxylates that 113, No. 721 preparation I makes-toluidine compound.For example, between suitable alkoxylate-toluidine compound include but not limited between-Tolylamine 2EO 10PO6EO ,-Tolylamine 16EO 10PO and-Tolylamine 2EO 14PO 8EO, wherein EO represents ethylene oxide residue, PO represents propylene oxide residue.Each of these compounds can be according to United States Patent (USP) the 4th, 113, and generalized method is used N among No. 721 the preparation I, the N-dihydroxy ethyl--Tolylamine the and suitably oxyethane and the propylene oxide of molar equivalent produce.

As mentioned above, this additive can be second polyolefine or other suitable olefin copolymers.For example, when the polyolefine that forms matrix was polyethylene, this additive can be a polypropylene.In some this embodiment kind, second polyolefine (for example, polypropylene) can be as the carrier of (multiple) nucleator and/or finings.Especially, nucleator and/or finings may be mixed in in the polyolefine (for example, polypropylene) to form masterbatch, then it are added in the polyolefine that forms matrix.And, although do not wish to stick to any concrete theory, believe that second polyolefine (for example, polypropylene) can play the polyolefinic nucleator of formation matrix and/or the effect of finings.In this embodiment, can use second polyolefine (for example, polypropylene) to substitute foregoing nucleator and/or finings.Therefore, in these embodiments, polymer composition comprises first polyolefine (for example, polypropylene) that forms matrix and is dispersed in wherein second polyolefine (for example, polypropylene) that this second polyolefine is as first polyolefinic nucleator and/or the finings.

(multiple) additive can any appropriate vol be present in the polymer composition.Usually, the amount that exists in polymer composition of (multiple) additive is enough to improve (multiple) nucleator and/or caused nucleation of finings and/or clarification; But (multiple) additive need not exist with this consumption.In some embodiments, for example when additive was second polyolefine (for example, polypropylene), the amount that this additive exists in polymer composition can be about 100ppm or more, about 1,000ppm or more, about 1,500ppm or more, about 2,000ppm or more, or about 2,500ppm or more (based on the weight of additive and the gross weights of polymer composition).In these embodiments, usually the amount that exists in composition of additive is about 100, and 000ppm or still less is about 50, and 000ppm or still less is about 25,000ppm or still less, or about 20,000ppm or still less.

In other embodiments, the amount that additive exists in composition is typically about 0.1ppm or more, approximately 0.5ppm or more, or about 1ppm or more.Those embodiment kinds that comprise two or more additives at polymer composition, the amount that every kind of additive exists in composition can be in one of above-mentioned scope, or in addition alternatively, the total amount of the multiple additives that comprises in the composition is in one of above-mentioned scope.

Polymer composition of the present invention can be by any suitable method production.For example, polymer composition can produce by nucleator and/or finings and any extra additive are joined to contain in the polyolefinic melt that forms the polymer composition matrix.In addition alternatively, nucleator and/or finings and any extra additive can dried forms with contain the polyolefinic masterbatch that forms matrix and mix, then batch mixing is further handled, to generate polymer composition.In another embodiment again, for example when additive was second polyolefine (for example, polypropylene), nucleator and/or finings and second polyolefine can merge the formation masterbatch, then with its with contain the polyolefinic another kind of masterbatch that forms matrix and mix.In this embodiment kind, then the batch mixing of masterbatch is further processed, to generate polymer composition.

Product application

Believe that polymer composition of the present invention will be particularly suitable for containing the molded of polyolefin articles.For example, believe that polymer composition of the present invention will be particularly suitable for injection molding technique, injection blow molding technology, extrusion blow moulding, rotoforming and other molding process.Although do not wish to stick to any concrete theory, but believe some polymer composition of the present invention nucleation more promptly, this point proves by increasing such as the Tc that contains poly polymer composition, must carry out the refrigerative time before it shifts out from mould reducing the goods of being made by polymer composition.This nucleation more rapidly of also believing some polymer composition of the present invention can reduce container required refrigerative time before being trimmed, because this container must cool off before finishing.

