CN1898311A - Polyester compositions - Google Patents
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- CN1898311A CN1898311A CN 200480038408 CN200480038408A CN1898311A CN 1898311 A CN1898311 A CN 1898311A CN 200480038408 CN200480038408 CN 200480038408 CN 200480038408 A CN200480038408 A CN 200480038408A CN 1898311 A CN1898311 A CN 1898311A
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Abstract
Disclosed are polyester compositions having a glass transition temperature of less than about 10 DEG C comprising (A) at least one polyester comprising aromatic dicarboxylic acid residues and non-aromatic dicarboxylic acids; diols selected from the group consisting of aliphatic diols, polyalkylene ethers, and cycloaliphatic diols; and (B) a plasticizing effective amount of a compatible plasticizer.
Description
The field of the invention
The present invention relates to some novel polymeric compositions.More particularly, the present invention relates to comprise the novel polymeric compositions of some biodegradable polyester and softening agent.
The background of invention
Polymer materials can be used for replacing other material to be used for many final application.This type of material provides the various performances identical with substitute material, and also gives additional, valuable performance.Chemical resistant properties, flexibility and " sense of touch " are some in these unique quality.Yet polymer materials is not flexible in some cases, does not have required sense of touch yet, can't be used for the expectation purposes in them.The polymkeric substance experience is known as a kind of transformation of second-order transition temperature or Tg.This temperature be often registered as along with variation of temperature in thermal capacity, density, the mid point of curve when occurring discontinuity regional on the performances such as obstruct.Under this temperature, polymkeric substance will be because of in the increase that is higher than molecular motion under this temperature or be lower than the stopping of molecular motion under this temperature (so polymkeric substance become more apparent rigidity) and basic (radical) takes place on performance change.Only be higher or lower than this product under a lot of situations of room temperature at Tg a little and be considered to flexible.Usually, this Tg is lower than room temperature more, and it will become flexible more.Product for the polymkeric substance that needs higher flexibility and Geng Gao softness sense of touch, lower modulus can realize by reducing Tg by two kinds of methods: the adjusting of forming by polymkeric substance (as using polyethylene and ethylene copolymers) allows this polymkeric substance be designed to have than hanging down the additive that Tg or interpolation are known as softening agent, and can the latter reduce the Tg of polymer composition to be fit to required use temperature.When the Tg of polymkeric substance was in or be lower than Normal Environmental Temperature (30 ℃ to 60 ℃), typically thinking did not need further to reduce Tg.Yet the further reduction of Tg is desirable, and for example, when (1) enhancing, shock resistance and/or increment additive are brought up to modulus on the product requirement; (2) environment use temperature and condition are variable, resemble under the situation of round-the-clock boots or footwear; (3) this polymer materials can only use under the temperature far below the Normal Environmental Temperature condition; (4) reduce Tg, make product under the Normal Environmental Temperature condition, have bigger softness sense of touch.
Though having inherently, the polymkeric substance of low Tg can design and prepare, but resulting polymers does not have other key property in some cases, for example, the polymkeric substance that has inherently low Tg may demonstrate the surface viscosity of raising and cause bigger binding property for the surface.Therefore, will adhere to they itself, reach the combination degree that allows goods or film coalescence become an integral body by the goods of this material manufacturing.A kind of mode that overcomes this shortcoming is to increase to form the crystalline potentiality that have far above the melt temperature of environment use or storage or transport temperature from the teeth outwards, thereby at goods, staying on the surface of film or sheet material can the bonded cortex.Another mode that overcomes surface viscosity is to introduce " antiblocking " additive, mineral or high-tg polymer more, their this on polymer surfaces, occur, new surface mainly is provided on film or goods, have the adhesion characteristic of additive.These two kinds of methods all tend to improve modulus,, improve rigidity that is, have partly negated required softness sense of touch.
Reduce the situation of the Tg of polymer materials for adding softening agent, desirable effect be by in addition have the interpolation of the material of lower Tg and/or higher reactivity (general much lower molecular weight) to realize than polymkeric substance.Suitable or compatible softening agent is incited somebody to action:
(1) be increased in oilness between the polymer chain and the end of the chain by blocking Intermolecular Forces, therefore reduce any three-dimensional interactions (formation gel structure) and prevent they structural transformation and, the ability that raising slides over each other;
(2) spacing of increase between the interaction chain produces bigger free volume on effect, thereby allows chain and their end of the chain and side chain bigger rotary freedom to be arranged, crawling movement and vibration;
(3) increase free volume by the sum that increases the end group contribution for matrix;
(4) between chain, produce liquid and allow chain accept continuous solvation and the desolvation of softening agent chain and end group;
(5) form crystal by improving organized potentiality, thereby or reduce crystal and reduce modulus.For example referring to, people such as Sears, The Technology of Plasticizers, 2 and 3 chapters, Wiley-interscience Publications/John Wiley and Sons, Inc., (1982) and Encyclopedia of Polymer Science and Technology, 4 volumes, JaquelineKroschwitz, executive editor, Wiley-interscience Publications/John Wileyand Sons, Inc., (2003).
Though plasticization effect listed above the most usually mentions that in the literature single theory can't successfully be applied to whole interactions of various softening agent and various polymkeric substance.Along with the arrival of NMR, have been found that this interaction is complicated more.People such as Sears, TheTechnology of Plasticizers provides plasticising theoretical and its broad interpretation of mechanism.
For some application, for example, instrument loading and unloading, sole and sports goods, the softness perception of increase and bigger flexible scope are that to satisfy the industrial requirements of the final application of being advised needed.
General introduction of the present invention
We find that now softness of feeling and flexible scope with some polyester that is lower than about 10 ℃ Tg can be improved by introduce some compatible plasticizer compounds in this kind polyester.Therefore, the invention provides polymer composition comprises: polymer composition comprises:
(A) second-order transition temperature is lower than about 10 ℃ and copolyesters composed of the following components:
(1) diacid residues comprises about 1-65mol% aromatic dicarboxylic acid residue; Contain the aliphatic dicarboxylic acid residue of 4-14 the carbon atom of having an appointment with being selected from of the about 99mol% of 35-and contain non-aromatics dicarboxylic acid residue in cycloaliphatic dicarboxylic acid's residue of 5-15 the carbon atom of having an appointment; Wherein total mol% of diacid residues equals 100mol%; With
(2) diol residue, it is selected from one or more aliphatic diols that contain 2-8 the carbon atom of having an appointment, and contains the polyalkylene ether of 2-8 the carbon atom of having an appointment and contains the cycloaliphatic diol of 4-12 the carbon atom of having an appointment; Wherein total mol% of diol residue equals 100mol%; With
(B) one or more compatible plasticizers of plasticising significant quantity.
Polyester of the present invention has improved softness and bigger flexible scope surprisingly, if they have be lower than about 10 ℃ Tg and with some softening agent blending.
Detailed description of the present invention
The present invention relates to polymer composition, comprising:
(A) second-order transition temperature is lower than about 10 ℃ and copolyesters composed of the following components:
(1) diacid residues, it comprises about 1-65mol%, preferably about 25-65mol%, more preferably 35-65mol% and even the aromatic dicarboxylic acid residue of 40-60mol% more preferably from about; With the about 35mol% of 99-, preferably about 75-35mol% and even being selected from the aliphatic dicarboxylic acid residue that contains 4-14 the carbon atom of having an appointment and containing non-aromatics dicarboxylic acid residue in cycloaliphatic dicarboxylic acid's residue of 5-15 the carbon atom of having an appointment of 60-40mol% more preferably from about; Wherein total mol% of diacid residues equals 100mol%; With
(2) diol residue, it is selected from one or more aliphatic diols that contain 2-8 the carbon atom of having an appointment, and contains the polyalkylene ether of 2-8 the carbon atom of having an appointment and contains the cycloaliphatic diol of 4-12 the carbon atom of having an appointment; Wherein total mol% of diol residue equals 100mol%; With
(B) compatible plasticizer of plasticising significant quantity (reducing the Tg of polymkeric substance).
