CN103897354B - There is the polymer blend of the melt viscosity of improvement - Google Patents
There is the polymer blend of the melt viscosity of improvement Download PDFInfo
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- CN103897354B CN103897354B CN201210568143.3A CN201210568143A CN103897354B CN 103897354 B CN103897354 B CN 103897354B CN 201210568143 A CN201210568143 A CN 201210568143A CN 103897354 B CN103897354 B CN 103897354B
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Abstract
The invention discloses polymer blend, its comprise the polyester of about 95 % by weight to about 99.99 % by weight, the formula 1 of about 0.01 % by weight to about 5 % by weight sucrose ester as melt viscosity properties-correcting agent and optional other additives existed.Polymer blend of the present invention has melt viscosity and the shock strength of improvement.Described composition is suitable for manufacturing moulded product, comprises automobile, Electrical and Electronic parts, and comprises the fiber product of long filament, fiber, yarn, fabric and carpet.
Description
Technical field
The present invention relates to the polymer blend comprising polyester, sucrose ester and optional other additives existed, and relate to the method for the melt viscosity improving polymer blend.The invention still further relates to the moulded parts and and fiber product that are obtained by described polymer blend.
Background technology
For polymer design slip-stick artist, keep physical strength to improve workability is common problem simultaneously.Process all relevant to the molecular weight of polymkeric substance in itself with performance.The high molecular of polymkeric substance causes because of its high melt viscosity being difficult to processing usually.Although reduce the workability that molecular weight can improve polymkeric substance, the product of gained has lower physical strength.Utilize and raise the difficulty that processing temperature can overcome high melt viscosity, but this can cause the undesired degraded of polymkeric substance, thus reduce its mechanical property.
Polyester is the base polymer containing ester functional group in its main chain.The most known polyester is polyalkylene terephthalates class, comprises polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT) and polybutylene terephthalate (PBT).Polyester is often applied to the various products of such as fiber, packing film, extrudate or parts and moulded product or parts.
The current trend of polymer processing, for moulded parts, is process with higher speed and manufacture more complicated and meticulous parts; For fiber product, be then in higher speed and/or carry out spinning at a lower temperature if possible.Therefore, the melt viscosity of polyester becomes the important factor relevant to processibility.Improvement melt viscosity mentioned in this article refers to the melt viscosity reducing polyester or the fluidity of molten increasing polyester, thus the lower processing temperature of permission and/or faster process velocity.
Therefore people expect to develop the polyester and resin composition having and improve melt viscosity, to improve the processibility of its molding and/or spinning.
Past has utilized various melt flow modifiers to improve the fluidity of molten of polyester.Such as, the such as small molecules of polyvalent alcohol (such as tetramethylolmethane), polyprotonic acid and polyamine and so on shows the good mobility reinforced effects to polyester.But the functional group in these molecules can cause the degraded of polyester in addition, and cause the mechanical property such as variation such as tension strain and shock strength.In addition, another problem is the surface that these small molecules can migrate to polyester.Dendroid or hyperbranched polymkeric substance are other the common flow ability modifying agents for polyester.Generally speaking, these polymkeric substance also comprise many reactive functional end of the chains such as, hydroxyl, carboxyl and amino, and it also can cause the unexpected degraded of polyester, and this is embodied in the mechanical property that they reduce.
Sucrose fatty ester is normally by with ester sucrose esterification prepared from the fatty acid methyl ester of natural origin as vegetables oil or animal tallow.These sucrose esters are known be can be used as aluminium rolling lubricant (aluminumrollinglubricant), human consumer with wax (for automobile, footwear etc.) and industrial wax.Such as, US2004/0238147 discloses a kind of die casting releasing agent containing lubricant, and wherein this lubricant can be the organic ester such as sucrose fatty ester with lipid acid.
Applicant of the present invention finds that the polymer blend of sucrose fatty ester and vibrin shows beyond thought improvement in melt viscosity.And, when vibrin is Poly(Trimethylene Terephthalate), composition of the present invention even in other mechanical propertiess as shown beyond thought improvement in toughness.
Summary of the invention
The invention provides polymer blend, it comprises following mixture or is substantially made up of following mixture or is obtained by following mixture:
(a) about 95 % by weight polyester of-Yue 99.99 % by weight, and
(b) about 0.01 % by weight the sucrose ester of formula 1 of-Yue 5 % by weight as melt flow modifiers:
Wherein
Each R is H, C independently of one another
8-C
26alkyl-carbonyl, or C
8-C
26alkenyl carbonyl;
When R is H, its sum is 0,1 or 2; And
Described % by weight is the gross weight based on described polymer blend.
In one embodiment, in polymer blend of the present invention, described polyester (a) is selected from polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate and any mixture thereof.
In one embodiment, in polymer blend of the present invention, described polyester is Poly(Trimethylene Terephthalate) homopolymer, Poly(Trimethylene Terephthalate) multipolymer or its any mixture, and wherein said Poly(Trimethylene Terephthalate) multipolymer comprises the propylene glycol ester terephthalate of at least 70mol% as main copolymerization units.
In one embodiment, in polymer blend of the present invention, described melt flow modifiers (b) comprises the sucrose octaester of at least 60 % by weight, and described % by weight is the gross weight based on described sucrose ester; And the molecular-weight average of described melt flow modifiers (b) is about 1,000-about 3,500.
In one embodiment, in polymer blend of the present invention, the content of described melt flow modifiers (b) is about 0.1 % by weight to about 3 % by weight, and described % by weight is the gross weight based on described polymer blend.
In one embodiment, polymer blend of the present invention also comprises (c) at least one additive, and described additive is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, hydrolysis-resisting agent, chain extension agent, fire retardant, softening agent, filler and arbitrary combination thereof.