The polyolefine that uses

As used herein term polyolefine or polyolefin resin comprise any material of being made up of at least a polyolefine.Example comprises polyethylene, isotaxy and syndiotactic polypropylene, poly-(4-methyl) amylene, polybutene and its any batch mixing or multipolymer, and no matter it is high-density or low density in composition.Polyolefin polymer of the present invention can comprise aliphatic polyolefin and the multipolymer of being made by at least a aliphatic olefin and one or more olefinic unsaturated comonomers.Polyethylene (PE) matrix can be made up of new LDPE (film grade) (LDPE), linear low density polyethylene (LLDPE), medium-density polyethylene (MDPE), high density polyethylene(HDPE) (HDPE) or its arbitrary combination.In addition, the invention still further relates to these compositions of use and make molded products or film.Can use these compositions to make blown film or cast film.Also can use composition of the present invention to make the injection molded polymer parts.

Bimodal (bimodal) polymkeric substance also can be used among the present invention, as shown in following embodiment 11, although embodiment herein is not limited to adopt polyethylene bimodal to implement mode of the present invention." bimodal " typically refers to the polymkeric substance that comprises at least two kinds of components, and wherein a kind of component molecular weight is relatively low, and another component molecular weight is higher relatively.This bimodal resin can be by making two kinds of different mixed with polymers of molecular weight, or usually make in multistage manufacture method alternatively in addition.For example, this bimodal polymkeric substance can use catalyst system or mixture with two or more different catalytic site to make in single reactor in stage division.Comonomer often is added in the polyethylene bimodal to regulate the characteristic of resin.Comonomer can be added in lower-molecular-weight component or the high molecular weight component.Sometimes need the comonomer of minimum is added in the lower-molecular-weight component.

Polyethylene bimodal can very usefully be used to implement the present invention, shown in the embodiment 11 of this paper.

And, also can make people can use polyolefine and/or can not produce the goods that the method manufacturing of the goods with some required optical characteristics has these required optical characteristics in the past for the improvement of the viewed optical characteristics of some polymer composition of the present invention.

Injection moulding (IM) is by in the mould that molten polymer is injected into clamping and be retained to polymkeric substance and have cured and make multiple parts always.Parts must be maintained at the activity that is enough to ejection of energy bearing part and downstream in the mould until solid.Parts in the injection mold eject to relate to pneumatic, mechanicalness or both array modes final part are shifted out from mould.

The minimizing of cycling time is subjected to the restriction of polymer cure in the mould in the injection moulding.Usually, injection moulding circulation most important part is cooling time.If it is too fast that parts are hit by a bullet out from mould, then soft-component can take place to change the warpage that causes by convergent force.This can cause the stickup that generation is not expected in mould, and also causes part quality inconsistent.

Extrusion blow (EBM) is by pushing the container of making hollow with parison in its expansion with before being trimmed to its net shape.When parts are cured to when being enough to bear downstream movable, can from mould, eject hollow container.Usually parts are shifted to carry out final part finishing, back finishing and resultant articles processing.

Reduce relevant cycling time among the EBM with the minimizing of blowing time.If the blowing time shortens, then speed is open and eject parts faster for mould, increases the productivity of process velocity and machine on the whole.Usually, because the curing of polymkeric substance is difficult to reduce the blowing time.The difficulty of flexible polymer is: be bonded in the mould, after repair and bear the convergent force that causes warpage.

Injection blow molding (IBM) is the combination of injection moulding and blowing.In the fs, the fused polymkeric substance is injected in the mould, in this mould, polymkeric substance is pre-formed as the shape of similar test tube.After standing minimum cooling, " preformed member " is transferred to blow mold, to be expanded to the final part shape.At last, parts are ejected, to carry out other downstream process.Polymkeric substance must keep in each stage until polymkeric substance can stand transfer to terminal stage.For EBM and IM, the minimizing of cycling time can be subjected to the restriction of polymer cure.Any minimizing of cooling or set time can produce low-quality parts.Can be material sagging, warpage, be bonded in the mould and analogue the round-robin limiting factor.

Rotational molding is with polymer beads or the fine grinding polymkeric substance method in the heated mould when slowly rotating with level and Z-axis of packing into.Heat simultaneously and rotate and make distribution of polymer on the internal surface of mould, merge the object that forms interconnection at this polymkeric substance.