Surprisingly, the invention provides blend polymer, it demonstrates combining of improved softness and improved flexible scope.
The copolyesters that can be used among the present invention is the aliphatics-aromatic copolyesters (being called AAPE here) that constitutes component of the present invention (1), comprises being described in United States Patent (USP) 5,661,193,5,599,858,5,580, in 911 and 5,446,079 those, its disclosure is hereby incorporated by reference.
Copolyesters of the present invention comprises that second-order transition temperature is lower than those polymkeric substance of-10 ℃.In other embodiments of the present invention, flexible biological polymer will have and be lower than approximately-20 ℃ and more preferably less than-30 ℃ second-order transition temperature approximately.
Except as otherwise noted, otherwise the amount of the expression composition that in specification sheets and claim, uses, performance such as molecular weight, all numerical value of reaction conditions or the like are understood that to be modified by term " about " in all instances.Therefore, unless opposite indication is arranged, that the desired properties that the numerical parameter that provides in specification sheets below and the claims is according to the present invention manages to obtain changes is approximate.At least, each numerical parameter should be at least according to the numerical value of the significant figure of being reported with by adopting the ordinary technology of rounding up to explain.In addition, the scope that provides in disclosure thing and claim is wished to comprise particularly gamut and is not only end points.For example, say that becoming is that the scope of 0-10 wishes to be included in the whole numerical value between 0 and 10, for example 1,2,3,4, or the like, the whole marks between 0 and 10, for example 1.5,2.3,4.57,6.1113, or the like, and end points 0 and 10.Simultaneously, with chemical substituted radical, for example, " C
1-C
5Hydrocarbon " relevant scope wishes to comprise particularly and disclose C
1And C
5Hydrocarbon and C
2, C
3, and C
4Hydrocarbon.
Although it is proximate expressing the numerical range and the parameter of wide region of the present invention, the numerical value that provides is in a particular embodiment reported as far as possible exactly.Yet any numerical value contains some error that standard deviation produced of finding from their experimental measurements separately inherently.
Here the term of Shi Yonging " polyester " wishes to comprise " copolyesters " and be interpreted as that finger is by the prepared synthetic polymer of the polycondensation of one or more dual functional carboxylic acids and one or more dual functional oxy-compound.Typically this dual functional carboxylic acid is that dicarboxylic acid and this dual functional oxy-compound are dihydroxy alcohols, for example dibasic alcohol and glycol.Here the term of Shi Yonging " residue " refers to be incorporated into any organic structure in polymkeric substance or the softening agent by corresponding monomeric polycondensation.Here the term of Shi Yonging " repeating unit " refers to have dicarboxylic acid residue and the organic structure of the diol residue that connects via the ketonic oxygen base key.Therefore, dicarboxylic acid residue can be from dicarboxylic acid monomer or its relevant carboxylic acid halides, ester, and salt, acid anhydrides, or their mixture forms.Therefore the term dicarboxylic acid that here uses is wished to comprise in the polycondensation process that can be used for glycol and is made the dicarboxylic acids of high molecular weight polyesters and any derivative of dicarboxylic acid, comprising its relevant carboxylic acid halides, ester, half ester, salt, half salt, acid anhydrides, mixed anhydride, or their mixture.
Comprise that polyester in the present invention contains the sour residue (100mol%) and the diol residue (100mol%) of equal molar ratio example substantially, both react according to the ratio that equates basically, make the total mole number of repeating unit equal 100mol%.Therefore, the molecular fraction that provides in this article can be with the total mole number of sour residue, the total mole number of diol residue, or the total mole number of repeating unit is the basis.For example, the copolyesters that contains 30mol% hexanodioic acid (based on the total acid residue) is meant that copolyesters contains the 30mol% hexanodioic acid residue that belongs in the 100mol% acid residue altogether.Therefore, 30 moles hexanodioic acid residue is arranged in per 100 moles sour residue.In another embodiment, contain 30mol%1, the copolyesters of 6-hexylene glycol (based on the total diol residue) is meant that this copolyesters contains the 30mol%1 that belongs in the 100mol% diol residue altogether, 6-hexylene glycol residue.Therefore, in per 100 moles diol residue, have 30 moles 1,6-hexylene glycol residue.
Polyester of the present invention typically demonstrates the second-order transition temperature (being abbreviated as " Tg " here) that is lower than 10 ℃, and for example dsc (" DSC ") is measured according to well-known technology.The polyester that is used for the present invention preferably has and is lower than about 5 ℃ and more preferably less than about 0 ℃ second-order transition temperature.
Polyester composition of the present invention comprises the compatible plasticizer of AAPE and plasticising significant quantity.This AAPE can be the linearity that comprises diol residue, the copolyesters of random copolyesters or branching and/or chain extension, this diol residue contains and is selected from the aliphatic diol that contains about 8 carbon atoms of 2-, the residue of the glycol of that contain the polyalkylene ether glycols of 2-8 carbon atom and contain one or more replacements in the cycloaliphatic diol of about 12 carbon atoms of the 4-that has an appointment or unsubstituted, linearity or branching.The glycol of this replacement typically, contains about 4 substituting groups of 1-, and this substituting group is independently selected from halogen, C
6-C
10Aryl, and C
1-C
4Alkoxyl group.The example of operable glycol includes, but not limited to ethylene glycol, glycol ether, propylene glycol, 1, ammediol, 2,1,3 butylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, polyoxyethylene glycol, glycol ether, 2,2,4-trimethylammonium-1,6-hexylene glycol, thiodiethanol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2,4,4-tetramethyl--1,3-tetramethylene glycol, triglycol, and Tetraglycol 99.Aliphatic diol is preferred, but does not require.Preferred glycol comprises and is selected from 1, the 4-butyleneglycol; 1, ammediol; Ethylene glycol; 1, the 6-hexylene glycol; Glycol ether; With one or more glycol in the 1,4 cyclohexane dimethanol.1, the 4-butyleneglycol, ethylene glycol and 1,4 cyclohexane dimethanol are singly planted or are combined, and are even preferred, but do not require.
