CN105440593A - Toughening composition containing polytrimethylene terephthalate - Google Patents
Toughening composition containing polytrimethylene terephthalate Download PDFInfo
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- CN105440593A CN105440593A CN201410437095.3A CN201410437095A CN105440593A CN 105440593 A CN105440593 A CN 105440593A CN 201410437095 A CN201410437095 A CN 201410437095A CN 105440593 A CN105440593 A CN 105440593A
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Abstract
The invention discloses a toughening composition containing polytrimethylene terephthalate, and a product produced by using the composition. The toughening composition comprises about 55-80wt% of polytrimethylene terephthalate resin, about 19.5-35wt% of a reactive impact modifier, about 0.5-10wt% of a zinc ionomer and about 0-10wt% of an additive.
Description
Technical field
The present invention relates to the toughening compositions comprising polytrimethylene terephthalate, response type impact modifying agent, ionomer and optional other additives existed, it has excellent toughness (shock-resistance).The invention still further relates to the goods obtained by described toughening compositions.
Background technology
Thermoplastic polymer composition is commonly used to the various moulded products for the preparation of different application, such as trolley part, food product containers, electronic unit etc.
Polyester is the analog thermoplastic polymkeric substance containing ester functional group in its main chain.Polyester is often applied to the various products preparing such as fiber, packing film, extrudate or parts and moulded product or parts.Because polyester has multiple advantageous property, such as: low water absorbable, high-dimensional stability, high-insulativity, chemical resistance, thermotolerance, heat-resistant aging, good colour stability and wear resistance etc.
The most known polyester is polyalkylene terephthalates resinoid, comprises polyethylene terephthalate (PET), Poly(Trimethylene Terephthalate) (PTT) and polybutylene terephthalate (PBT).
When polyester being applied to goods such as preparing trolley part, sports apparatus or baking oven/microwave oven double-purpose pallet or parts, also these goods of extra demand or parts must have high tenacity, the resistance to fracture namely when it is hit usually.Therefore, adding the toughness improving polyester material in impact modifying agent to polyester is common means.Known conventional impact modifying agent comprises styrene block copolymer, ethylene/octene, polyacrylic core/shell particle and ethene/acrylic ester multipolymer, such as purchased from E.I.duPontdeNemoursandCompanyofWilmington, Del. (hereinafter referred to as " DuPont ")
aC and
pTW.Such as, WO8503718 discloses a kind of toughness reinforcing thermoplastic polyester composition, it comprise 60-97 % by weight vibrin (as, PET or PBT) and the ethylene copolymer (e.g., ethylene/acrylic acid positive butyl ester/glycidyl methacrylate terpolymer) of 3-40 % by weight.
But, the toughness being the impact modifying agent adding about 20-30 % by weight and no doubt effectively can improving this polyester product well known to those skilled in the art, but its rigidity (or physical strength) also can be made to be deteriorated simultaneously.Although reinforcing filler can be added if glass fibre is to improve its rigidity in polymer blend, which again increases unit weight and the cost of this material.Such as, CN10140274 discloses a kind of glass fiber reinforced polyethylene terephthalate matrix material, and it is made up of following raw material: PET100 part, 30 parts, glass fibre, composite elastic body compatibilization and toughening agent 5-20 part, composite nucleating agent 1-3 part, crystallization promoter 3-8 part and other multiple auxiliary agents etc.In addition, CN103849124A also discloses a kind of polymer blend of toughen and intensify, and it comprises at least one additive of the polyester of (a) about 30-85 % by weight, the mineral filler of (b) about 1-30 % by weight, the response type impact modifying agent of (c) about 10-30 % by weight, the zinc ionomer of (d) about 0.5-10 % by weight and (e) about 0.1-10 % by weight.
US4912167 discloses a kind of blow moldable polymer blend, it comprise the hemicrystalline polyester of (a) 70-90 weight part, (b) 10-30 weight part containing the multipolymer of epoxy group(ing) and the catalytic positively charged ion of (c) 0.01-3.0 weight part, wherein said catalytic positively charged ion is selected from the metal-salt of monocarboxylic acid, di-carboxylic acid, polycarboxylic acid and carboxylic polymkeric substance, and the positively charged ion of described metal-salt is selected from Al
+ 3, Cd
+ 2, Co
+ 2, Cu
+ 2, Fe
+ 2, In
+ 3, Mn
+ 2, Nd
+ 3, Sb
+ 3, Sn
+ 2, Sn
+ 2and Zn
+ 2; Condition is the cationic amount of this catalytic, with the total restatement of the component (a) of every 100 grams with (b), is 0.05-0.5 mmole.The object of this invention prepares hollow piece or parts to solve polyester to be applied to, as container, trolley part etc., although preferably use blow moulding to prepare, and the problem that the melt viscosity of routine commercially polyester is not high enough.Its technical scheme is the melt viscosity that catalytic positively charged ion by adding component (c) improves polymer blend.What is interesting is, when described component (c) is for zinc ionomer, its consumption is preferably less than 1 % by weight.Because along with its consumption be increased to 1% or more time, the melt viscosity of the polymer blend obtained declines on the contrary.In addition, in specification sheets preferably and embodiment polyester used be PBT resin and PET resin.