Polymer composition can use method well known in the art to be used for the molded polyolefinic goods that contain.For example, polymer composition of the present invention can be used for typical injection moulding, injection blow molding forming method or extrusion blow forming method.In these methods, polyolefine, (multiple) nucleator and/or the finings and any extra additive that form matrix can mix with dried forms before being directed into molding apparatus.In addition alternatively, for example when additive was second polyolefine (for example polypropylene), (multiple) nucleator and/or finings and polyolefine can be re-dubbed masterbatch, then it were mixed with the polyolefine (for example polyethylene) that forms matrix.This batch mixing can be joined in the molding apparatus then.

The following examples further specify the present invention, but these embodiment should not be construed as limiting the scope of the invention by any way certainly.

Embodiment 1

Present embodiment has proved the calorifics that polymer composition as herein described is shown and the variation of optical property.Use four kinds of commercially available polyvinyl resins composite with the masterbatch of about 2.0wt% (based on the gross weight of polymer composition), prepare 4 samples (1A-1D), above-mentioned masterbatch contains commercially available 1 of about 10wt% (based on the gross weight of masterbatch), 3:2, two (3, the 4-dimethyl benzylidene) the Sorbitol Powder nucleators of 4-( 3988, available from Milliken Chemical) and the about atactic copolymerized polypropene of 90wt% (based on the gross weight of masterbatch).Therefore, every kind of composite polymer composition comprises 0.2wt%1,3:2, two (3, the 4-dimethyl benzylidene) Sorbitol Powder nucleator and the 1.8wt% atactic copolymerized polypropenes of 4-.

Composite sample uses the injection moulding of Arburg 40-ton injection moulding machine to become the thin plate (plaque) of 50 mils.After molded thin plate is preserved at least 12 hours, mist degree and the transparency of using BYK-GardnerHaze-Gard Plus to test this thin plate, use BYK Gardner GlossMeter to detect glossiness, use Perkin-Elmer DSC 7 to detect the variation of Tc.Listed the different resins sample of being estimated in the following table.

Table 1: the melt flow rate (MFR) of sample 1A-1D and density measurement.

Sample	Resinous type	MI (g/10 minute)	Density (g/cc)
				1A	LDPE	24	0.921
1B	LLDPE	25	0.917
				1C	HDPE	20	0.955
1D	HDPE	19	0.952

As shown in following table 2, the change by optical characteristics and the increase of Tc have proved the nucleation of adding the polyvinyl resin that masterbatch provides.Particularly, this table has compared the various optics and the physical properties of sample 1A-1D and corresponding original polyvinyl resin (being labeled as " contrast ").

Table 2: the optics of sample 1A-1D and physical properties

Sample	Resinous type	Mist degree (%)	Transparency (%)	Tc(℃)
					The 1A contrast	LDPE	62.0	97.3	90.7
1A	LDPE	36.2	97.3	93.4
					The 1B contrast	LLDPE	92.6	95.2	100.6
1B	LLDPE	68.3	96.3	108.6
					The 1C contrast	HDPE	100	5.5	109.4
1C	HDPE	100	79.5	111.5
					The 1D contrast	HDPE	99.1	70.4	109.1
1D	HDPE	88.7	94.9	109.8

Digital proof as shown in table 2 is compared with original resin, and each among the sample 1A-1D all demonstrates identical or lower mist degree, identical or higher transparency and higher Tc.

Embodiment 2:

The manufacturing of cup

Use Husky S-90 injection moulding machine to produce a series of cups, its weight in average is about 20g, and nominal wall thickness is 25 mils (0.025 inches).Being used for the polymer composition of production sample contains the embodiment 9 described masterbatch of about 2wt% (based on the gross weight of composition) embodiment 1 described masterbatch and 2wt%.

Embodiment 3

Produce the 3rd group of cup (sample 3A-3B) by the method identical with embodiment 2.The polymer composition that is used for producing cup comprises reference substance (sample 3A), this reference substance comprises commercially available HDPE resin, and according to fluoropolymer resin of the present invention (sample 3B), this resin comprises the masterbatch of identical HDPE resin and 2.5wt% (based on the gross weight of this polymer composition), this masterbatch comprises two commercially available ring [2.2.1] heptane-2 of 4wt% (based on the gross weight of masterbatch), 3-dicarboxylic acid disodium nucleator (

HPN-68L is available from MillikenChemical) and the homo-polypropylene of 96wt%.