The present invention also provides moulded product, and it comprises above-mentioned polymer blend or is substantially made up of above-mentioned polymer blend or is obtained by above-mentioned polymer blend.
In one embodiment, described moulded product is Electrical and Electronic device feature, trolley part, machine part or device housings.
The invention still further relates to fiber product, it comprises above-mentioned polymer blend or is substantially made up of above-mentioned polymer blend or is obtained by above-mentioned polymer blend.In one embodiment, fiber product of the present invention is long filament (filaments), fiber, yarn, fabric or carpet.
The present invention also provides the method for the melt viscosity improving polymer blend, it comprises: mixed by the sucrose ester of the polyester of about 95 % by weight to about 99.99 % by weight with the formula as defined above 1 of about 0.01 % by weight to about 5 % by weight, wherein % by weight is the gross weight based on described polymer blend.
With reference to following explanation, embodiment and the claims of enclosing, other features various of the present invention, considering will be more obvious with advantage.
Embodiment
All publications mentioned in this article, patent application, patent and other reference, unless otherwise indicated, all quote its full content clearly and add herein, as by them in this article by full disclosure.
Unless otherwise defined, all scientific and technical terminologies used herein have the identical implication usually understood with one skilled in the art of the present invention.When there is contradiction, be then as the criterion with the definition in this specification sheets.
Unless otherwise indicated, all percentage ratio, number, ratio etc. are all by weight.
In this article, term " by ... obtained " be equal to " comprising ".Term used herein " comprises ", " comprising ", " having ", " having ", " containing " or its any other variant are intended to contain comprising of non-exclusionism.Such as, comprise the composition of a series of key element, technique, method, goods or equipment and might not be only limited to those key elements, but can also comprise these compositions, technique, method, goods or equipment the key element clearly do not enumerated or other intrinsic key elements.
Conjunction " by ... composition/form " do not comprise any key element, step or the composition clearly do not enumerated.If there is in the claims, this conjunction does not comprise making this claim be limited to described material the material do not described, but still comprises the impurity usually relevant to the material described by those.When conjunction " by ... composition/form " appears at the characteristic of claim, but not immediately preamble time, it is only limitted to the key element set forth in characteristic; Other key elements are not required to get rid of in entirety by Accessory Right.
Conjunction " substantially by ... composition/form " is for also comprising the composition of other material, step, feature, component or key element, method or equipment outside definite division literal described those materials, step, feature, component or key element, prerequisite is essential characteristic and the novel feature that these other material, step, feature, component or key elements substantially do not affect invention required for protection.Term " substantially by ... composition/form " be in " comprise/comprise " and " by ... composition/formation " between intermediate zone.
Conjunction " does not substantially comprise/comprises " or " being substantially devoid of " component represents polymer blend of the present invention, based on the gross weight of described polymer blend, should comprise lower than 1 % by weight or lower than 0.5 % by weight lower than 0.1 % by weight or be 0 % by weight this component.
Term " comprises/comprises " intention and comprises term " substantially by ... composition/form " and " by ... composition/formation " embodiment of containing.Similarly, term " substantially by ... composition/form " intention comprises term " by ... the composition/form " embodiment that contains.
When providing quantity, concentration or other numerical value or parameter with scope, preferable range or a series of upper limit preferred value and lower preferable values, should understand it and specifically disclose all scopes formed by any logarithmic value of any larger range limit or preferred value and any less range limit or preferred value, and no matter whether scope is disclosed respectively.Such as, when describing the scope of " 1 to 5 ", described scope is understood to include the scope of " 1 to 4 ", " 1 to 3 ", " 1 to 2 ", " 1 to 2 and 4 to 5 ", " 1 to 3 and 5 " etc.Unless otherwise indicated, describe numerical range part herein, described scope intention comprises range endpoints and all integers within the scope of this and mark.
When term " about " is for describing the endpoint value of numerical value or scope, disclosed content is understood to include occurrence or the end value of indication.
In addition, contrary unless expressly stated, " or (or) " refers to " or (or) " of pardon, but not exclusive " or (or) ".Such as, below arbitrary condition all applicable elements A "or" B:A be true (or existence) and B is false (or not existing), A is false (or not existing) and B is true (or existence), and A and B is very (or existence).
In addition, the indefinite article " " before key element of the present invention or component and " one " intention represent that appearance (the namely occurring) number of times of described key element or component is not restricted.Therefore " one " or " one " is understood to include one or at least one, and quantity is odd number unless expressly stated, otherwise the described key element of singulative or component also comprise the situation of plural number.
" mol% " refers to molar percentage.
In specification sheets of the present invention and claims, term " homopolymer " refers to the polymkeric substance obtained by a kind of polymerization of repeating unit.Such as, term " Poly(Trimethylene Terephthalate) homopolymer " refers to any polymkeric substance be substantially made up of the repeating unit of a kind of propylene glycol ester terephthalate.
As used herein, term " multipolymer " refers to the polymkeric substance comprising the copolymerization units obtained by two or more comonomer." copolymer " refers to the polymkeric substance be substantially made up of the unit being derived from two kinds of comonomers, and " terpolymer " refers to the multipolymer be substantially made up of the unit being derived from three kinds of comonomers.Such as, term " Poly(Trimethylene Terephthalate) multipolymer " refers to any polymkeric substance comprising or derive from the propylene glycol ester terephthalate at least about 70mol% or higher, and other parts of described polymkeric substance derive from except terephthalic acid and 1,3-PD or form its ester equivalent except monomer.Term " pet copolymer " and " polybutylene terephthalate multipolymer " are also similarly define.
Embodiment of the present invention, be included in embodiment of the present invention described in summary of the invention part and any other following embodiment herein, all can at random combine, and polymer blend of the present invention is not only applicable to for the description of variable in embodiment, but also is applicable to moulded product prepared therefrom and fibre product.