In a word, the polymer blend of good-toughness is all benefited from aforementioned many application, and people are it is more desirable that can obtain a kind of new polymer blend, and it is under the condition of not adding reinforcing filler, there is excellent shock resistance and physical strength simultaneously, and can with low cost manufacture.
Summary of the invention
The invention provides toughening compositions, it comprises following component, substantially composed of the following components or prepared by following component:
The polytrimethylene terephthalate of (a) 55-80 % by weight;
The response type impact modifying agent of (b) 19.5-35 % by weight, described response type impact modifying agent is ethene/(methyl) alkyl acrylate copolymer comprising at least one reactive functional groups, and described reactive functional groups is selected from epoxy group(ing) and anhydride group;
The zinc ionomer of (c) 0.5-10 % by weight; With
The additive of (d) 0-10 % by weight; Described additive is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, flow ability modifying agent, chain propagation agent, fire retardant, softening agent and arbitrary combination thereof;
Wherein, described % by weight based on the gross weight of described toughening compositions.
In one embodiment, in toughening compositions of the present invention, the polytrimethylene terephthalate of described component (a) is Poly(Trimethylene Terephthalate) homopolymer, Poly(Trimethylene Terephthalate) multipolymer or Poly(Trimethylene Terephthalate) blend.。
In another embodiment, in toughening compositions of the present invention, the limiting viscosity of the polytrimethylene terephthalate of described component (a) is 0.6dL/g-1.5dL/g.
In one embodiment, in toughening compositions of the present invention, the response type impact modifying agent of described component (b) comprises ethene/(methyl) methyl acrylate/maleic anhydride terpolymer, ethene/(methyl) ethyl propenoate/maleic anhydride terpolymer, ethene/(methyl) isobutyl acrylate/maleic anhydride terpolymer, ethene/(methyl) n-butyl acrylate/maleic anhydride terpolymer, ethene/(methyl) methyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) ethyl propenoate/glycidyl methacrylate terpolymer, ethene/(methyl) isobutyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) n-butyl acrylate/glycidyl methacrylate terpolymer, or its arbitrary combination.
In another embodiment, in toughening compositions of the present invention, the response type impact modifying agent of described component (b) comprises ethene/(methyl) methyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) ethyl propenoate/glycidyl methacrylate terpolymer, ethene/(methyl) isobutyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) n-butyl acrylate/glycidyl methacrylate terpolymer or its arbitrary combination.
In one embodiment, in toughening compositions of the present invention, the zinc ionomer of described component (c) comprises ethylene/methacrylic acid or ethylene/acrylic acid copolymer, its have zine ion as in and gegenion, and its neutralization ratio is about 0.4-about 0.9.
The present invention goes back the goods that providing package contains toughening compositions of the present invention or the goods obtained by toughening compositions of the present invention.
In one embodiment, goods of the present invention are the parts in outdoor activity equipment; Parts in transportation means; Or the shell of power tool, electric notor and household electrical appliance or wherein parts; Wherein said transportation means is automobile, train, aircraft or steamer.
The present invention also provides goods of the present invention as the parts in outdoor activity equipment, parts in transportation means, or the purposes of the shell of power tool, electric notor and household electrical appliance or wherein parts, wherein said transportation means is automobile, train, aircraft or steamer.
With reference to the following description, 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 represent toughening compositions of the present invention based on the gross weight of described toughening compositions should comprise lower than 1 % by weight lower than 0.5 % by weight or 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 50mol% 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 define similarly.
When describing some polymkeric substance, the application applicant sometimes should be understood by the monomer preparing polymkeric substance and use or prepare the amount of monomer that polymkeric substance uses and describe this polymkeric substance.But, this description may not comprise the concrete name of this final polymkeric substance, or the term of method-restriction-product may not be comprised, for monomer or its any statement of measuring, be interpreted as polymkeric substance and its corresponding polymkeric substance and composition that expression comprises those monomers (i.e. the copolymerization units of those monomers) or amount of monomer.
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 toughening compositions of the present invention is not only applicable to for the description of variable in embodiment, but also is applicable to the goods that obtained by described toughening compositions.
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 toughening compositions
(a) polytrimethylene terephthalate
Poly(Trimethylene Terephthalate) (usually referred to as " PTT ", " PPT " or " 3GT ") is a kind of new aromatic polyester after polyethylene terephthalate (being usually called for short " PET ") and polybutylene terephthalate (being usually called for short " PBT ").
Being applicable to PTT resin of the present invention can be PTT homopolymer, PTT multipolymer or PTT blend.Preferably PTT homopolymer.