Preserve after at least 12 hours, use BYK Gardner Haze-Gard Plus that sample is estimated to measure mist degree and transparency.

The optical characteristics of table 4. sample 3A-3B.

Sample	Mist degree (%)	Transparency (%)
			3A	94.5	67.6
3B	56.4	97.7

As seen data as shown in table 4 use the cup of polymer composition production of the present invention to compare lower mist degree of demonstration and higher transparency with the cup that uses original production of resins.

Embodiment 4

The thin plate (sample 4A-4E) (every group contains 10 thin plates) of 5 group of 50 mil is used the injection moulding under the molding temperature of 160 ℃ barrel zone temperature and 21 ℃ of Arburg 40-ton injection moulding machine.Each sample all comprises commercially available high-density polyethylene resin, and the melt flow rate (MFR) of this resin is about 19g/10 minute, and density is about 0.952g/cm ³Sample 4A is a reference substance, and it only contains the HDPE resin.Sample 4B and 4C also comprise 0.2wt% and 2.0wt% (based on the gross weight of polymer composition) embodiment 1 described masterbatch respectively.Sample 4D and 4E comprise the masterbatch of 0.2wt% and 2.0wt% (based on the gross weight of polymer composition) respectively, and this masterbatch comprises two ring [2.2.1] heptane-2 that 5wt% (based on the gross weight of masterbatch) is commercially available, 3-dicarboxylic acid disodium nucleator (

HPN-68L is available from Milliken Chemical), crushing-resistant copolymerization polypropylene and the 50wt% lime carbonate of 45wt%.

Use BYK-Gardner Haze-Gard Plus to detect mist degree and transparency, use BYKGardner Gloss Meter to detect glossiness, and use Perkin-Elmer DSC 7 to detect Tc.Use the polymer chips of 20 mil thick of sample to measure the peak Tc Tc of the polymer composition that generates, sample is heated to 220 ℃ with 20 ℃/minute from 50 ℃, kept 2 minutes down, be cooled to 50 ℃ with 20 ℃/minute then at 220 ℃.Measure for the Tc that uses 160 ℃ of methods, the sample of 20 mil thick is heated to 160 ℃ with 20 ℃/minute from 50 ℃, kept 1 minute down, be cooled to 50 ℃ with 20 ℃/minute then at 160 ℃.The standard error of the peak Tc that measures by the whole bag of tricks is+and/-0.2 ℃.

The mist degree of table 5. sample 4A-4E, glossiness, transparency and Tc observed value.

Sample	Mist degree (%)	Glossiness	Transparency (%)	Tc(℃)	Tc (℃) (160 ℃ of methods)
						4A	99.1	68.2	70.4	114.3	-
4B	100.0	67.3	36.5	114.0	114.6
						4C	88.7	68.1	94.9	115.0	116.3/117.0
4D	97.3	70.3	81.1	115.6	117.3
						4E	100.0	46.7	51.0	117.0	118.6

Digital proof as shown in table 5, the peak Tc of sample 4C, 4D and 4E is significantly higher than the Tc of sample 4A.The additive that uses among sample 4C, 4D and the 4E is effective nucleator of HDPE.In addition, for sample 4C, 4D and 4E, use 160 ℃ of methods, the peak Tc also is higher than the Tc of control sample 4A and sample 4C, 4D and 4E.When using 160 ℃ of methods to measure the peak Tc, the polypropylene that adds by masterbatch can not be melted to any significant degree.As if the polypropylene content among sample 4C, 4D and the 4E has improved the nucleation efficient of the additive that uses among sample 4C, 4D and the 4E.

Embodiment 5

Use Arburg 40-ton injection moulding machine molded 28 groups of test bars under the molding temperature of 230 ℃ machine barrel ℃ and 25 ℃.Each control test rod all uses the polymer composition that comprises commercially available high-density polyethylene resin to make, and the melt flow rate (MFR) of above-mentioned resin is about 19g/10 minute, and density is about 0.952g/cm ³The polymer composition that is used for producing the test bars of 14 basic inventions comprises that further the masterbatch of about 1wt%, this masterbatch comprise two ring [2.2.1] heptane-2 that 5wt% (based on the gross weight of masterbatch) is commercially available, 3-dicarboxylic acid disodium nucleator (

HPN-68L is available from Milliken Chemical) and the crushing-resistant copolymerization polypropylene of 45wt% and the lime carbonate of 50wt%.