Unless specifically stated, material described herein, method and example are only illustrative, and not restrictive.Although with those methods as herein described and material type like or the method that is equal to and material enforcement used in the present invention or test, still describe suitable method and material herein.
Below describe the present invention in detail.
the component of polymer blend
(a) polyester
According to the present invention, polyester (a) comprises any polycondensation product obtained by carrying out esterification or transesterify to alcohol and dicarboxylic acid (comprising its carboxylate).
The example of described alcohol comprises: carbonatoms is the glycol of 2-10, such as ethylene glycol, 1,2-PD, 1, ammediol, 1,3 butylene glycol, BDO, 1,5-pentanediol, 2,2-dimethyl-1,3-propylene glycol, 1,6-hexylene glycol, glycol ether, triglycol, polyoxyethylene glycol, 1,2-, 1,3-and 1,4 cyclohexane dimethanol; And the more glycol of long-chain and polyvalent alcohol, such as polytetramethylene ether glycol (it is the reaction product of glycol or polyvalent alcohol and epoxy alkane); Or wherein two or more combination.
The example of described dicarboxylic acid comprises: terephthalic acid, m-phthalic acid, phthalic acid, succsinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, 1,12-dodecanedicarboxylic acid; And derivative, the dimethyl ester of such as these dicarboxylic acid, diethyl ester, dipropyl; Or wherein two or more combination.
Described polyester can be homopolymer or multipolymer.When adopting multipolymer, the dicarboxylic acid component forming multipolymer can be selected from following compound by one or more and prepare: (1) carbonatoms is the aliphatic dicarboxylic acid of straight chain, ring-type and the branching of 4-12, such as succsinic acid, pentanedioic acid, hexanodioic acid, nonane diacid, sebacic acid, 1,12-dodecanedicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid; (2) carbonatoms is the aromatic dicarboxylic acid of 8-12, such as phthalic acid, m-phthalic acid, terephthalic acid or 2,6-naphthalene dicarboxylic acids; Or the equivalent of the formed ester of these dicarboxylic acid.In addition, the diol component forming multipolymer can be selected from following compound by one or more to be prepared: (3) carbonatoms is the aliphatic diol of straight chain, ring-type and the branching of 2-8, such as ethylene glycol, 1,2-propylene glycol, 1, ammediol, BDO, 1,6-hexylene glycol, 3-methyl isophthalic acid, 5-pentanediol, 2,2-dimethyl-1,3-propylene glycol, 2-methyl isophthalic acid, ammediol, 1,4-cyclohexanedimethanol or Isosorbide-5-Nitrae-cyclohexane diol; And (4) carbonatoms is aliphatic series and the aromatic oxide glycol of 4-10, two (2-hydroxyethyl) ether of such as quinhydrones.
These dicarboxylic acid and/or glycol can be used alone, or use with the form of the mixture of two or more copolymerization units.Main copolymerization units can be present in described multipolymer at least about 50mol%, the preferably amount of about 70mol% or more.
In one embodiment, in polymer blend of the present invention, described polyester (a) is polyester homopolymer or the polyester copolymer with two or more copolymerization units, and wherein the main amount of copolymerization units in described multipolymer is at least about 70mol%.
According to the present invention, the preferred polyester (a) for described polymer blend is selected from polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT), polybutylene terephthalate (PBT) and any blend thereof.
PET is polycondensation by ethylene glycol and terephthalic acid or ethylene glycol and dimethyl terephthalate (DMT) and the polyester prepared.PET can be PET homopolymer, PET multipolymer or its any blend.PET multipolymer preferably comprises at least about 70mol%, or at least about 80mol%, or at least about 90mol%, or at least about the ethylene glycol terephthalate of 95mol% as main copolymerization units.PET multipolymer can comprise other one or more the secondary copolymerization units to 30mol%, and described secondary copolymerization units is prepared by the glycol except ethylene glycol or the dicarboxylic acid except terephthalic acid.Preferred polyester (a) is PET homopolymer.
PTT is polycondensation by 1,3-PD and terephthalic acid or 1,3-PD and dimethyl terephthalate (DMT) and the polyester prepared.1,3-PD for the preparation of PTT is preferably obtained (" biogenetic derivation " 1,3-PD) from renewable source by biochemical method.PTT can be PTT homopolymer, PTT multipolymer or its any blend.PTT multipolymer preferably comprises at least about 70mol%, or at least about 80mol%, or at least about 90mol%, or at least about the propylene glycol ester terephthalate of 95mol% as main copolymerization units.PTT multipolymer can comprise other one or more secondary copolymerization units of the most nearly 30mol%, and described secondary copolymerization units is prepared by the glycol except 1,3-PD or the dicarboxylic acid except terephthalic acid.Preferred polyester (a) is PTT homopolymer.
According to the present invention, the preferred polyester (a) for described polymer blend is selected from PTT homopolymer, comprises the propylene glycol ester terephthalate of 70mol% or more as the PTT multipolymer of main copolymerization units or its any blend.Preferred polyester (a) is PTT homopolymer.
PBT is polycondensation by BDO and terephthalic acid or BDO and dimethyl terephthalate (DMT) and the polyester prepared.PBT can be PBT homopolymer, PBT multipolymer or its any blend.PBT multipolymer preferably comprises at least about 70mol%, or at least about 80mol%, or at least about 90mol%, or at least about the mutual-phenenyl two acid bromide two alcohol ester of 95mol% as main copolymerization units.PBT multipolymer can comprise other one or more secondary copolymerization units of the most nearly 30mol%, and described secondary copolymerization units is prepared by the glycol except BDO or the dicarboxylic acid except terephthalic acid.Preferred polyester (a) is PBT homopolymer.