In the present invention, " PTT homopolymer " refers to the polymkeric substance obtained by the polycondensation of 1,3-PD and terephthalic acid or terephthalic acid equivalent.Wherein, " terephthalic acid equivalent " refer to glycol reaction in show substantially with the compound of terephthalic acid same nature.For the object of the invention, terephthalic acid equivalent comprises the ester (such as dimethyl terephthalate (DMT)) of such as terephthalic acid and forms the derivative (such as carboxylic acid halides and acid anhydrides) of ester.Generally speaking, preferred terephthalic acid and terephthalate.1,3-PD for the preparation of PTT is preferably obtained (" biogenetic derivation " 1,3-PD) from renewable source by biochemical method.
In the present invention, " PTT multipolymer " is preferably containing 70mol% or higher or containing 80mol% or higher or containing 90mol% or higher or the propylene glycol ester terephthalate containing 95mol% or higher, other parts are derived from removing terephthalic acid and 1, monomer (such as other dicarboxylic acid: m-phthalic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid etc. outside ammediol; And/or other glycol: ethylene glycol, butyleneglycol etc.) polymkeric substance.
Term " blend " refers to the mixture mixed by two or more components.In the present invention, " PTT blend " is by preparing PTT homopolymer or the mixing of PTT multipolymer; Preferably comprise based on PTT blend gross weight about 80 % by weight or higher or containing 90 % by weight or higher or containing 95 % by weight or higher PTT homopolymer or PTT multipolymer.
The method preparing PTT homopolymer, PTT multipolymer or PTT blend is well-known to those skilled in the art, such as United States Patent (USP) 6,277,947,6,281,325 and 7, and 531,617 disclose the method for the preparation of PTT.
Being applicable to PTT homopolymer of the present invention also can be commercially available, and the commodity of such as E.I.Du Pont De Nemours and Co. of the U.S. (DuPontE.I.duPontdeNemoursandCompany is hereafter called " Du Pont ") are called
product, such as, being divided into according to its dulling agent content has greatly light, partly has the different sortses such as light, half delustring, full-dull; Each kind comprises again the PTT that several have different qualities viscosity (IV).
Consider the mouldability of toughening compositions of the present invention, the limiting viscosity of the PTT resin of described component (a) is at least about 0.6dL/g, is preferably at least about 0.8dL/g; Be up to about 1.5dL/g, be preferably up to about 1.3dL/g.In toughening compositions of the present invention, based on the gross weight of described toughening compositions, the content of the PTT resin of described component (a) is about 55 % by weight-Yue 80 % by weight or about 57 % by weight-Yue 79 % by weight,, or about 59 % by weight-Yue 77 % by weight, or about 61 % by weight-Yue 75 % by weight.
(b) response type impact modifying agent
In order to obtain good interfacial adhesion, and reducing the interfacial tension between component, in toughening compositions of the present invention, preferably adding response type impact modifying agent as component (b).
The response type impact modifying agent of described component (b) is preferably ethene/(methyl) alkyl acrylate copolymer, its comprise at least one reactive functional groups (such as epoxy group(ing), anhydride group etc.) in case with the hydroxyl of the Poly(Trimethylene Terephthalate) end group of component (a) or carboxyl reaction.
Term " (methyl) alkyl acrylate " described in the disclosure means alkyl acrylate or alkyl methacrylate, and ethene/(methyl) alkyl acrylate copolymer described in the disclosure is the multipolymer of the polymerized unit of at least one (methyl) alkyl acrylate comprising vinyl polymerization unit and about 6-40 % by weight.The moieties of (methyl) alkyl acrylate can contain 1-6 or 1-4 carbon atom, can be selected from methyl, ethyl and branching or nonbranched propyl group, butyl, amyl group and hexyl.The polarity of (methyl) alkyl acrylate comonomer can be controlled by the relative quantity and identity changing the alkyl be present in comonomer.Exemplary alkyl acrylate includes, but not limited to methyl acrylate, ethyl propenoate, isobutyl acrylate and n-butyl acrylate.Similarly, methacrylic acid C can be used
1-C
6alkyl ester comonomer is as comonomer.These comonomers comprise methyl methacrylate, β-dimethyl-aminoethylmethacrylate, Propenoic acid, 2-methyl, isobutyl ester and n-BMA.
Preferred alkyl comprises methyl, ethyl and butyl, and two or more the combination in these groups is also preferred.Preferred ethene/(methyl) alkyl acrylate copolymer comprises ethene/(methyl) n-butyl acrylate, ethene/(methyl) isobutyl acrylate, ethene/(methyl) ethyl propenoate and ethene/(methyl) methyl acrylate.
Described reactive functional groups, i.e. maleic anhydride (MAH) or glycidyl methacrylate (GMA), add in ethene/(methyl) alkyl acrylate copolymer by copolymerization or graft reaction.Response type ethene/(methyl) alkyl acrylate copolymer has MAH or GMA of about 2-20 % by weight content usually.