This AAPE also comprises diacid residues, it contains the residue of the non-aromatic dicarboxylic acid of one or more replacements of the about 99mol% of the 35-that has an appointment (based on the total mole number of sour residue) or unsubstituted, linearity or branching, and this dicarboxylic acid is selected from aliphatic dicarboxylic acid that contains about 12 carbon atoms of 2-and the cycloaliphatic dicarboxylic acid who contains about 10 carbon atoms of the 5-that has an appointment.The non-aromatic dicarboxylic acid of this replacement typically contains about 4 substituting groups of 1-, and this substituting group is selected from halogen, C
6-C
10Aryl, and C
1-C
4Alkoxyl group.The non-limitative example of aliphatics and cycloaliphatic dicarboxylic acid's acid comprises propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, nonane diacid, sebacic acid, fumaric acid, 2,2-dimethylated pentanedioic acid, suberic acid, 1,3-pentamethylene dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, 1, the 3-cyclohexane dicarboxylic acid, Glyoxylic acid hydrate, methylene-succinic acid, toxilic acid and 2,5-norbornane dicarboxylic acid.Unless outside the aromatic dicarboxylic acid, this AAPE also comprises one or more replacements that contain about 10 carbon atoms of 6-of the about 65mol% of about 1-(based on the total mole number of sour residue) or the residue of unsubstituted aromatic dicarboxylic acid.For the situation of using the aromatic dicarboxylic acid that replaces, they will typically contain about 4 substituting groups of 1-, and this substituting group is selected from halogen, C
6-C
10Aryl, and C
1-C
4Alkoxyl group.The non-limitative example that can be used for the aromatic dicarboxylic acid among the AAPE of the present invention is a terephthalic acid, m-phthalic acid, the salt of 5-sulfoisophthalic acid and 2,6-naphthalene dicarboxylic acids.In another embodiment, this AAPE comprises: diol residue, and this diol residue comprises the residue of one or more following alcohol: 1, the 4-butyleneglycol; 1, ammediol; Ethylene glycol; 1, the 6-hexylene glycol; Glycol ether; Or 1,4 cyclohexane dimethanol; And diacid residues, this diacid residues comprises the pentanedioic acid that is selected from of the about 95mol% of (i) about 35-(based on the total mole number of sour residue), Glyoxylic acid hydrate, succsinic acid, 1, the 4-cyclohexane dicarboxylic acid, and hexanodioic acid is (preferred, the residue of one or more the non-aromatic dicarboxylic acids pentanedioic acid and hexanodioic acid, single plant or both combine); The residue that is selected from one or more aromatic dicarboxylic acids in terephthalic acid and the m-phthalic acid of the about 65mol% of (ii) about 5-(based on the total mole number of sour residue).More preferably, this non-aromatic dicarboxylic acid will comprise hexanodioic acid, and this aromatic dicarboxylic acid will comprise that terephthalic acid and this glycol will comprise 1, the 4-butyleneglycol.
Other preferred compositions of AAPE of the present invention be from following two pure and mild dicarboxylic acid (or its copolyesters forms with equivalent such as diester) according to those of following mol% (based on the diacid component of 100mol% and the diol component of 100mol%) preparation:
(1) pentanedioic acid (about 30-about 75%); Terephthalic acid (about 25-about 70%); 1,4-butyleneglycol (about 90-100%); With modification glycol (0-about 10%);
(2) succsinic acid (about 30-about 95%); Terephthalic acid (about 5-about 70%); 1,4-butyleneglycol (about 90-100%); With modification glycol (0-about 10%); With
(3) hexanodioic acid (about 30-about 75%); Terephthalic acid (about 25-about 70%); 1,4-butyleneglycol (about 90-100%); With modification glycol (0-about 10%).
The modification glycol preferably is selected from 1,4 cyclohexane dimethanol, triglycol, polyoxyethylene glycol and neopentyl glycol.Most preferred AAPE is linear, the copolyesters of branching or chain extension, and it comprises the about 60mol% hexanodioic acid of about 50-residue, about 50mol% terephthalic acid residue of about 40-and 95mol%1 at least, 4-butyleneglycol residue.More preferably, this hexanodioic acid residue is the about 60mol% of about 55-, and the terephthalic acid residue is the about 45mol% of about 40-and 1, and 4-butyleneglycol residue is about 95-100mol%.This based composition can be with trade mark Eastar Bio copolyesters from EastmanChemical Company, Kingsport, and TN is purchased.
The additional specific examples of preferred AAPE comprises: poly-(tetramethylene glutarate-copolymerization-terephthalate), it contains (a) 50mol% pentanedioic acid residue, 50mol% terephthalic acid residue and 100mol%1,4-butyleneglycol residue, (b) 60mol% pentanedioic acid residue, 40mol% terephthalic acid residue and 100mol%1,4-butyleneglycol residue or (c) 40mol% pentanedioic acid residue, 60mol% terephthalic acid residue and 100mol%1,4-butyleneglycol residue; Poly-(tetramethylene succinate-copolymerization-terephthalate), it contains (a) 85mol% succsinic acid residue, 15mol% terephthalic acid residue and 100mol%1,4-butyleneglycol residue or (b) 70mol% succsinic acid residue, 30mol% terephthalic acid residue and 100mol%1,4-butyleneglycol residue; Poly-(ethylidene succinic acid ester-copolymerization-terephthalate), it contains 70mol% succsinic acid residue, 30mol% terephthalic acid residue and 100mol% glycol residue; With poly-(tetramethylene adipic acid ester-copolymerization-terephthalate), it contains (a) 85mol% hexanodioic acid residue, 15mol% terephthalic acid residue and 100mol%1,4-butyleneglycol residue or (b) 55mol% hexanodioic acid residue, 45mol% terephthalic acid residue and 100mol%1,4-butyleneglycol residue.
This AAPE preferably includes about 1,000 repeating unit of about 10-and preferred, about 600 repeating units of about 15-.This AAPE preferably also has the about 2.0dL/g of about 0.4-, the limiting viscosity of the about 1.4dL/g of 0.7-more preferably from about, according under 25 ℃ the temperature by using the concentration in phenol/tetrachloroethane (60/40 weight ratio) solution of 0.5 gram copolyesters at 100ml measured.
The optional residue that contains branching agent of this AAPE.The wt% scope of branching agent is the about 2 weight % of about 0-(wt% in the present invention refers to weight %), and about 1wt% of preferably about 0.1-and the about 0.5wt% of 0.1-most preferably from about are based on the gross weight of AAPE.This branching agent preferably has about 50 to about 5000, more preferably from about 92 to about 3000 weight-average molecular weight and about 3 to about 6 functionality.For example, branching agent can be the polyvalent alcohol with 3 to 6 hydroxyls, has the poly carboxylic acid (or its ester form use equivalent) of 3 or 4 carboxyls or has altogether the alcohol ester residue of 3 to 6 hydroxyls and carboxyl.
Can comprise glycerine, TriMethylolPropane(TMP), trimethylolethane, polyether triol as the representative low molecular weight polyols of branching agent, glycerine, 1,2,4-butane triol, tetramethylolmethane, 1,2,6-hexane triol, Sorbitol Powder, 1,1,4,4-four (methylol) hexanaphthene, three (2-hydroxyethyl) isocyanuric acid ester, and Dipentaerythritol.The more special branching agent example of high molecular weight polyols (MW 400-3000) is the triol that is obtained by the alkylene oxide with 2-3 carbon atom such as oxyethane and propylene oxide and polyol initiator condensation.Can comprise hemimellitic acid, trimellitic acid (1,2, the 4-benzene tricarbonic acid) and acid anhydrides as the representative poly carboxylic acid of branching agent, trimesic acid (1,3, the 5-benzene tricarbonic acid), pyromellitic acid and acid anhydrides, the benzene tertacarbonic acid, benzophenone tetracarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, 1,1,2-ethane tricarboxylic acid, 1,3,5-pentane tricarboxylic acid, with 1,2,3,4-pentamethylene tetracarboxylic acid.Though this acid can be used as it is, preferably they are to use with their lower alkyl esters or the form of their cyclic acid anhydride (in the time can forming cyclic acid anhydride).Representative alkyd as branching agent comprises oxysuccinic acid, citric acid, tartrate, 3-hydroxyl pentanedioic acid, tetrahydroxyadipic acid, trihydroxy glutaric acid, 4-carboxyl Tetra hydro Phthalic anhydride, hydroxyisophthalic acid, and 4-(beta-hydroxyethyl) phthalic acid.This type of alkyd contains the associating group of 3 or a plurality of hydroxyl and carboxyl.Especially preferred branching agent comprises trimellitic acid, trimesic acid, tetramethylolmethane, TriMethylolPropane(TMP) and 1,2,4-trihydroxybutane.