Polyester and the method for the preparation of them are well-known to those skilled in the art.United States Patent (USP) 6,277,947 and 7,531,617 disclose the method for the preparation of PTT.For concise and to the point object, omit prepared by PET and PBT further describe herein.
In the present invention, the limiting viscosity of polyester used is not particularly limited, and mediates as long as described resin can be melted.But consider mouldability, the limiting viscosity of polymer blend of the present invention is at least about 0.4dL/g, is preferably at least about 0.7dL/g, is more preferably at least about 0.9dL/g, and most preferably is at least about 1.0dL/g.The limiting viscosity of polymer blend of the present invention is up to about 2.0dL/g, is preferably up to about 1.8dL/g, is more preferably up to about 1.5dL/g, and is most preferably up to about 1.2dL/g.
In one embodiment, in polymer blend of the present invention, polyester homopolymer or the polyester copolymer of described polyester (a) to be limiting viscosity be 0.4-2.0dL/g.In another embodiment, in polymer blend of the present invention, PET homopolymer or the PET multipolymer of described polyester to be limiting viscosity be about 0.4-1.0dL/g.In still another embodiment, in polymer blend of the present invention, PTT homopolymer or the PTT multipolymer of described polyester to be limiting viscosity be about 0.6-2.0dL/g.In still another embodiment, in polymer blend of the present invention, PBT homopolymer or the PBT multipolymer of described polyester to be limiting viscosity be about 0.7-2.0dL/g.
Suitable polyester can available from commercial sources, such as, from Yuanfang Industry (Shanghai) Co., Ltd.
from BASF's
from DuPont's
from Invista's
from SKChemicals's
from TorayIndustries, Inc
pBT and from Changchun, Taiwan chemical industry
The content of the polyester (a) in polymer blend of the present invention is about 95 % by weight to about 99.99 % by weight of described polymer blend gross weight, or about 97 % by weight to about 99.99 % by weight, or about 98 % by weight to about 99.5 % by weight, or about 95 % by weight to about 99.5 % by weight.
(b) melt flow modifiers
The melt flow modifiers (b) joined in polymer blend of the present invention is with the sucrose ester of undefined formula 1:
Wherein
Each R is H, C independently of one another
8-C
26alkyl-carbonyl, or C
8-C
26alkenyl carbonyl;
When R is H, its sum is 0,1 or 2.
Term " fatty acid " in this article " refer to linear monocarboxylic acid containing 8-26 carbon atom chain (comprising the carbonyl carbon of hydroxy-acid group).Lipid acid, preferably containing 12-24 carbon atom, more preferably contains 14-20 carbon atom." unsaturated fatty acids " is containing the unsaturated position of at least one carbon-to-carbon, i.e. at least one carbon-to-carbon double bond.Usually known unsaturated fatty acids can have one or more double bond, and such as oleic acid has a double bond, and linolic acid has two double bonds, and alpha-linolenic acid has three double bonds.Term " sucrose fatty ester " or " sucrose ester " are used interchangeably in this article.
Sucrose is disaccharide, and it contains 8 hydroxyls at esterified front each molecule.The hydroxyl that the sucrose ester of suitable formula 1 means described sucrose with can be identical or different fatty acid esterification.In addition, all hydroxyls of described sucrose all fatty acid esterification will do not used.Preferably, the sucrose ester of formula 1 has and is no more than 2 non-esterified hydroxyls, and meaning described sucrose ester can be sucrose six ester, sucrose seven ester or sucrose octaester.
The sucrose ester of formula 1 can be formed by the reaction of sucrose and lipid acid or fatty acid ester, and wherein this lipid acid can be saturated or undersaturated.Fatty acid ester as parent material is preferably C
1-C
4alkyl ester, is more preferably methyl ester.
Be well-known with lipid acid or fatty acid ester by the condition of alcohol esterification, and do not need special condition at this.Normally, described reaction carries out, to obtain commercial rational speed of reaction at the temperature (such as 80 ° of C-220 ° of C) raised.(when making reactant with lipid acid, its by product is water to help removing condensation by-product normally to adopt subatmospheric pressure; When using fatty acid ester, its by product is lower alcohol) and molecular balance is moved towards wanted ester products direction.Catalyzer as tin catalyst, titanium catalyst or salt of wormwood can exist to increase its speed of response.Described reaction can be carried out in the presence of a solvent or diluent.
For cost reason, the lipid acid that lipid acid or fatty acid ester as parent material are preferably obtained by vegetables oil and/or animal tallow or fatty acid ester blends.Vegetables oil and animal tallow are the triglyceride level of fatty acids; Fatty acid component wherein can from initial triglyceride level in a known way through hydrolysis formed lipid acid or with lower alcohol particularly Methanolysis form the lower alkyl ester of lipid acid and obtain as the methyl esters of lipid acid.The mixture of the fatty acid component of most vegetables oil and animal tallow normally two or more materials that chain length and/or unsaturated positional number can be different.The content of the fatty acid mixt obtained in any particular case depends on as this oil or adipose-derived specific plant or animal species, and in less degree, depend on this oil or fatty provenance and (particularly for plant oil condition) this oil or fatty the produced time period in this year and other growth conditionss.In many cases, from least some fatty acid or ester that vegetables oil or animal tallow obtain are saturate.Such as, many usual available vegetables oil have saturated and unsaturated type in its fatty acid component simultaneously.
The example of suitable vegetables oil comprises soybean oil, Thistle oil, Oleum Gossypii semen, Toenol 1140, peanut oil, sweet oil, sunflower seed oil, Tower rape oil (canolaoil), rapeseed oil, Semen Maydis oil, Viscotrol C, plam oil, cannabis oil or two or more combination arbitrarily.Initial vegetables oil can from genetically modified plant as genetically engineered soybean, Sunflower Receptacle or canola obtain.