The preferred embodiment of the response type impact modifying agent of described component (b) comprises ethene/(methyl) methyl acrylate/maleic anhydride terpolymer, ethene/(methyl) ethyl propenoate/maleic anhydride terpolymer, ethene/(methyl) isobutyl acrylate/maleic anhydride terpolymer, ethene/(methyl) n-butyl acrylate/maleic anhydride terpolymer, ethene/(methyl) methyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) ethyl propenoate/glycidyl methacrylate terpolymer, ethene/(methyl) isobutyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) n-butyl acrylate/glycidyl methacrylate terpolymer or its arbitrary combination.
The method of preparation feedback type ethene/(methyl) alkyl acrylate copolymer is well known in the art.See, such as United States Patent (USP) 4,388,448 disclose the homopolymer of glycidyl methacrylate and the preparation of multipolymer.
An example of described response type ethene/acrylic ester multipolymer is that Arkema sells
aX8900, it is that it comprises the GMA of about 8 % by weight by the obtained terpolymer of ethene, methyl methacrylate and glycidyl methacrylate.Another example is purchased from DuPont
pTW, it is that it comprises the GMA of about 5 % by weight by the obtained terpolymer of ethene, n-butyl acrylate and glycidyl methacrylate.
In toughening compositions of the present invention, based on the gross weight of described toughening compositions, the amount of the response type impact modifying agent of described component (b) is about 19.5 % by weight-Yue 35 % by weight or about 20-34 % by weight or about 21-33 % by weight or about 22-32 % by weight.
(c) zinc ionomer
Term used herein " ionomer ", that be used alone or use with derivative form (such as " from poly-property "), refer to the multipolymer that its precursor acids multipolymer has been used neutralizing agent (such as mineral alkali) and neutralized at least in part, and it comprises the carboxylate salt with the gegenion deriving from neutralizing agent.
As used herein, term " acid copolymer " refers to the polymkeric substance containing alpha-olefin, α, β-ethylenic unsaturated carboxylic acid and optional other suitable comonomers (such as α, β-ethylenically-unsaturated carboxylic acid ester) existed.
As the precursor acids multipolymer in ionomer source, to comprise comonomer be carbonatoms is the alpha-olefin of 2-10; And based on the gross weight of described precursor acids multipolymer, the comonomer of about 5-30 % by weight, about 5-25 % by weight or about 10-25 % by weight to be carbonatoms the be α of 3-8, β-ethylenic unsaturated carboxylic acid.
Suitable alpha-olefin comonomer includes but not limited to the mixture of two or more in ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 3-methyl-1-butene, 4-methyl-1-pentene etc. and these alpha-olefins.Preferably, alpha-olefin is ethene.
Suitable α, β-ethylenic unsaturated carboxylic acid comonomer includes but not limited to the mixture of two or more in vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid, maleic anhydride, fumaric acid, monomethyl maleic acid and these sour comonomers.Preferably, α, β-ethylenic unsaturated carboxylic acid is selected from vinylformic acid and methacrylic acid.
Described precursor acids multipolymer also can comprise other one or more comonomers, such as α, β-ethylenically-unsaturated carboxylic acid ester.The example of preferred suitable comonomer includes but not limited to methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl acrylate, glycidyl methacrylate, vinyl-acetic ester and the mixture of two or more wherein.But preferably, described precursor acids multipolymer does not comprise other comonomers of any remarkable content.
The mixture of precursor acids multipolymer is also suitable, as long as the character of described multipolymer is in scope as herein described.Such as, the copolymer of two or more can be used, carboxylic acid comonomers's content of wherein institute's copolymerization can not identical or its melting index can not be identical.In addition, the mixture comprising the precursor acids multipolymer of copolymer and terpolymer may also be suitable.
In order to obtain described ionomer, partially or even wholly neutralizing described precursor acids multipolymer with alkali, making the carboxylic acid group in described precursor acids multipolymer react and form carboxylate salt.The ionomeric exact level be neutralized is called as neutralization ratio.After being neutralized, ionomer can comprise any feasible unit price or divalent cation usually, such as, and lithium, sodium, potassium, magnesium, calcium, barium, copper, zinc or ammonium ion etc.
By experiment, applicant of the present invention finds that the ionomer of applicable toughening compositions of the present invention is zinc ionomer, and this zinc ionomer can have the hydrogen atom that about 40mol%-is about the carboxylic acid group of the precursor acids multipolymer of 90mol% is replaced (i.e. the neutralization ratio of about 0.4-about 0.9) by zine ion.
Described zinc ionomer preferably comprises neutralization ratio for about 0.4-about 0.9, or about 0.4-about 0.7, or the ethylene/methacrylic acid of about 0.43-about 0.6 or ethylene/acrylic acid copolymer.
Described zinc ionomer can have the melt flow index (MFI) of about 0.3-25g/10min or about 0.5-10g/10min or about 0.6-5g/10min, and it measures according to ASTM method D1238 under 190 DEG C and 2.16kg.