Aliphatics-aromatic polyester of the present invention comprises that also one or more contain the ionic monomer to improve their melt viscosity.Preferably, containing the ionic monomer is to be selected from the salt of sulfoisophthalic acid or its derivative.The monomeric representative instance of this type is the dimethyl ester of sodium sulfonate m-phthalic acid or sodium sulfonate m-phthalic acid.Contain the monomeric preferred concentration range of ionic and be the about 5.0mol% of about 0.3-and, more preferably, the about 2.0mol% of about 0.3-is based on the total mole number of sour residue.
The example of branching AAPE of the present invention is to contain 100mol%1,4-butyleneglycol residue, 43mol% terephthalic acid residue and 57mol% hexanodioic acid residue and poly-(tetramethylene adipic acid ester-copolymerization-terephthalate) the about 0.5wt% tetramethylolmethane branching of quilt.This AAPE can pass through dimethyl adipate, dimethyl terephthalate (DMT), and tetramethylolmethane and 1, the transesterification and the polycondensation of 4-butyleneglycol are produced.This AAPE can be by in a vacuum in the presence of the Ti that exists as titanium tetraisopropylate at first of 100ppm, monomer was heated 1 hour down at 190 ℃, heated 2 hours down at 200 ℃, heated 1 hour down at 210 ℃, what heating prepared in 1.5 hours under 250 ℃ then.
Another example of branching AAPE is to contain 100mol%1,4-butyleneglycol residue, 43mol% terephthalic acid residue and 57mol% hexanodioic acid residue and poly-(tetramethylene adipic acid ester-copolymerization-terephthalate) the about 0.3wt% pyromellitic acid dianhydride branching of quilt.This AAPE is by using forcing machine, being produced by the linearity poly-(tetramethylene adipic acid ester-copolymerization-terephthalate) and the reaction extrusion process of pyromellitic acid dianhydride.
Polyester composition of the present invention can also comprise from one or more chain propagation agents of the about 5wt% of 0-(based on the gross weight of composition).Exemplary chain propagation agent is a divinyl ether, as is disclosed in US patent No.5, and those in 817,721, or vulcabond for example are disclosed in US patent No.6, those in 303,677.Representative divinyl ether is 1,4-butyleneglycol divinyl ether, 1,5-hexylene glycol divinyl ether and 1,4 cyclohexane dimethanol divinyl ether.
Representative vulcabond is a toluene 2, the 4-vulcabond, toluene 2,6-vulcabond, 2,4 '-'-diphenylmethane diisocyanate, naphthalene-1,5-vulcabond, eylylene diisocyanate, hexamethylene diisocyanate, isoflurane chalcone diisocyanate and methylene-bis (2-isocyanato-hexanaphthene).Preferred vulcabond is a hexamethylene diisocyanate.Based on the overall weight percent of AAPE, weight percentage scope about 3.5wt% of preferably about 0.3-and the about 2.5wt% of 0.5-most preferably from about.Also might use functional group to be no less than 3 the trifunctional isocyanate compound that contains isocyanuric acid ester and/or hydrazo-dicarbonamide group in principle, or by three-or polyisocyanates partly substitute diisocyanate cpd.
AAPE of the present invention easily passes through to use typical polycondensation condition from suitable dicarboxylic acid, ester, acid anhydrides, or salt, suitable glycol or diol mixture and the preparation of any branching agent.They can be by by continuously, and semicontinuous and operator scheme is intermittently carried out, and can use various type of reactor.The example of suitable reactors type includes, but not limited to stirred pot, continuously stirring jar, slurry type, tubular type, scraped film type, falling film type, or extrusion reaction device.Here the term of Shi Yonging " continuously " refers to discontinuous manner not reactant be introduced and discharged simultaneously a kind of method of product.Basically or fully is successive for " continuously " this method in operation, different with " intermittently " method." continuously " in any case do not mean that and on the continuity of method, forbid normal interruption, for example owing to start, reactor servicing, or schedule shutdown period of arranging.Here the term of Shi Yonging " intermittently " method is meant that whole reactants is added into a kind of method that the reactor neutralization is handled according to the prior defined procedure of reaction then, does not join any raw material or move in the reactor in this process.Term " semi continuous (semicontinuous) " is meant a kind of method, wherein some in the reactant be the beginning of this process with regard to add and residual reactant along with the carrying out that reacts adds continuously.Additionally, semicontinuous method can comprise also and the similar method of discontinuous method that wherein whole reactants just adds in the beginning of this process, and just along with reaction is carried out, one or more product is discharged continuously.For economic reason with in order to obtain the dominant color effects of polymkeric substance, this method is advantageously operated as continuation method, can damage outward appearance because if stop this copolyesters of oversize time at elevated temperatures in reactor.
AAPE of the present invention is known and for example be described in US patent No.2 by the person skilled in the art, and the program in 012,267 prepares.This type of reaction normally under the temperature in 150 ℃ to 300 ℃ scopes at polycondensation catalyst alkoxy titanium compound for example, alkali metal hydroxide and alkoxide, the salt of organic carboxyl acid, Alkyzin compound carries out under the existence of metal oxide etc.This catalyzer uses with the amount based on the 10-1000ppm of the gross weight of reactant typically.
The reaction of two pure and mild dicarboxylic acid can be undertaken by using common copolyesters polymeric reaction condition.For example, when utilizing transesterification reaction (promptly from dicarboxylic acid component ester-formin) preparation copolyesters, this reaction method comprises two steps.In first step, diol component and dicarboxylic acid component, dimethyl terephthalate (DMT) for example, be at elevated temperatures, typically about 150 ℃ to about 250 ℃, reacted about 0.5 hour to about 8 hours down to the pressure in about 414kPa gauge pressure (60 pounds/square inch, " psig ") scope in about 0.0kPa gauge pressure.Preferably, the temperature of transesterification reaction scope is about 180 ℃ to about 230 ℃ and experiences about 1 to about 4 hours, and the preferred pressure scope is that about 103kPa gauge pressure (15psig) is to about 276kPa gauge pressure (40psig).Thereafter, reaction product is adding thermosetting AAPE and the glycol of cancellation simultaneously under the higher temperature and under the pressure that is reducing, and this glycol volatilizees easily under these conditions and removes from this system.This second step, or condensation polymerization step, be in higher vacuum with generally at about 230 ℃ to about 350 ℃, preferred about 250 ℃ to about 310 ℃ and, most preferably from about proceed about 0.1 hour to about 6 hours under the temperature between 260 ℃ to about 290 ℃, or preferred, about 0.2 hour to about 2 hours, till having obtained to have the polymkeric substance of the required polymerization degree (by characteristic viscosity determining).This condensation polymerization step can be carried out under the decompression of about 53kPa (400 torr) in about 0.013kPa (0.1 torr) scope.Stirring or appropriate condition are used for two stages to guarantee the Surface Renewal of enough heat passage and reaction mixtures.The speed of reaction in two stages can be quickened by appropriate catalyst, titanium tetrachloride for example, diacetic acid manganese, weisspiessglanz, diacetic acid dibutyl tin, zinc chloride, or their binding substances.Triphasic manufacturing course, and at US patent No.5, the program of describing in 290,631 is similar, also can use, especially when using the mix monomer raw material of sour and ester.For example, typical aliphatics-aromatic copolyesters, contain 30mol% terephthalic acid residue poly-(tetramethylene glutarate-copolymerization-terephthalate), can by in a vacuum in the presence of the Ti that exists at first of 100ppm as titanium tetraisopropylate at first with Methyl glutarate, dimethyl terephthalate (DMT), with 1, the 4-butyleneglycol was 200 ℃ of following heating 1 hour and descend heating to prepare in 0.9 hour at 245 ℃ then.