Sucrose ester necessarily a kind of mixture of the formula 1 using the fatty acid mixt being derived from vegetables oil or animal tallow to prepare.If need more highly purified sucrose fatty ester, then can by the purifying mixture of lipid acid (or ester) before esterify sucrose.Depending on its specification, described purifying can be more or less strict.In some cases, the lipid acid (or ester) of single kind can be separated for preparing sucrose fatty ester from mixture.In other cases, lipid acid (or ester) mixture by more strictly purifying, to increase the concentration of one or more of desired fats acid (or ester), can reduce the concentration of those more unwanted lipid acid (or ester) simultaneously.Such as, the concentration increasing saturated fatty acid or ester can be needed before preparing sucrose fatty ester.By in minimized for unsaturated fatty acid content situation, lipid acid (or ester) mixture can be converted to completely saturated lipid acid (or ester) mixture by hydrogenation.
But in many cases, directly can use the fatty acid or ester composition obtained from vegetables oil or animal tallow, it is slightly through separating treatment or the fatty acid or ester composition without separating treatment.From the economic point of view, this is often ideal.
Molecular weight for the sucrose ester of formula 1 has no particular limits.But in order to avoid migration problem, the molecular-weight average of sucrose ester (b) is preferably at least 1000, and is not more than 3500, or is more preferably 2000-3000.The molecular-weight average of the sucrose ester of formula 1 is by using high performance liquid chromatography, mass spectroscopy, and/or other analysis tools are determined.
In sucrose fatty ester, the amount of degree of unsaturation is by its iodine value/or determination of iodine value, iodine value/or iodine number the quality (unit for gram) of iodine that consumes by 100 grams of chemical substances.The double bond existed in this sucrose fatty ester of the less expression of its value is fewer.
United States Patent (USP) 6,620,952 and 6,887,947 disclose the preparation of sucrose-fatty and the method for purifying.
The example of commercially available sucrose fatty ester comprises the commodity that Proctor & Gamble sells and is called
product.
Based on the gross weight of described polymer blend, the consumption of described melt flow modifiers (b) (i.e. the sucrose ester of formula 1) is about 0.01 % by weight to about 5 % by weight, or about 0.1 % by weight to about 3 % by weight, or about 0.5 % by weight to about 2 % by weight.
(c) other additives
Described polymer blend also can comprise (c) at least one additive, and it is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, hydrolysis-resisting agent, chain extension agent, fire retardant, softening agent, filler and arbitrary combination thereof.
The appropriate level of these additives and the method for these additives being mixed polymer composition are well known by persons skilled in the art.See such as ModernPlasticsEncyclopedia.
Suitable antioxidant includes but not limited to: hindered phenol compound, comprises such as commodity and is called
with
four (methylene radical (3,5-bis-(uncle) butyl-4-hydroxy hydrocinnamate)) methane, all can purchased from BASF.Other suitable antioxidants comprise phosphorite, and such as GESpecialtyChemical (Morgantown, W.Va., USA) sells
626 Hes
and BASF sells
(three (2,4-di-tert-butyl-phenyl) phosphorous acid ester).
The amount that these additives exist in described polymer blend is generally about 0.01 % by weight to about 15 % by weight, or about 0.01 % by weight to about 10 % by weight, wherein % by weight is the gross weight based on described polymer blend, as long as they do not impair the basic of described polymer blend do not produce significant disadvantageous effect with novelty and to the performance of described polymer blend.
The present invention is by means of the melt flow characteristics of use melt flow modifiers (b) (i.e. the sucrose ester of formula 1) to come melt viscosity that providing package reduces containing the polymer blend of polyester or improvement.Therefore, present invention teaches and molecular-weight average is at least 1, formula 1 compound of 000 mixes in polymer blend as melt flow modifiers (b).
Polymer blend of the present invention is the blend in melting-mixing, wherein all polymeric constituents are dispersed in each other well, and all non-polymeric ingredients are also scattered in wherein equably, and are combined with polymeric matrix, described blend is made to form unified entirety.Any melting-blending means can be used by component (a), (b) and (c) are obtained by mixing described blend.Use melt mixer, such as singe screw or twin screw extruder, blender, kneader, Banbury mixer etc., can mix described constituent materials and obtain resin combination.Or, the part in described material can be mixed in melting-mixing machine, and then the remainder in described material is added, and further melting-mixing is until evenly.
The mixing order prepared in polymer blend of the present invention can be by the charging of each component and melting, or can by filler (if existence) and/or the charger charging from the side of other components etc., and this is understood by one of ordinary skill in the art.
Embodiment to comprise described composition directly with powder or particle form melt blending, is extruded by this blend, and cuts into pellet or other suitable shapes.Term " pellet " is made broad sense at this and is used, and itself and shape have nothing to do, and sometimes can be called as " chip ", " sheet stock " etc.Also comprise first for described composition dry type mixing in addition, then mix with molten state in an extruder.
Mixing temperature should higher than the fusing point of each component, but lower than its lowest decomposition temperature, and correspondingly must adjust for any composition specifically of polyester (a) and melt flow modifiers (b).Depend on the polyester (a) that the present invention is concrete and melt flow modifiers (b), described mixing temperature, usually at about 180 ° of C-about 290 ° of C, is preferably at least about 228 ° of C, and is up to the scope of about 270 ° of C.
Polymer blend of the present invention has much desirable character such as, but not limited to, good mobility, good mechanical properties, good resistance to hydrolysis and high chemical resistance.
The invention still further relates to the moulded product or fiber product that comprise polymer blend of the present invention or obtained by polymer blend of the present invention.
comprise the moulded product of polymer blend
Use method known to those skilled in the art polymer blend as herein described can be shaped to goods, described method comprises injection moulding, extrusion molding, blowing, injection moulding altogether, compression moulding, crosses molding (overmolding) and profile extrusion.Preferably, described goods are by injection moulding or extrusion moulding.