In order to obtain zinc ionomer used herein, described precursor acids multipolymer by any ordinary method, such as United States Patent (USP) 3,404,134 and 6,518, the method disclosed in 365 neutralizes.
Multiple preferred zinc ionomer can from DuPont with trade(brand)name
9xxx series be commercially available, it is ethylene/methacrylic acid.In addition,
295 Hes
295A is the zinc ionomer buied from HoneywellCo., Ltd. (USA), and it derives from ethylene/acrylic acid copolymer.
For the amount of the zinc ionomer (c) in toughening compositions of the present invention, based on the gross weight of described toughening compositions, be about 0.5-10 % by weight or about 1-9 % by weight or about 2-8 % by weight or about 3-7 % by weight.
(d) other additives
Described toughening compositions also optionally comprises the no more than at least one additive of about 10 % by weight, it is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, flow ability modifying agent, chain propagation agent, fire retardant, softening agent and arbitrary combination thereof, as long as described additive does not reduce the mechanical property desired by goods or surface properties that are obtained by described toughening compositions.
The suitable amounts 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.
In one embodiment, in toughening compositions of the present invention, the content of the additive of described component (d) is about 0.1 % by weight-Yue 10 % by weight.
Proper lubrication agent includes but not limited to: LoxiolP861/3.5, LoxiolPTSHOB7119 that Cognis sells, and ClariantCorp., LicomontET132, LicomontET141 and LicomontwaxOP that (Charlotte, N.C., USA) sells.
Suitable antioxidant includes but not limited to: hindered phenol compound, comprises such as commodity and is called
1010 Hes
four (methylene radical (3,5-bis-(uncle) butyl-4-hydroxy hydrocinnamate)) methane of 1076, all can purchased from BASF.Other suitable antioxidants comprise phosphorite, the ULTRANOX626 that such as GESpecialtyChemical (Morgantown, W.Va., USA) sells and
619.BASF sells
168 (three (2,4-di-tert-butyl-phenyl) phosphorous acid esters) are thermo-stabilizers, use usually used as auxiliary antioxidant.
Suitable fire retardant includes but not limited to the compound (such as P contained compound etc.) of halide-containing (such as brominated Polystyrene etc.), charcoal becoming or discharges compound (zinc borate etc.) or its any mixture of water type.Described fire retardant is known component, and it is commercially available or obtain by currently known methods.Not halogen-containing fire retardant is preferred, such as organophosphate or ester fire retardant.Commercially available organophosphate or ester fire retardant include but not limited to that RDP, BDP, RDX and Doher-7000 can purchased from DaihachiChemicalIndustry and Zhejiang Province Wansheng Chemical Co., Ltd.
the preparation of toughening compositions
Toughening compositions 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), (c) and (d) 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 toughening compositions of the present invention can be by the charging of each component and melting, or can by filler and/or the charger charging from the side of other components etc., and this is understood by one of ordinary skill in the art.
An embodiment comprises: by described composition directly with powder or particle form melt blending, 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.
Described mixing temperature should higher than the fusing point of each component (a), (b), (c) and/or (d), but lower than its lowest decomposition temperature, and correspondingly must adjust for any specific composition.Described mixing temperature, usually about 180 DEG C of-Yue 290 DEG C, is preferably at least about 250 DEG C, and is up to the scope of about 270 DEG C.
comprise the goods of toughening compositions
The invention still further relates to the goods comprising toughening compositions of the present invention or obtained by toughening compositions of the present invention.
Use method known to those skilled in the art toughening compositions as herein described can be shaped to goods, described method comprises injection moulding, extrusion molding, blowing, injection moulding altogether, compression moulding, crosses molding and profile extrusion.Preferably, described goods are by injection moulding or extrusion moulding.Preparation examples comprises film, laminated product or other moulded products, such as transportation means parts, engine parts or electrical/electronic components.
Can be applicable in multiple transportation means assembly through molding or the goods extruded, it meets following one or more requirement: high-impact; Significant weight saving (such as conventional metal material); Resistant of high or low temperature; Oil-proofness; Chemical resistance (such as refrigerant and road salt); And noise abatement, make Products Design compacter and have more integraty.
These goods are specially adapted to the parts in outdoor activity equipment, such as ice skate etc.; Trolley part, such as body panels and other external components are as mud guard, fuel tank cap, casing of rearview mirror; And for the manufacture of electronics and electric installation, such as televisor, computer, mobile communication equipment; With the shell of office automation devices.
embodiment
Abbreviation " E " expression " embodiment ", " CE " expression " comparative example ", numeral has thereafter prepared described toughening compositions in which embodiment or comparative example.The comparative example of all embodiments and its correspondence is prepared all in a similar manner and tests.Unless otherwise noted, percentage ratio is all based on weighing scale.
material
The each composition used is listed in embodiment and comparative example in table 1.