Be driven to fully in order to ensure the reaction that will utilize transesterification reaction between diol component and dicarboxylic acid component, sometimes wish to use about 1.05 to arrive about 2.5 moles diol component with respect to 1 moles of dicarboxylic acids component.Yet those of skill in the art will be appreciated that diol component and dicarboxylic acid component's ratio is determined by the DESIGN OF REACTOR of carrying out this reaction process.
When utilizing direct esterification (that is) preparation copolyesters, by allowing the mixture of dicarboxylic acid or dicarboxylic acid and the mixture and the branched monomer component reaction of diol component or diol component produce polyester from dicarboxylic acid component's sour form.Reaction is at the pressure of about 7kPa gauge pressure (1psig) between about 1379kPa gauge pressure (200psig), preferably is lower than under the 689kPa (100psig) and carries out, and produces the low molecular weight copolyesters product with mean polymerisation degree of about 1.4 to about 10.Employed temperature is about typically 180 ℃-Yue 280 ℃ in the direct esterification reaction process, more preferably from about 220 ℃-Yue 270 ℃.This low-molecular weight polymer comes polymerization by polycondensation then.
Here the term of Shi Yonging " plasticising significant quantity " means the effect that the softening agent of this consumption is enough to have softening polymkeric substance or reduces its Tg.The about 40wt% of the about typically 5-of the amount of the softening agent that uses in polyester composition is based on the overall weight percent of copolyesters.In one embodiment, the amount that is used for the softening agent of polyester composition is the about 20wt% of about 5-, based on the overall weight percent of copolyesters.
Here the term of Shi Yonging " compatible plasticizer " is meant that softening agent should can be miscible with AAPE.Be understood that to refer to that for the employed term of softening agent " compatible plasticizer " softening agent and AAPE mix the stable mixture of formation here, the latter can not be divided into a plurality of phases apace under processing conditions or working conditions, some of softening agent are oozed out and are difficult to avoid subsequently.This industry is described as this phenomenon " frosting (blooming) ", this refers to that softening agent oozes out at leisure as time passes from mixture (polymkeric substance+softening agent+additive), wherein the softening agent of great majority (mainly) is retained in this mixture under regular service condition He in duration of service.Therefore, wish to comprise simultaneously " solubility " mixture (wherein softening agent and AAPE form true solution) and " compatible " mixture for the employed term of softening agent " compatible plasticizer ", the mixture that means softening agent and AAPE needn't form true solution and only be stable blend.Generally, though not under the top and bottom, the solubility parameter value of solvent softening agent is 2 (cal/cc) at the numerical value that belongs to polymkeric substance itself
1/2Within.For the not measurable softening agent of solubility parameter, the temperature when forming clear solution by observing plasticized dose of dissolving of polymkeric substance is determined this solubleness.
This polyester composition also can comprise phosphonium flame retardant, though the existence of fire retardant is not crucial for the present invention.Phosphonium flame retardant should can be miscible with AAPE.Preferably, this P contained compound be non-halogenated organic compounds as, for example contain the phosphoric acid ester of organic substituent.This fire retardant can comprise various known in the prior art phosphorus compounds, phosphine for example, phosphorous acid ester, phosphinate, phosphinate, phosphinate, phosphonic acid ester, phosphine oxide, and phosphoric acid ester.The example of phosphonium flame retardant comprises tributyl phosphate, triethyl phosphate, tricresyl phosphate-butoxy ethyl ester, diphenylphosphoric acid tert-butyl-phenyl ester, diphenylphosphoric acid 2-(ethyl hexyl) ester, dimethyl phosphoric acid ethyl ester, diphenylphosphoric acid isodecyl ester, the tricresyl phosphate Lauryl Ester, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (xylyl) ester, diphenylphosphoric acid tert-butyl-phenyl ester, two (diphenylphosphoric acid) esters of Resorcinol, tricresyl phosphate benzyl ester, the phosphoric acid phenylethylester, thion tricresyl phosphate methyl ester, thion phosphoric acid phenylethylester, methyl-phosphorous acid dimethyl esters, the methyl-phosphorous acid diethyl ester, amyl group phosphonic acids diethyl ester, methyl-phosphorous acid dilauryl ester, methyl-phosphorous acid diphenyl, methyl-phosphorous acid dibenzyl ester, tolyl phosphonic acids diphenyl, tolyl phosphonic acids dimethyl esters, methyl thion phosphonic acids dimethyl esters, phenylbenzene phosphonous acid phenylester, phenylbenzene phosphonous acid benzyl ester, phenylbenzene phosphonous acid methyl ester, trimethyl-phosphine oxide compound, triphenylphosphine oxidation thing, the tribenzyl phosphine oxide, 4-methyldiphenyl base phosphine oxide, tricresyl phosphite ethyl ester, the tricresyl phosphite butyl ester, the tricresyl phosphite Lauryl Ester, tricresyl phosphite phenylester, tricresyl phosphite benzyl ester, phosphorous acid diethylamino phenyl base ester, phosphorous acid phenyl dimethyl esters, phosphorous acid benzyl dimethyl ester, methyl phosphonous acid dimethyl esters, amyl group phosphonous acid diethyl ester, methyl phosphonous acid diphenyl, methyl phosphonous acid dibenzyl ester, tolyl phosphonous acid dimethyl esters, dimethyl phosphonous acid methyl ester, diethyl phospho acid methyl ester, diphenyl phosphonic acid phenylester, diphenyl phosphonic acid methyl ester, the diphenyl phosphonic acid benzyl ester, triphenylphosphine, tribenzyl phosphine and methyldiphenyl base phosphine.
Fire retardant can be added in the polyester composition with the concentration based on the about 40wt% of about 5wt%-of the gross weight of polyester composition.
Oxidation stabilizer also can be included in the polyester composition of the present invention so that prevent oxidative degradation in the course of processing of fusing or semi-molten material.This type of stablizer comprises the ester class, as thio-2 acid distearyl ester or thiodipropionate dilauryl; Phenol stabilizer is as the IRGANOX 1010 that obtains from Ciba-Geigy AG, from the ETHANOX 330 and the butyric acid esterification hydroxytoluene of Ethyl Corporation acquisition; With the phosphorated stablizer as Irgafos that obtains from Ciba-Geigy AG and the WESTON stablizer that obtains from GE Specialty Chemicals.These stablizers can separately or be used in combination.