The polymer blend of liquidity costs of the present invention can be used for almost any injection moulding or extrusion molding application.Due to the melt viscosity improved, melt temperature can be reduced and/or greatly can shorten the whole cycle production cost of injection moulding (reduce) of injection moulding or extrusion process.In addition, the polyester improving melt viscosity can be used to prepare thin-walled application, and its high fluidity of molten is key request.
The moulded product obtained by polymer blend of the present invention is suitable for various application, comprises the parts electrically or in electronic installation or shell; Inside and outside parts/the component of automobile; The component of domestic electric appliance; The component of gardening and leisure area application.
The Electrical and Electronic device of polymer blend manufacture of the present invention can be utilized to be socket, socket component, socket type connector, bunch of cables component, circuit carriers, circuit carriers component, the circuit carriers of three-dimensional injection moulding, electrical connector element, electromechanical integration component, and optoelectronic integration component.
In the possible purposes of automotive interior be: dashboard, lock for steering column, chair component, headrest, central control station, transmission components and door module; And possible automobile external component is: door knob, headlight component, exterior mirror component, screen washer component, screen washer guard shield, grid, roof support, skylight sash and outside car body component.
The possible purposes of polymer blend of the present invention in kitchen and household field produces the component of galley equipment, described galley equipment such as, frying pan, flatiron, button (buttons), and the application of gardening and leisure area, such as, the component of irrigation system or gardening equipment.
In medicine technology field, polymer blend of the present invention can be used to produce exhales sucker shell and their component.
comprise the fiber product of polymer blend
Polymer blend of the present invention can be become long filament by Direct Spinning; Or be easily then spun into long filament from the pellet conversion, the again melting that are obtained by polymer blend of the present invention.
Long filament can be used for fiber product, such as, and clothes, earth material, and other application needing long filament, and conventional polymkeric substance and throwing equipment can be used to prepare.As other premises described herein, polymer blend of the present invention provides favourable change relative to described polyester itself in melt viscosity properties.
For the present invention, term " fiber product " comprises long filament, fiber, yarn, fabric, or finished product, such as clothes, home furnishings, carpet and other consumer's goods.
Term " fiber " refers to the material that length-to-diameter ratio is greater than about 10.Fiber is sorted out according to its fineness (or linear density) usually.Fiber is commonly defined as the fiber fineness having and be greater than about 15 DENIER, is usually greater than about 30 DENIER.Thin denier fiber typically refers to the fiber that fineness is less than about 15 DENIER.
Term " filament fiber " comprises " mono filament fiber " and " how long silky fibre ", refer to the fiber of the natural or synthetic materials long filament of the one or more strands of continuous print comprising uncertain (namely not making a reservation for) length, corresponding with " staple fibre ", described " staple fibre " is the discontinuous fiber strand (namely one has been cut or has been divided into the segment with predetermined length) that length is certain.
Fiber product of the present invention can be the fiber comprising at least one long filament obtained by polymer blend of the present invention.
Term " yarn " refers to that natural materials for weaving or weave or synthetic materials are as the continuous bundle of twisting thread of wool, nylon or polyester.Term " fiber " and " yarn " are used interchangeably in this article.
Fiber product of the present invention can be yarn, and it comprises at least one long filament obtained by polymer blend of the present invention, fiber or staple fibre.
Fiber product of the present invention can be fabric, and it can braided fabric, woven fabric or nonwoven fabric obtained by the fiber comprising polymer blend of the present invention.Nonwoven fabric of the present invention is the staple fibre that comprises polymer blend of the present invention by applying heat, tangle and/or pressure and the reticulation that is connected or felt pan.
Particularly preferred fiber product of the present invention comprises long filament, fiber, yarn, fabric and carpet.
Without the need to being described in further detail, believing and can apply the present invention fully by above-mentioned explanation those skilled in the art.Therefore, following examples are interpreted as being only exemplary, and absolutely not to the restriction of disclosure.
Embodiment
Abbreviation " E " expression " embodiment ", " CE " expression " comparative example ", numeral has thereafter prepared described polymer blend in which embodiment or comparative example.All embodiments and comparative example are prepared all in a similar manner and test.Unless otherwise noted, percentage ratio is all based on weighing scale.
The each composition used is listed in embodiment and comparative example in table 1.
Table 1
the method of compounding of embodiment 1-11 and comparative example 1-5
Before compounding, in forced air circulation baking oven (forcedair-circulatingoven), by polyester granules drying about 6 hours under 130 ° of C.
According to table 2 and table 3, the composition of each embodiment and comparative example is dropped in batches there are 12 heating modules structures twin screw extruder (KraussmaffeiBerstorffZE25) to obtain the pellet of corresponding polymer blend.Batch size used is between 2.5 kilograms and 15 kilograms.
For the polyester granules comprising PBT and PTT, the temperature of forcing machine is set to 60/240/245/245/245/245/245/245/245/245/245/245 ° of C, and die head temperature is 245 ° of C; Temperature for the polyester granules forcing machine comprising PET is set to 60/250/260/260/260/260/260/260/260/260/260/260 ° of C, and die head temperature is 260 ° of C; And screw speed is 300rpm, output is 20Kg/ hour.
the molding methods of embodiment 1-9 and comparative example 1-4
After molding, the pellet extruded is dried to water content lower than 40ppm.For carrying out measuring mechanical property, at Sumitomo100 ton mould machine (screw diameter 32mm; Nozzle diameter 5mm) on according to ISO3167 molding multi-usage test bars.For the pellet (E1-E6, E9andCE1-CE2, CE4) comprising PTT or PBT, barrel temperatures set is 250 ° of C; For the pellet (E7, E8 and CE3) comprising PET, barrel temperatures set is 270 ° of C; And die temperature is 80 ° of C.Multi-usage test bars has basic dumb-bell shape, long 150mm, and stage casing is of a size of wide 10mm, thick 4mm, long 80mm.