Table 1
detailed step
A) mix: the composition comprised in each embodiment of PTT or PBT and comparative example is mixed by blender, then by its from have 12 heating modules structures twin screw extruder (KraussmaffeiBerstorffZE25) front endfeed and obtain corresponding toughening compositions pellet.For the comparative example of the embodiment and PBT that comprise PTT, the temperature of forcing machine is set to 60/180/250/250/250/250/250/250/250/250/250/250 DEG C; 60/180/260/260/260/260/260/260/260/260/260/260 DEG C is set to for the comparative example comprising PET.Die head temperature is 270 DEG C, and screw speed is 300rpm, and output is 20Kg/ hour.
B) molding: before molding the pellet extruded is dried to moisture content lower than 40ppm.For carrying out measuring mechanical property, the Sumitomo100Ton mould machine of the nozzle diameter of the screw diameter and 5mm with 32mm prepares multi-usage test bars according to the standard method of ISO3167.For the comparative example of the embodiment and PBT that comprise PTT, barrel zone temperature is set to 260 DEG C, and die temperature (moldtemperature) is 80 DEG C; For the comparative example comprising PET, cylinder temperature is set to 270 DEG C, and die temperature is 80 DEG C.This 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.
testing method
According to ISO178:2001 (E), Instron5567 test macro is tested the maximum stress in bend (maximumflexuralstress) under the strain of 3.5%.Report that numerical value is the average measurement value of 5 test bars, described sample has high value person for good.According to the method for ISO527:1993 (E), test mechanical performance on Instron5567 test macro, such as tensile break stress (tensilestressatbreak) and elongation at break (elongationatbreak).Gained observed value is the mean value of 5 test bars, and described sample has high value person for good.
Use ISO179/1eA standard method, CEAST impact tester is tested but shellfish (Charpy) notched Izod impact strength.Gained observed value is the mean value of 10 test bars, the sample that described numerical value is higher represent its shock resistance or toughness better.
Limit embodiment of the present invention further below in an example.The composition of embodiment and comparative example and evaluation result are shown in table 2-5.
Table 2
" * " represents that this comparative example is reference sample, and other comparative examples or embodiment are calculate for benchmark with the numerical value of this reference sample at the velocity of variation of its properties.
Obvious from result the following stated content of table 2.
Relatively the performance data of CE2 and CE1 just finds: after replace the response type impact modifying agent based on the composition moderate of PTT resin with a small amount of sodium ionomer (namely, the amount maintaining component (a) is 70 % by weight), although the elongation at break of described CE2 composition slightly improves (25%), its resistance to impact shock is any increase and decrease not.On the contrary, relatively the performance data of E1, E2, E3 and CE1 but finds: the composition based on PTT resin that with the addition of the zinc ionomer of 2.6-6 % by weight, the i.e. specific embodiment of toughening compositions of the present invention, not only its elongation at break increases significantly (113-319%) than this value not containing ionomeric composition (CE1); More unexpectedly, when reducing the actual amount of response type impact modifying agent of its component (b), unexpectedly improve its resistance to impact shock and being about 455-645%.So, in the composition showing based on PTT resin by the performance data comparing CE2 and E3 only using zine ion as in and the ionomer of gegenion desirable resistance to impact shock just can be provided to improve.
Whether be not limited to following theoretical correctness, a small amount of zinc ionomer why can shockingly improve in toughening compositions of the present invention described toughening compositions resistance to impact shock and or other mechanical propertys (as, elongation at break), be perhaps attributable to the blended homogeneity that zinc ionomer can promote between PTT resin and response type impact modifying agent.
Table 3
" * " represents that this comparative example is reference sample, and other comparative examples or embodiment are calculate for benchmark with the numerical value of this reference sample at the velocity of variation of its properties.
But, even if show that PBT, PET and PTT belong to thermoplastic polyester one base polymer by the result of comparison sheet 3, because of the difference of their monomer structures, a small amount of zinc ionomer is added (namely in the Comparative composition based on PBT resin or PET resin, relatively CE4 and CE3, or CE6 and CE5) but only find zinc ionomer to its resistance to impact shock almost without impact (CE4:+5%, CE6:-2%).As can be seen here, only have the toughening compositions of the present invention based on PTT resin, zinc ionomer just can be considered it is the synergist of component (b) response type impact modifying agent.
Table 4
" * " represents that this comparative example is reference sample, and other comparative examples or embodiment are calculate for benchmark with the numerical value of this reference sample at the velocity of variation of its properties.
From the result of table 4, for toughening compositions of the present invention, when the amount of component (a) PTT resin is increased to 75 % by weight by 70 % by weight, also can obtain the same conclusions as the former.
Relatively the performance data of CE8 and CE7 can find: the ionomeric CE8 composition of the sodium containing 3.6 % by weight, and its resistance to impact shock and elongation at break all slightly reduce (about 11-15%) relative to this value not containing ionomeric CE7 composition.