The every rod that generates is ejecting the time point (be shown as shelf time table) of back in strictness control from injection moulding machine, use the multi-functional detection machine of MTS (MTS Universal testingmachine) to use 3 bending jigs to detect, to determine its modulus in flexure.Specifically, two rods, one is the reference substance by original HDPE production of resins, second is to use and produces according to polymer composition of the present invention, they are detecting with the interval that is roughly the same after ejecting from injection moulding machine, to determine any difference of the modulus in flexure aspects that these rods are shown.

The modulus in flexure of table 6. HDPE test bar when the different storage times

Storage time (minute)	Reference substance modulus in flexure (MPa)	Modulus in flexure of the present invention (MPa)
			0.5	171.09	204.65
1.0	221.46	271.90
			1.5	276.77	339.23
2.0	311.19	416.08
			2.5	361.08	468.63
3.0	412.11	480.86
			3.5	418.92	507.77
4.0	444.67	529.35
			5.0	490.19	572.89
6.0	544.52	581.63
			7.0	562.67	638.41
8.0	587.60	639.99
			9.0	608.43	632.72
10.0	610.07	654.87

Digital proof as shown in table 6 uses the rod of polymer composition production of the present invention to demonstrate higher modulus in flexure with respect to the similar rod that uses original HDPE production of resins.

Embodiment 6

On WMB 4100-16 extrusion blow shaper, produce three groups 1 liter HDPE bottle (sample 6A-6C).Each sample all is to be produced by the polymer composition that comprises commercially available HDPE resin, and the melt flow rate (MFR) that this resin shows is about 0.89g/10 minute, and density is about 0.958g/cm ³Sample 6A is the reference substance that only contains HDPE.Except HDPE, sample 6B and 6C also comprise 0.5wt% and 1.5wt% embodiment 5 described masterbatch respectively.By basic resin and masterbatch are mixed at extrusion blow machine place with dry batch mixing form, generate preparation.

In order to estimate the optimum cycle time between reference substance and the nucleation sample, every kind of polymer composition is similarly being processed under the processing conditions, and strict control ground reduces the blowing part of this complete processing.Estimate the quality and the technology stability of bottle by machine operation person through specialized training.When reduce cycling time, occurred by shortening caused consistence defective cycling time.The optimum cycle time rule is the fastest cycling time of producing the bottle with the typical consistence quality of production environment.Table 7 has been enumerated the different preparations and the cycling time thereof of assessment.

Table 7: the composition of sample 6A-6C

Sample	Resin	Masterbatch (%)	Cycling time (second)	The blowing time (second)
					6A	HDPE	0	18.2	13
6B	HDPE	0.5	16.7	11.5
					6C	HDPE	1.5	15.7	10.5

Embodiment 7

Use twin-screw extruder to produce 5 kinds of masterbatch (sample 7A-7E).Every kind of masterbatch comprises the commercially available polypropylene of about 98wt% and about 2wt% (7D contains 10wt% except sample) nucleator and/or finings.As nucleator and/or finings, sample 7A contains Sodium Benzoate, sample 7B contains 2,2 '-methylene radical-two-(4, the 6-di-tert-butyl-phenyl) phosphoric acid ester, sample 7C contains two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium, sample 7D contains oxyacetic acid zinc, and sample 7E contains the calcium salt of cis-hexahydrophthalic acid.

The Husky S-90 injection moulding machine that use is set in standard conditions is injection molded into sample on the dish of 80 mils.These dishes are single chamber dishes of trumpet assembly, and diameter is 4 inches, and nominal thickness is 0.080 inch.

Collect the dish that generates, and use the Metier-ToledoMT822e DSC that calibrates according to the recommendation of production firm to carry out Tc and measure.Use the polymer chips of 20 mil thick of polymer samples to measure the peak Tc Tc of polymkeric substance, sample is heated to 220 ℃ with 20 ℃/minute from 50 ℃, keeps 2 minutes down at 220 ℃, is cooled to 50 ℃ with 20 ℃/minute then.Measure for the Tc that uses 160 ℃ of methods, the sample of 20 mil thick is heated to 160 ℃ with 20 ℃/minute from 50 ℃, keeps 1 minute down at 160 ℃, is cooled to 50 ℃ with 20 ℃/minute then.The result of these measurements is presented in the following table 8.