In addition, polyester composition can contain dyestuff, pigment, and processing aid, and as filler, matting agent, antiblocking agent, static inhibitor, whipping agent, chopped strand, glass, anti-impact modifier, carbon black, talcum, TiO
2And analogue, it is fixed to come as required.Tinting material is sometimes referred to as toning agent, can be added for copolyesters and goods to give needed neutralc tint and/or luminance brightness.The representative example of processing aid comprises lime carbonate, talcum, clay, TiO2, NH
4Cl, silica, calcium oxide, sodium sulfate, and calcium phosphate.Other example of processing aid level is about 25wt% of about 5-and the about 20wt% of about 10-in polyester composition of the present invention.Preferably, this processing aid also can be a biodegradation promotor, that is, this processing aid improves or the biodegradation rate of acceleration in environment.The contriver finds, also can be used for changing the processing aid of the pH of compost treatment environment, lime carbonate for example, and calcium hydroxide, calcium oxide, barium oxide, hydrated barta, water glass, calcium phosphate, magnesium oxide etc. also can quicken this biodegradation process.Polyester composition of the present invention can contain biodegradable additive to strengthen in environment their disassociation and biodegradability.The representative example that can be included in the biodegradable additive in the polyester composition of the present invention comprises Microcrystalline Cellulose, poly(lactic acid), poly butyric ester, poly-hydroxyl valerate, polyvinyl alcohol, thermoplastic starch or other carbohydrate, or their binding substances.Preferably, biodegradable additive is a thermoplastic starch.Thermoplastic starch is to produce the starch that gelatinization takes place the destructive crystalline structure by extrusion cooking." thermoplastic starch " that here uses wished to comprise and for example is described in Bastioli, C.DegradablePolymers, 1995, Chapman ﹠amp; Hall:London, " modified starch " in the 112-137 page or leaf and " pasted starch ".As for gelatinization, it refers to starch granules swelling and disintegrating fully, makes them form smooth viscosity dispersion in water.Gelatinization is undertaken by any known program, as heating in the presence of the water or the aqueous solution under about 60 ℃ temperature.Alkaline exists knownly can promote this process.This thermoplastic starch can be from from grain or root crop such as corn; wheat; rice; any unmodified starch of potato and tapioca (flour); amylose starch and amylopectin component from starch; prepare as the starch of partly depolymerization and deutero-starch with from starch graft copolymer from the treated starch product.Thermoplastic starch can be purchased from National StarchCompany.
For the term " biodegradable " of here using about AAPE "; polyester composition of the present invention is degraded under environmental influence in the defined suitable and evincible time span of D6340-98 being the ASTM Standard Method of " Standard Test Methods for DeterminingAerobic Biodegradation of Radiolabeled Plastic Materials in an Aqueousor Compost Environment " by title for example.AAPE, polyester composition of the present invention also can be " biological dissociable ", this means that according to DIN method 54900 these materials are bitty easily in the compost treatment environment.This AAPE, composition utilize heat at first, water, and air, microorganism and acting on of other factor are reduced molecular weight in the environment.This reduction of molecular weight can cause the loss of physicals (film toughness) and usually cause film rupture.In case the molecular weight of AAPE is enough low, this monomer and oligopolymer are digested by microorganism.In oxygenated environment, these monomers or oligopolymer finally are oxidized to CO
2, H
2O and new cellular biomass.In anaerobic environment, this monomer or oligopolymer finally are oxidized to CO
2, H
2, acetic ester, methane, and cellular biomass.Direct physics contact is set up in successful biological degradation requirement between biodegradable material and living microorganism colony or the enzyme by the generation of living microorganism colony.The film of the present invention that is used to degrade, the living microorganism colony of copolyesters and polyester composition generally can obtain from the equipment of any municipal or Industrial Wastewater Treatment or compost treatment equipment.In addition, successful biological degradation requires to satisfy some minimum physics and chemical requirement, as suitable pH, and temperature, oxygen concn, suitable nutrition, and moisture content.
The various components of polyester composition, fire retardant for example, release additives, other processing aid, and toning agent can be intermittently, and be semicontinuous, or blending in the successive processes.On a small scale batch of material can be before calendering or other thermal treatment preparation easily in the known any high strength mixing equipment of technician such as the Banbury mixer in the art.These components also can the solution in suitable solvent in blending.The melt blending method comprises copolyesters, and additive and any additional non-polymeric component are carried out blending being enough to melt at least in part under the temperature of this copolyesters.This blend can cool off with granulation for further use or the fusing blend can directly be processed into for example film, sheet or moulded product from this fusing blend.Here use term " fusing " include, but not limited to only soften this AAPE.For general known melting mixing method in polymer technology, referring to " Mixing and Compounding ofPolymers " (I.Manas-Zloczower ﹠amp; Z.Tadmor edits, and Carl (HanserVerlag Publisher, 1994, New York, N.Y.).When needs pigmented product (for example sheet, moulded product or film), pigment or tinting material can be included in the polyester composition in the reaction process of two pure and mild dicarboxylic acid or they and preformed copolyesters melt blending.The preferred method of introducing tinting material is to use the tinting material with the heat-staple organic coloring compound that contains reaction active groups, makes tinting material copolymerization and introducing in this copolyesters to improve its tone.For example, tinting material includes but not limited to that as having the dyestuff of reactive hydroxyl groups and/or carboxyl the blue and red anthraquinone that replaces can enter in the polymer chain in copolymerization.When dyestuff was used as tinting material, they can be added to this copolyesters reaction process after transesterify or direct esterification reaction.
Polymer composition of the present invention comprises the softening agent with polymkeric substance blending described here.The existence of softening agent can be used for strengthening the good mechanical properties of flexibility and gained film or sheet material or molded object.This softening agent also helps to reduce the processing temperature of polyester.Softening agent typically comprises one or more aromatic rings.Preferred plasticizer dissolves in the polyester, and this can show by under 160 ℃ or lower temperature the dissolving of 5-mil (0.127mm) thick film of polyester being obtained clear solution.More preferably, softening agent dissolves in the polyester, and this can show by under 150 ℃ or lower temperature the dissolving of 5-mil (0.127mm) thick film of polyester being obtained clear solution.The solubleness of softening agent in polyester can be measured as follows:
1. in little phial, put into 1/2 inch fragment of canonical reference film, 5 mils (0.127mm) thickness and approximate the width of phial greatly.
2. softening agent is added in the phial, till film is capped fully.
3. will there be the phial of film and softening agent to place on the top of the shelf, after l hour He once more, after 4 hours, observe.Note the outward appearance of film and liquid.
4. after under envrionment conditions, observing, the outward appearances of putting into phial in the well heater and allowing temperature under 75 ℃, keep constant 1 hour and to observe film and liquid then.
For each following temperature (℃) repeating step 4:100,140,150 and 160.