But, the composition of E4 and the E5 of the zinc ionomer containing 2.1-3.6 % by weight, i.e. some specific embodiments of toughening compositions of the present invention, its elongation at break is be significantly improved (37-121%) relative to this value not containing ionomeric CE7 composition; Particularly in the actual content situation reducing its response type impact modifying agent, its resistance to impact shock presents the raising (385-408%) of unexpectedly several times.
Table 5
" * " represents that this comparative example is reference sample, and other comparative examples or embodiment are calculate for benchmark with the numerical value of this reference sample at the velocity of variation of its properties.
From the result of table 5, be that the composition containing 65 % by weight PPT resins also can obtain being similar to aforesaid conclusion for embodiment.
Relatively the performance data of E6, E7, E8 and CE9 can find: when the toughening compositions based on PTT resin contains the zinc ionomer of 2-7 % by weight, and the existence of described zinc ionomer provides beat all significantly improving for the resistance to impact shock of described composition.Meanwhile, also (71-217%) is significantly improved to the elongation at break of described composition.In addition, when comparing other mechanical properties data, the flexural strength of toughening compositions of the present invention and tensile strength are sent out also than will slightly not increase containing this value of the composition of ionomeric CE9.In other words, based on the toughening compositions of PTT resin under the condition of not adding reinforcing filler, the excellent shock resistance of said composition and physical strength can just be given by adding a small amount of zinc ionomer.In addition, toughening compositions of the present invention also has the advantage reducing manufacturing cost, because without the need to adding reinforcing filler.
Known reinforcing filler can be categorized as (1) mineral, such as clay, kaolin, sepiolite, talcum, wollastonite, mica and calcium carbonate; (2) various forms of glass, such as glass fibre, milled glass, solid or hollow glass sphere; (3) carbon, such as carbon black or carbon fiber; (4) titanium dioxide; (5) be the aramid fiber of staple fibre, fibril or fibrid; Or its arbitrary combination.See HansZweifel (editor), PlasticsAdditivesHandbook, the 5th edition, 901-948 page, HanserPublishers, Munchen (Germany) 2001.Concrete examples of fillers comprises glass fibre, graphite fibre, Kevlar, glass flake, granulated glass sphere, clay, kaolin, sepiolite, talcum, wollastonite, mica, calcium carbonate, calcium sulfate, magnesium sulfate, silicon-dioxide whisker, potassium titanate and arbitrary combination thereof.
In one embodiment, toughening compositions of the present invention does not comprise filler substantially, and described filler is selected from glass fibre, graphite fibre, Kevlar, glass flake, granulated glass sphere, clay, kaolin, sepiolite, talcum, wollastonite, mica, calcium carbonate, calcium sulfate, magnesium sulfate, silicon-dioxide whisker, potassium titanate and arbitrary combination thereof.
In some embodiments, described toughening compositions comprises following component, substantially composed of the following components, or is prepared by following component:
Poly(Trimethylene Terephthalate) (PTT) resin of (a) 55-80 % by weight;
The response type impact modifying agent of (b) 19.5-35 % by weight, described response type impact modifying agent is ethene/(methyl) alkyl acrylate copolymer comprising at least one reactive functional groups, and described reactive functional groups is selected from epoxy group(ing) and anhydride group;
The zinc ionomer of (c) 0.5-10 % by weight; With
The additive of (d) 0-10 % by weight; Described additive is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, flow ability modifying agent, chain propagation agent, fire retardant, softening agent and arbitrary combination thereof;
Wherein, described % by weight based on the gross weight of described toughening compositions;
The polytrimethylene terephthalate of described component (a) is Poly(Trimethylene Terephthalate) homopolymer, Poly(Trimethylene Terephthalate) multipolymer or Poly(Trimethylene Terephthalate) blend; And its limiting viscosity is 0.6dL/g-1.5dL/g;
The response type impact modifying agent of described component (b) comprises ethene/(methyl) methyl acrylate/maleic anhydride terpolymer, ethene/(methyl) ethyl propenoate/maleic anhydride terpolymer, ethene/(methyl) isobutyl acrylate/maleic anhydride terpolymer, ethene/(methyl) n-butyl acrylate/maleic anhydride terpolymer, ethene/(methyl) methyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) ethyl propenoate/glycidyl methacrylate terpolymer, ethene/(methyl) isobutyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) n-butyl acrylate/glycidyl methacrylate terpolymer, or its arbitrary combination,
The zinc ionomer of described component (c) comprises ethylene/methacrylic acid or ethylene/acrylic acid copolymer, its have zine ion as in and gegenion, and its neutralization ratio is about 0.4-about 0.9; And
Described toughening compositions does not comprise filler substantially, and described filler is selected from glass fibre, graphite fibre, Kevlar, glass flake, granulated glass sphere, clay, kaolin, sepiolite, talcum, wollastonite, mica, calcium carbonate, calcium sulfate, magnesium sulfate, silicon-dioxide whisker, potassium titanate and arbitrary combination thereof.