The Tc observed value of table 8. sample 7A-7E

Sample

Nucleator carrying capacity (ppm)

Tc(℃)

Tc (℃) (160 ℃ of methods)

7A	500	115.9	119.5
				7B	500	115.9	119.3
7C	500	117.3	120.0
				7D	500	113.8	117.0
7E	400	117.3	119.5

Data as shown in table 8 visible (using any DSC method), the peak Tc of nucleation HDPE7A-7C, 7E is significantly higher than the peak Tc of the sample 4A of original HDPE of standard such as embodiment 4.In addition, as if as embodiment 4 DSC result proved, the polypropylene content among the sample 7A-7E had improved the nucleation efficient of additive used among the sample 7A-7E.

Embodiment 8

Use Husky S-90 injection moulding machine 4 samples (sample 8A-8D) to be injection molded into the dish of 80 mils.These dishes are single chamber dishes of trumpet assembly, and diameter is 4 inches, and nominal thickness is 0.080 inch.Each sample comprises commercially available HDPE resin, and the melt flow rate (MFR) that this resin shows is about 19g/10 minute, and density is about 0.952g/cm ³Sample 8A is the reference substance that only contains HDPE.Sample 8B and 8D comprise the phthalocyanine blue pigment in the commercially available LLDPE carrier of about 1wt%, and sample 8C and 8D comprise the masterbatch described in the embodiment 5 of about 1wt%.

Use the polymer samples of 20 mil thick to measure the peak Tc Tc of polymkeric substance, sample is heated to 220 ℃ with 20 ℃/minute from 50 ℃, kept 2 minutes down, be cooled to 50 ℃ with 20 ℃/minute then at 220 ℃.Measure for the Tc that uses 160 ℃ of methods, the sample of 20 mil thick is heated to 160 ℃ with 20 ℃/minute from 50 ℃, kept 1 minute down, be cooled to 50 ℃ with 20 ℃/minute then at 160 ℃.

Table 9: the Tc of sample 8A-8D.

Sample	Tc(℃)	Tc (℃) (160 ℃ of methods)
			8A	113.7	-
8B	115.2	115.3
			8C	115.8	119.2
8D	115.8	119.2

Data as shown in table 9 visible (using any DSC method), the peak Tc of nucleation HDPE sample 8B-8D is significantly higher than the peak Tc of original HDPE sample 8A.In addition, as if as proving among the DSC result of embodiment 4 and 7, the polypropylene content among the sample 8C-8D has improved the nucleation efficient of the additive that uses among the sample 8C-8D.

After the sample injection moulding, collect each dish, and be cut into 10 micron thickness with ultramicrotome.Use has the section that the light microscopy of cross polarization spectral filter obtains.Photomicrograph from the section of sample 8A-8D is depicted in Fig. 1-4 respectively.As the size grades of observed granular feature from Photomicrograph as can be seen, the crystallite among the sample 8B-8D is littler than the crystallite among the sample 8A, is the evidence of nucleation.

Embodiment 9

Use identical commercially available HDPE resin and the Husky S-90 injection moulding machine described in the embodiment 2 to produce 6 groups of cups (sample 9A-9F).Be used for all polymer compositions of production sample contain about 0.2wt% commercially available 1,3:2, two (3, the 4-dimethyl benzylidene) the Sorbitol Powder nucleators of 4-.Being used for the polymer composition of production sample 9B-9B comprises that the masterbatch of 2.0wt%, this masterbatch comprise between the 2.5wt% alkoxylate-the HDPE resin of toluidine compound and 97.5wt%.The improvement of optical property is presented in the table 10.