The example that can be used for to potentiality the softening agent among the present invention be following these.Although some in these softening agent are compatible with polymer blend of the present invention, can't estimate that they all are compatible:
Table A-softening agent
| The hexanodioic acid derivative |
| Octyl adipate |
| Two-(2-ethylhexyl adipic acid ester) |
| Hexanodioic acid two (n-heptyl, n-nonyl) ester |
| Diisobutyl adipate |
| Diisodecyl adipate |
| Dinonyl adipate |
| Hexanodioic acid two-(tridecyl) ester |
| Azelaic acid derivant |
| Two-(2-ethylhexyl azelate) |
| Nonane diacid diiso decyl ester |
| Nonane diacid diisooctyl ester |
| Dimethyl azelate |
| Di n hexyl azelate |
| Benzoic acid derivative |
| Dibenzoic diglycol laurate (DEGDB) |
| Dibenzoic acid dipropylene glycol ester |
| Dipropylene glycol dibenzoate |
| The Macrogol 200 dibenzoate |
| Neopentyl glycol dibenzoate |
| Citric acid derivant |
| Ethanoyl citric acid three-n-butyl |
| CitroflexA-2 |
| Citric acid three-n-butyl |
| Triethyl citrate |
| The dimeracid derivative |
| Two-(2-hydroxyethyl dimeric dibasic acid ester) (bis-(2-hydroxyethyl dimerate)) |
| Epoxy derivative |
| Epoxy linseed oil |
| Epoxidised soybean oil |
| Resins, epoxy acid 2-(ethyl hexyl) ester |
| Fumaric acid derivatives |
| Dibutyl fumarate |
| Glycerol derivative |
| Tribenzoin |
| Triacetin |
| Glycerine diacetic acid esters mono-laurate |
| The isobutyrate derivative |
| 2,2,4-trimethylammonium-1,3-pentanediol, diisobutyrate |
| The Texanol diisobutyrate |
| The m-phthalic acid derivative |
| Dimethyl isophthalate |
| The m-phthalic acid diphenyl |
| Phthalic acid di-n-butyl ester |
| The lauric acid derivative |
| Laurate methyl |
| Linoleic acid derivative |
| Methyl linoleate, 75% |
| Maleic acid derivatives |
| Toxilic acid two-(2-ethylhexyl) ester |
| N-butyl maleate |
| Trimellitate class (Mellitates) |
| Trioctyl trimellitate |
| Tri trimellitate isodecyl ester |
| Tri trimellitate-(n-octyl, positive decyl) ester |
| The different nonyl ester of tri trimellitate (Triisonyl trimellitate) |
| The tetradecanoic acid derivative |
| Isopropyl myristate |
| The oleic acid derivative |
| Butyl oleate |
| Glyceryl monooleate |
| Triolein |
| Witconol 2301 |
| N propyl oleate |
| Oleic acid tetrahydrochysene chaff quinone |
| The palmitinic acid derivative |
| Wickenol 111 |
| Uniphat A60 |
| Alkane derivative |
| The clorafin hydrocarbon, 41% chlorine |
| The clorafin hydrocarbon, 50% chlorine |
| The clorafin hydrocarbon, 60% chlorine |
| The clorafin hydrocarbon, 70% chlorine |
| Phosphoric acid derivatives |
| Diphenylphosphoric acid 2-(ethyl hexyl) ester |
| Diphenylphosphoric acid isodecyl ester |
| Diphenylphosphoric acid tert-butyl-phenyl ester |
| Resorcinol two (diphenyl phosphoester) (RDP) |
| 100％RDP |
| 75%RDP, the blend of 25%DEGDB (by weight) |
| 50%RDP, the blend of 50%DEGDB (by weight) |
| 25%RDP, the blend of 75%DEGDB (by weight) |
| Tricresyl phosphate-butoxy ethyl ester |
| Tributyl phosphate |
| Lindol |
| Triphenylphosphate |
| Phthalic acid derivatives |
| Butyl benzyl phthalate |
| Texanol benzyl phthalic ester |
| Phthalic acid butyl octyl ester |
| Dioctyl phthalate (DOP) |
| Dicyclohexyl phthalate |
| Two-(2-ethylhexyl) phthalic esters |
| Diethyl phthalate |
| Phthalic acid dihexyl ester |
| Diisobutyl phthalate |
| Di Iso Decyl Phthalate |
| Diisoheptyl phthalate |
| Diisononyl phthalate |
| Dimixo-octyl phthalate |
| Dimethyl phthalate |
| Ditridecyl phthalate |
| The two undecyl esters of phthalic acid |
| The ricinoleic acid derivative |
| The ricinoleic acid butyl ester |
| Three (ethanoyl) ricinoleic acid glyceryl ester |
| Ethanoyl ricinoleic acid methyl ester |
| The ricinoleic acid methyl ester |
| Ethanoyl ricinoleic acid n-butyl |
| The propylene glycol ricinoleate |
| Sebacic acid derivative |
| Uniflex DBS |
| Two-(2-ethylhexyl) sebates |
| Dimethyl sebacate |
| Stearic aeic derivative |
| Tego-stearate |
| Glyceryl monostearate |
| The Unimac 5680 isopropyl esters |
| Methyl stearate |
| The stearic acid n-butyl |
| Propylene glycolmonostearate |
| Succinic acid derivative |
| Ethyl succinate |
| Sulfonic acid |
| N-ethyl o, the p-toluol sulfonamide |
| O, the p-toluol sulfonamide |
Be described among the The Technology of Plasticizers by J.Kern Sears and Joseph R.Darby with above similar test, by Society of Plastic Engineers/Wiley and Sons, New York publishes, and 1982, the 136-137 page or leaf.In this test, with polymer particulates put into the heating microscope stage on the softening agent drop in.If polymkeric substance disappears, then its dissolving.This softening agent can also be classified according to their solubility parameter.The solubility parameter of softening agent or the square root of cohesive energy density(CED) can be by the methods of people such as Coleman description, and Polymer 31,1187 (1990) calculates.General understand, the solubility parameter of softening agent should be within 2.0 units of the solubility parameter of polyester, preferably is lower than 1.5 units and more preferably of the solubility parameter of polyester, is lower than 1.0 units of the solubility parameter of polyester.
The example of operable softening agent is the ester class according to the present invention, and it comprises: the sour residue that (i) comprises following one or more residues in these: phthalic acid, hexanodioic acid, trimellitic acid, phenylformic acid, nonane diacid, terephthalic acid, m-phthalic acid, butyric acid, pentanedioic acid, citric acid or phosphoric acid; (ii) comprise the aliphatics that contains about at the most 20 carbon atoms, the pure residue of one or more residues of cyclic aliphatic or aromatic alcohol.In addition, the non-limitative example of the pure residue of softening agent comprises methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, Stearyl alcohol, lauryl alcohol, phenol, benzylalcohol, quinhydrones, catechol, Resorcinol, ethylene glycol, neopentyl glycol, 1,4 cyclohexane dimethanol and glycol ether.This softening agent can also comprise one or more benzoic ethers, phthalic ester, phosphoric acid ester, or isophthalic ester.
In one embodiment; preferred plasticizer is selected from N-ethyl-o; the p-toluol sulfonamide; diphenylphosphoric acid 2-(ethyl hexyl) ester; diphenylphosphoric acid isodecyl ester; tributyl phosphate, diphenylphosphoric acid tert-butyl-phenyl ester, lindol; clorafin hydrocarbon (60% chlorine); clorafin hydrocarbon (50% chlorine), ethyl succinate, toxilic acid di-n-butyl ester; two-(2-ethylhexyl) maleic acid esters; the stearic acid n-butyl, CitroflexA-2, triethyl citrate; three-normal-butyl citrate; ethanoyl three-normal-butyl citrate, Witconol 2301, dibutyl fumarate; diisobutyl adipate; dimethyl azelate, epoxy linseed oil, glyceryl monooleate; the ethanoyl methyl ricinoleate; ethanoyl ricinoleic acid n-butyl, ricinoleic acid propylene glycol ester, Macrogol 200 dibenzoate; dibenzoic diglycol laurate; dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate; phthalic acid di-n-butyl ester; diisobutyl phthalate, butyl benzyl phthalate, and triacetin.