general test method
The test of limiting viscosity (IV) uses black formula viscosity tube 1C, is that the phenol/tetrachloroethane of 1:1 is solvent, tests under 30 ° of C with mass ratio.First test solvent flows out the time of black formula viscosity tube under 30 ° of C, is designated as t
0(repeat 3 times, average), then tests 1.0%(weight/volume) polymer samples of the concentration solution that is dissolved in solvent flows out time of black formula viscosity tube under 30 ° of C, is designated as t
1; Each sample test 5 times, gets the rear mean value measured for 3 times.The limiting viscosity of sample is according to following formulae discovery:
η
sp=η
r-1
In formula:
C: sample solution concentration, g/dL
η
r: relative viscosity
η
sp: specific viscosity
[η]: limiting viscosity, dL/g
T
0: solvent elution time, second
T
1: sample solution flows out the time, second
Melt viscosity (MV) uses DynicLCR7001 capillary rheometer determining.In test process, make dry pellet through capillary rheometer, utilize shearing rate and shearing force to evaluate shear viscosity.The fusion time of all samples is 240 seconds.Although be included in 250 ° of C (comprising the sample of PBT and PTT) or 280 ° of C (comprising the sample of PET) and 2 kinds of shearing rate (1000s in each embodiment of this report or the MV data of comparative example
-1and 5000s
-1) under record those, but for the ease of contrast, unless otherwise indicated, the reduction degree of the melt viscosity of certain embodiment or comparative example refers to 1000s
-1shearing rate obtain data.
According to ISO527:1993 (E), on test macro Instron5567, measure tensile modulus.
According to ISO179, CEAST shock-testing machine is tested Charpy notch (NotchedCharpy) shock strength.
fiber sprinning and drawing-off processing procedure
Before melt-spinning, by the pellet extruded in an oven dry 10 hours of 80 ° of C, then 130 ° of C drier 15 little up to water content lower than 20ppm.
Melt-spinning: the pellet of drying is metered into and there are 4 is set as in the single screw extrusion machine (FujiE0200) of the heating module of 248/256/265/265 ° of C, thus produce partially oriented yarn (POY).Fuji melting-Spinning machine (ABE type) is equipped with 36 hole spinning jets, and plate surface diameter is 100 millimeters, and each pore has the diameter of 0.3 millimeter and length (L/Dratio) is 2, and winding speed is 1011 ms/min.The spinning temperature of each embodiment and comparative example is listed in table 4.
Drawing-off: nascent fibre uses that heat roller temperature is 65 ° of C, hot plate temperature is 135 ° of C and the drawing speed drawing-off crimping machine that is 400m/min (Suzhou spy send out dynamo-electric company limited, VC403-0111) carries out drawing-off.The drafting multiple of each embodiment and comparative example is listed in table 4.
fiber characterizes
The length of fiber sample first uses length meter measuring engine (Changzhou Hong Guang Textile Machinery Co., Ltd, YG086), and reel speed is 30 revs/min; From yarn bag, cut the yarn of designated length (L), i.e. the yarn of 100 meters, then claim its weight.The weight (W) of this yarn samples is gram to represent.Weight and length ratio (W/L) take advantage of 10000 to represent the linear density of this yarn with " dtex ".Or W/L takes advantage of 9000 to represent the linear density of this yarn with " DENIER ".The data reported are that the mean value measured for 10 times is listed in table 4.
Intensity measures being equipped with in the universal testing machine of two fixtures of the gauge length anchor yarns of 250 millimeters (Shimadzu AG-X series).Under the relative humidity of 25 ° of C and 65%, sample yarn is by the elongation speed tensile of 500 mm/min.Load cell record data, and obtain stress-strain curve.Intensity is the linear density of disruptive force divided by yarn, represents with cN/dtex.When elongation at break is fracture, the change of sample length is divided by its original length, represents with per-cent.The intensity reported and elongation at break data are that the mean value measured for 10 times is listed in table 4.Define embodiment of the present invention further in the examples below.The composite formula of each embodiment and comparative example and the evaluation result of its moulded product or fiber product are as reported in tables 2-4.
Table 2
According to the result of table 2, content is below obvious.
By the comparison of E1-E4 and CE1, can find out and mix the melt flow modifiers (b-1) (i.e. the compound of formula 1) of 0.5-2 % by weight with polyester (a-1) (i.e. PTT) and the polymer blend obtained respectively provides at 1000s
-1(23%-63%) and 5000s
-1(12%-64%) significantly reduced melt viscosity under velocity of shear.In addition, along with the increase of the amount of the melt flow modifiers used in PTT composition (b-1), the improvement of its mobility also increases.
For the comparison of 3 kinds of PTT (a-1) and the 1 % by weight different mixture E 2 of sucrose fatty ester, the melt viscosity data of E5 and E6, all samples all demonstrate the remarkable improvement of melt viscosity.Therefore, use the sucrose ester of the formula 1 with saturated or unsaturated fatty acids substituting group and different molecular-weight average, all found the improvement of melt viscosity.
Notice that the polymer blend of E1-E6 not only shows fluidity of molten and increases but also show beyond thought toughness increase (that is, as indicated in impact strength data).
In order to confirm that the sucrose ester of formula 1 also improves its shock strength, by adding known impact modifying agent, i.e. the Lotader of Arkema sale
tMaX8900, prepares CE2.The impact strength data of E2, E5 and E6 and CE2 are compared, the sucrose ester of result expression 1 has other advantages except the melt viscosity improving polymer blend really.
Table 3
According to the result of table 3, content is below obvious.