Table 10: the optical property of sample 9A-9F

Sample	Be total to additive	Be total to the carrying capacity (ppm) of additive	Mist degree (%)	Transparency (%)
					9A	-	500	94.1	78.6
9B	Between-Tolylamine 16EO 10PO	500	54.0	96.8
					9C	Between-Tolylamine 2EO 10PO 6EO	500	54.2	96.4
9D	Between-Tolylamine 2EO 14PO 8EO	500	54.2	96.6
					9E	PEG 1000	500	58.8	96.1
9F	EP PO segmented copolymer	500	55.6	96.7

Embodiment 10

A series of nucleators are formulated in the 0.25MI HDPE resin that density is 0.963g/cc.The nominal component weight that use is processed on Bekum H-121 extrusion blow molding machine is the bottle of 350ml of 30 grams, the improvement of assess sample extrusion-blown modling cycling time.

Except the sample nucleator, every kind of sample added 500ppm Irganox1010 and 1000ppm Irgafos 168 powder before composite.Be that 5%HPN-68L masterbatch in the 25MILLDPE resin of 0.917g/cc imports the HPN-68L sample by density.

Use every kind of resin of typical working condition processing.For each sample, cycling time, systematicness reduced 0.5 second, made technology become stable, and estimated the quality of bottle.The minimal circulation time that records is the minimum cycling time of consistence ground production good quality bottles.Reduce when too much when cycling time, warpage occurs, prove that bottle is low-quality along bottle near substrate.What table 11 showed is the minimal circulation time of each sample.The sample that is marked with " * " is restricted material, further the minimizing of evaluation cycle time.The cycling time of nucleation sample is faster than the cycling time of nucleation reference substance not.

Table 11: the minimal circulation time of the HDPE bottle of extrusion-blown modling

*-sample limits by resin demand.The data represented minimal circulation time of estimating.

Reduce the cycling time among the embodiment 11:EBM

1 liter the HDPE bottle of producing on WMB 4 100-16 extrusion blow molding machines is carried out a series of tests.Sample comprises the commercially available bimodal resin (density is 0.954g/cc, and melt index is 0.30g/10 minute HDPE) that combines with various nucleator enriched materials.Enriched material adds with the 2wt% of resin total amount in the EBM test.The enriched material that uses among the embodiment 11A-11E is/10 minutes homopolymer polypropylenes of 3.5 grams based on melt flow index.The concentration that nucleator exists is 2wt%.Sample 11A contains Sodium Benzoate, sample 11B contains [2,2 '-methylene radical-two-(4, the 6-di-tert-butyl-phenyl) phosphoric acid] sodium, sample 11C contain hydroxyl two [2,2 '-methylene radical-two-(4, the 6-di-tert-butyl-phenyl) phosphoric acid] aluminium, sample 11D contains the calcium salt of cis-hexahydrophthalic acid, and sample 11E contains two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium.The enriched material that uses among the embodiment 11F-11J is based on the bimodal high density polyethylene polyethylene polymers, and its melt index is 0.30 gram/10 minutes, and density is 0.954g/cc.The concentration that nucleator exists is 2wt%.Sample 11F contains Sodium Benzoate, sample 11G contains [2,2 '-methylene radical-two-(4, the 6-di-tert-butyl-phenyl) phosphoric acid] sodium, sample 11H contain hydroxyl two [2,2 '-methylene radical-two-(4, the 6-di-tert-butyl-phenyl) phosphoric acid] aluminium, sample 11I contains the calcium salt of cis-hexahydrophthalic acid, and sample 11J contains two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium.

In order to estimate the optimum cycle time between reference substance and the nucleation sample, all resins are processed under similar processing conditions, and strict control ground reduces the blowing part of complete processing.Parallel and measure bottle diameter by slide calliper rule (bottom and top) on two height of bottle perpendicular to joint line.Second measurement index of bottle quality is the bottleneck diameter that is parallel and perpendicular to joint line.

To be bottle diameter with the bottle diameter of control material under the normal cycle time (promptly 19.3 seconds) equate the optimum cycle timing definition and the cycling time when very low with the deviation of ideal circular.Table 12 has been listed optimum cycle time of being measured by bottle diameter and than the minimizing of control material.