In other embodiments, described toughening compositions comprises following component, substantially composed of the following components or prepared by following component:
The polytrimethylene terephthalate of (a) 59-77 % by weight;
The response type impact modifying agent of (b) 21-33 % by weight;
The zinc ionomer of (c) 2-8 % by weight; With
The additive of (d) 0-10 % by weight; Described additive is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, flow ability modifying agent, chain propagation agent, fire retardant, softening agent and arbitrary combination thereof;
Wherein, described % by weight based on the gross weight of described toughening compositions;
The polytrimethylene terephthalate of described component (a) is Poly(Trimethylene Terephthalate) homopolymer; And its limiting viscosity is 0.8dL/g-1.3dL/g;
The response type impact modifying agent of described component (b) comprises ethene/(methyl) methyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) ethyl propenoate/glycidyl methacrylate terpolymer, ethene/(methyl) isobutyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) n-butyl acrylate/glycidyl methacrylate terpolymer or its arbitrary combination;
The zinc ionomer of described component (c) comprises ethylene/methacrylic acid or ethylene/acrylic acid copolymer, its have zine ion as in and gegenion, and neutralization ratio is about 0.4-about 0.9; And
Described toughening compositions does not comprise filler substantially, and described filler is selected from glass fibre, graphite fibre, Kevlar, glass flake, granulated glass sphere, clay, kaolin, sepiolite, talcum, wollastonite, mica, calcium carbonate, calcium sulfate, magnesium sulfate, silicon-dioxide whisker, potassium titanate and arbitrary combination thereof.
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. toughening compositions, it comprises:
The polytrimethylene terephthalate of (a) 55-80 % by weight;
The response type impact modifying agent of (b) 19.5-35 % by weight, described response type impact modifying agent is ethene/(methyl) alkyl acrylate copolymer comprising at least one reactive functional groups, and described reactive functional groups is selected from epoxy group(ing) and anhydride group;
The zinc ionomer of (c) 0.5-10 % by weight; With
The additive of (d) 0-10 % by weight; Described additive is selected from antioxidant, thermo-stabilizer, UV light stabilizing agent, the tinting material comprising dyestuff and pigment, lubricant, hydrolysis-resisting agent, releasing agent, flow ability modifying agent, chain propagation agent, fire retardant, softening agent and arbitrary combination thereof;
Wherein, described % by weight based on the gross weight of described toughening compositions.
2. the toughening compositions of claim 1, the polytrimethylene terephthalate of wherein said component (a) is Poly(Trimethylene Terephthalate) homopolymer, Poly(Trimethylene Terephthalate) multipolymer or Poly(Trimethylene Terephthalate) blend; And its limiting viscosity is 0.6dL/g-1.5dL/g.
3. the toughening compositions of claim 1, the response type impact modifying agent of wherein said component (b) comprises ethene/(methyl) methyl acrylate/maleic anhydride terpolymer, ethene/(methyl) ethyl propenoate/maleic anhydride terpolymer, ethene/(methyl) isobutyl acrylate/maleic anhydride terpolymer, ethene/(methyl) n-butyl acrylate/maleic anhydride terpolymer, ethene/(methyl) methyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) ethyl propenoate/glycidyl methacrylate terpolymer, ethene/(methyl) isobutyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) n-butyl acrylate/glycidyl methacrylate terpolymer, or its arbitrary combination.
4. the toughening compositions of claim 3, the response type impact modifying agent of wherein said component (b) comprises ethene/(methyl) methyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) ethyl propenoate/glycidyl methacrylate terpolymer, ethene/(methyl) isobutyl acrylate/glycidyl methacrylate terpolymer, ethene/(methyl) n-butyl acrylate/glycidyl methacrylate terpolymer or its arbitrary combination.
5. the toughening compositions of claim 1, the zinc ionomer of wherein said component (c) comprises ethylene/methacrylic acid or ethylene/acrylic acid copolymer, its have zine ion as in and gegenion, and its neutralization ratio is 0.4-0.9.
6. the toughening compositions of claim 1, wherein said toughening compositions does not comprise filler substantially, and described filler is selected from glass fibre, graphite fibre, Kevlar, glass flake, granulated glass sphere, clay, kaolin, sepiolite, talcum, wollastonite, mica, calcium carbonate, calcium sulfate, magnesium sulfate, silicon-dioxide whisker, potassium titanate and arbitrary combination thereof.
7. goods, it comprises toughening compositions any one of claim 1-6 or its toughening compositions any one of claim 1-6 obtains.
8. the goods of claim 7, it is the parts in outdoor activity equipment; Parts in transportation means; Or the shell of power tool, electric notor and household electrical appliance or wherein parts; Wherein said transportation means is automobile, train, aircraft or steamer.
9. the goods of claim 7 are used as the parts in outdoor activity equipment; Parts in transportation means; Or the purposes of the shell of power tool, electric notor and household electrical appliance or wherein parts; Wherein said transportation means is automobile, train, aircraft or steamer.
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