According to the comparison of E7 and CE3, the PET composition of the melt flow modifiers (b-1) (i.e. the compound of formula 1) containing 1 % by weight provides at velocity of shear 1000s
-1and 5000s
-1under, the increase of the fluidity of molten of about 6%.Similarly, the polymer blend of E9 and CE4 also shows at velocity of shear 1000s
-1and 5000s
-1under, the increase of the fluidity of molten of about 5%.But, along with the increase of the amount of the sucrose ester of polymer blend Chinese style 1, the melt viscosity improvement of higher degree also it is expected to.What is interesting is, compare E7, the impact strength data of E8 and CE3 and E9 and CE4, embodiments of the invention also show the toughness slightly increased.
When polyester (a) is PTT (E2, E5 and E6) compared with it for PET (E7) or PBT (E9), the sucrose ester of formula 1 more effectively can improve the melt viscosity of gained polymer blend apparently.
Table 4
(1) spinning property grading: " ++ " represent endless tow (nascent fibre (spunfiber)) be continuous print, without any fracture and there is good gloss; "+" represents that nascent fibre is continuous print, has several fracture of wires occasionally or fly silk just to occur.
(2) drawability grading: ++ " represent continuous drafting fiber and without any fracture; "+" represents the fiber of continuous drafting, but has fracture (1 ruptures/8 hours) once in a while.
According to the result of table 4, content is below obvious.
Polymer blend of the present invention demonstrates good in acceptable spinning and drawing-off performance, although these processing condition are not yet optimized for scale operation.Notice the melt viscosity owing to improving, E10 and E11 is spinning at the temperature lower than CE5.Result represents that use polymer blend of the present invention can carry out save energy by carrying out spinning at a lower temperature for the manufacture of fiber product (long filament, fiber).In addition, the fiber product manufactured at a lower temperature has less degraded, therefore shows that there is better properties mechanical properties aspect.Such as, the intensity data of the fiber of E10 and E11 is higher than the intensity data of the fiber of CE5.
In one embodiment, polymer blend comprises following mixture or is substantially made up of following mixture or is obtained by following mixture:
The Poly(Trimethylene Terephthalate) of (a) about 95 % by weight to about 99.99 % by weight;
(b) about 0.01 % by weight to about 5 % by weight the sucrose ester of formula 1 as melt flow modifiers;
And
At least one additive of (c) about 0.01 % by weight to about 15 % by weight, it is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, hydrolysis-resisting agent, chain extension agent, fire retardant, softening agent, filler and arbitrary combination thereof;
Wherein
Each R is H, C independently of one another
8-C
26alkyl-carbonyl or C
8-C
26alkenyl carbonyl;
When r ish, it adds up to 0,1 or 2; And
% by weight is the gross weight based on polymer blend.
Although with typical embodiment example and describe the present invention, its intention is limited in shown details, this is owing to may to have various amendment and alternative under spirit of the present invention not deviating from.Thus, when those skilled in the art by means of only routine test just can obtain with amendment of the present invention disclosed herein and etc. simultaneously, then believe all such modifications and to be equivalently included in as defined in the claims within the spirit and scope of the present invention.
Claims (9)
1. polymer blend, it has the melt viscosity of improvement, and it comprises:
The polyester of (a) 95 % by weight to 99.99 % by weight; With
B the sucrose ester of the formula 1 of () 0.01 % by weight to 5 % by weight is as melt flow modifiers:
Wherein
Each R is H, C independently of one another
8-C
26alkyl-carbonyl, or C
8-C
26alkenyl carbonyl;
When R is H, its sum is 0,1 or 2;
Described polyester (a) being is selected from polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate and any mixture thereof; And
Described % by weight is the gross weight based on described polymer blend.
2. the polymer blend of claim 1, wherein said polyester (a) is Poly(Trimethylene Terephthalate) homopolymer, Poly(Trimethylene Terephthalate) multipolymer or its any mixture, and wherein said Poly(Trimethylene Terephthalate) multipolymer comprises the propylene glycol ester terephthalate of at least 70mol% as main copolymerization units.
3. the polymer blend of claim 1, wherein said melt flow modifiers (b) comprises the sucrose octaester of at least 60 % by weight, and described % by weight is the gross weight based on described sucrose ester; And the molecular-weight average of described melt flow modifiers (b) is 1,000 to 3,500.
4. the polymer blend of claim 1, the content of wherein said melt flow modifiers (b) is 0.1 % by weight to 3 % by weight, and described % by weight is the gross weight based on described polymer blend.
5. the polymer blend of claim 1, it also comprises (c) at least one additive, and it is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, hydrolysis-resisting agent, chain extension agent, fire retardant, softening agent, filler and arbitrary combination thereof.
6. moulded product, it comprises the polymer blend any one of claim 1-5 or the polymer blend any one of claim 1-5 obtains.
7. fiber product, it comprises the polymer blend any one of claim 1-5 or the polymer blend any one of claim 1-5 obtains.
8. the fiber product of claim 7 is long filament, fiber, yarn, fabric or carpet.
9. improve the method for melt viscosity of polymer blend, it comprises: by the polyester of 95 % by weight to 99.99 % by weight with 0.01 % by weight to 5 % by weight formula 1 sucrose ester mix:
Wherein
Each R is H, C independently of one another
8-C
26alkyl-carbonyl, or C
8-C
26alkenyl carbonyl;
When R is H, its sum is 0,1 or 2;
Described polyester (a) being is selected from polyethylene terephthalate, Poly(Trimethylene Terephthalate), polybutylene terephthalate and any mixture thereof; And
Described % by weight is the gross weight based on described polymer blend.
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|---|---|---|---|---|
| CN1345221A (en) * | 1999-02-05 | 2002-04-17 | 荷兰联合利华有限公司 | Hair treatment compositions comprising C20 or higher unsaturated fatty acid polyester of cyclic polyols |
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|---|---|---|---|---|
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