Table 12: optimum cycle time and reduce, measure by bottle diameter than cycling time of control material

Sample	The optimum cycle time (s)	The minimizing of cycling time (%)
			Reference substance	19.3	-
11A	19.3	0.0
			11B	16.5	14.5
11C	17.0	11.9
			11D	15.7	18.7
11E	14.7	23.8
			11F	18.8	2.6
11G	16.8	13.0
			11H	16.8	13.0
11I	14.2	26.4
			11J	15.7	18.7

As can be seen, many samples demonstrate the minimizing of cycling time.In addition, sample 11D, 11E, 11I and 11J demonstrate and reduce per-cent (%) maximum cycling time.Sample 11D and 11I have shown good especially and unpredictable consequence, and this is to use the sample of hexahydrophthalic acid calcium salt (being Ca HHPA).Sample 11E and 11J use Milliken ﹠amp; The HPN-68L of Company (two ring [2.2.1] heptane-2,3-dicarboxylic acid disodium).

Those of ordinary skills can understand, and disclosure book has only been described exemplary embodiment, are not the aspect that will limit broad of the present invention, and the aspect of its broad is embodied in the exemplary lexical or textual analysis.The present invention is presented in the claims by embodiment.

Claims (20)

1. composition, it comprises:

(a) polyethylene and

(b) nucleator or finings, described nucleator or finings are selected from: the benzoate of benzoate, replacement, dicarboxylic acid metal salts, hexahydrophthalic acid metal-salt, Sorbitol Powder acetal, phosphate ester salt, glycerinate, two-, three-and four-acid amides, rosin derivative, 2,6-aphthalimide, polyvinyl eyclohexane, high-crystallinity polypropylene, branched p 0 lypropylene, talcum and pigment; With

(c) extra additive, it is selected from: between second polyolefine, octadecyldiethanol amine, alkoxylate-toluidine compound, poly-(ethylene glycol), poly-(ethylene glycol) derivative and contain the multipolymer of oxyethane.

2. composition according to claim 1, wherein said extra additive comprises second polyolefine, and wherein said second polyolefine is a nucleation.

3. composition according to claim 2, wherein said second polyolefine is a polypropylene.

4. composition according to claim 3, wherein said nucleator or finings comprise the benzoate of benzoate or replacement.

5. composition according to claim 3, wherein said nucleator or finings comprise dicarboxylic acid metal salts.

6. composition according to claim 3, wherein said nucleator or finings comprise the hexahydrophthalic acid metal-salt.

7. composition according to claim 3, wherein said nucleator or finings comprise hexahydrophthalic acid calcium metal-salt.

8. composition according to claim 3, wherein said nucleator or finings comprise the Sorbitol Powder acetal.

9. composition according to claim 3, wherein said nucleator or finings comprise two-, three-or four-acid amides.

10. composition according to claim 3, wherein said nucleator or finings comprise polyvinyl eyclohexane.

11. composition according to claim 3, wherein said nucleator or finings comprise the high-crystallinity polypropylene.

12. composition according to claim 3, wherein said nucleator or finings comprise branched p 0 lypropylene.

13. molded products that comprises the described composition of claim 1.

14. composition according to claim 1, wherein said polyethylene is bimodal.

15. goods that comprise composition according to claim 1.

16. goods according to claim 15, wherein said goods are films.

17. goods according to claim 15, wherein said goods comprise the container of extrusion blow.

18. the manufacture method based on poly polymeric object said method comprising the steps of:

(a) provide and contain polyolefinic composition, described composition comprises polyethylene;

(b) provide nucleator or finings,

(c) provide extra additive, it is selected from: between second polyolefine, octadecyldiethanol amine, alkoxylate-toluidine compound, poly-(ethylene glycol), poly-(ethylene glycol) derivative, contain the multipolymer of oxyethane,

(d) described reagent and described extra additive and described polyethylene are merged, to form the composite of nucleation based on poly polymkeric substance; With

(e) be goods with the composite of described nucleation based on poly forming polymer.

19. method according to claim 18, wherein said nucleator or finings are selected from: the benzoate of benzoate, replacement, dicarboxylic acid metal salts, hexahydrophthalic acid metal-salt, Sorbitol Powder acetal, phosphate ester salt, glycerinate, two-, three-and four-acid amides, rosin derivative, 2,6-aphthalimide, polyvinyl eyclohexane, high-crystallinity polypropylene, branched p 0 lypropylene, talcum and pigment.

20. method according to claim 18, wherein said extra additive comprises polypropylene.

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