In second embodiment, preferred plasticizer is selected from N-ethyl-o, the p-toluol sulfonamide; diphenylphosphoric acid 2-(ethyl hexyl) ester, diphenylphosphoric acid isodecyl ester, tributyl phosphate; diphenylphosphoric acid tert-butyl-phenyl ester, lindol, clorafin hydrocarbon (60% chlorine); clorafin hydrocarbon (50% chlorine); ethyl succinate, n-butyl maleate, toxilic acid two-(2-ethylhexyl) ester; the stearic acid n-butyl; CitroflexA-2, triethyl citrate, citric acid three-n-butyl; dimethyl azelate; the Macrogol 200 dibenzoate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester; dimethyl phthalate; diethyl phthalate, phthalic acid di-n-butyl ester, diisobutyl phthalate; butyl benzyl phthalate, or triacetin.
In the 3rd embodiment, preferred plasticizer is to be selected from N-ethyl-o, p-toluol sulfonamide, diphenylphosphoric acid 2-(ethyl hexyl) ester, diphenylphosphoric acid isodecyl ester, diphenylphosphoric acid tert-butyl-phenyl ester, lindol, clorafin hydrocarbon (60% chlorine), clorafin hydrocarbon (50% chlorine), ethyl succinate, n-butyl maleate, stearic acid n-butyl, the Macrogol 200 dibenzoate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate, phthalic acid di-n-butyl ester, diisobutyl phthalate, or butyl benzyl phthalate.
In the 4th embodiment, preferred plasticizer is to be selected from N-ethyl-o, the p-toluol sulfonamide, 2-ethylhexyl diphenylphosphoric acid, isodecyl diphenylphosphoric acid, diphenylphosphoric acid tert-butyl-phenyl ester, Tritolyl Phosphate, clorafin hydrocarbon (60% chlorine), Macrogol 200 dibenzoate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate, phthalic acid di-n-butyl ester, or butyl benzyl phthalate.
In the 5th embodiment, preferred plasticizer is to be selected from N-ethyl-o, the p-toluol sulfonamide, diphenylphosphoric acid tert-butyl-phenyl ester, Tritolyl Phosphate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate, or butyl benzyl phthalate.
In the 6th embodiment, preferred plasticizer is to be selected from N-ethyl-o, p-toluol sulfonamide, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, or dimethyl phthalate.
In the 7th embodiment, dibenzoic diglycol laurate is a preferred plasticizer.
This novel polymeric compositions preferably contains phosphorus catalyst quencher component (C), typically one or more phosphorus compounds such as phosphoric acid, for example, phosphoric acid and/or phosphorous acid, or the ester of phosphoric acid such as phosphoric acid ester or phosphorous acid ester.Other example of phosphorus catalyst quencher is described in US patent 5,907,026 and 6,448, in 334.The amount of existing phosphorus catalyst quencher typically provides about 0-0.5wt%, and the element phosphor content of preferred 0.05-0.3wt% is based on (A) and gross weight (B).
This novel polymeric compositions preferably contains phosphorus catalyst quencher component (C), typically one or more phosphorus compounds such as phosphoric acid, for example, phosphoric acid and/or phosphorous acid, or the ester of phosphoric acid such as phosphoric acid ester or phosphorous acid ester.Other example of phosphorus catalyst quencher is described in US patent 5,907,026 and 6,448, in 334.The amount of existing phosphorus catalyst quencher typically provides about 0-0.5wt%, and the element phosphor content of preferred 0.05-0.3wt% is based on the gross weight of polyestercarbonate (A) and polyester (A) n.
This polymer blend also can use the known many methods of those skilled in the art (including but not limited to extrude injection moulding, extrusion molding and calendering) to be configured as film, moulded parts or sheet material.In extrusion, this polyester (typically presenting pellet form) is mixed together in rotating cylinder, and the hopper of putting into forcing machine then is used for melt compounded processing.Additionally, this pellet can add in the hopper of forcing machine by various material feeders, and this material feeder measures these pellets according to the desired weight ratio of pellet.After leaving this forcing machine, copolyester blends is configured as film or moulded parts uniformly now.In no case limit the shape of film or moulded parts.For example, film can be plain film shape film or periosteum.The film that is obtained can stretch, for example, and on certain direction 2 of the stretching original dimensions to 6 times.
The drawing process of film can be any in the method well known in the prior art, and as the roller drawing process, the slit crack stretches, tenter machine stretching method and tubular type stretching method.Utilize any in these methods, might carry out biaxial stretching in succession, biaxial stretching simultaneously, uniaxial extension, or these combination.Utilize above-mentioned biaxial stretching method, the stretching on vertical and horizontal can be carried out simultaneously.Equally, this stretching can be carried out at first in one direction, carries out on another direction then, causes effective biaxial stretching.
Polymer composition also demonstrates the increase of softness, the surface viscosity of anti-zoned property and reduction.
In some embodiments, disclose and made this based article, film, the method for sheet material and/or fiber comprises polymer composition of the present invention is carried out injection moulding, extrusion-blown modling, the step that film/sheet material is extruded or rolled.
The present invention illustrates in greater detail by specific embodiment given below.Should be appreciated that these embodiment are exemplary embodiments and are not limitation of the present invention, but within the scope of claims and content, broadly explain.
Embodiment
All cpds is estimated plasticizer activity by using copolyesters as component (1), and this copolyesters contains the 44mol% terephthalic acid, 1 of 56mol% hexanodioic acid and 100mol%, and the 4-butyleneglycol is known as EASTARTM
TMThe BIO copolyesters can obtain from EastmanChemical Company in the past, has about-35 ℃ Tg and～115 ℃ crystalline melting point.Preferred plasticizer can dissolved polyester film, obtain clear solution being lower than under about 160 ℃ temperature.This performance of softening agent is known as its solubleness.Whether the determination test compound is that 1.77 * 1.77cm (0.5 * 0.5 inch) square sample of the copolyester film of the program of the suitable plasticizers of component (1) copolyesters (1 mil) thickness that is to have 25 microns is put in the little phial.Add the test compound mulch film.After 1 hour and 4 hours, observe film down, find the considerable change of film in room temperature (RT).Then film is put in the test tube well heater and elevated temperature, after 1 hour and 4 hours, under following temperature, observed similarly: 40,50,60,70,80,90,100 and 110 ℃ with the room temperature sample.This temperature variation comprises from room temperature to the scope near the peak value crystalline melting point of copolyesters.The outward appearance of polymkeric substance and phial content at each temperature can be next with digit score according to following yardstick what be used to estimate in the end of each section period:
The 0=softening agent is a liquid, and film does not have obvious variation
The 1=film is clarifying (film is vaporific at first)
The 2=film is fully clear and bright
The 3=film is lost stiffness and no longer can be controlled oneself in phial
The 4=film has been lost structure; Polymkeric substance is an aggregation in the bottom of phial
5=film/polymkeric substance takes place to disperse and dissolving
6=liquid is muddy, is difficult for seeing polymkeric substance
7=liquid is transparent
In order to allow test compound be considered to component (2) softening agent, this test compound typically should have 4 value under 110 ℃ or lower temperature, and wherein the film of AAPE copolyesters changes into the amorphism aggregation of copolyesters.According to predicting that the order that this softening agent is used for the more active solvent characteristic of copolyesters can observe 6 by paying close attention to when observing 7 scoring subsequently to the grading of test compound, the minimum temperature when observing 5 scoring is more then carried out.Table 1 is as follows
Table 1
| Test temperature, ℃ | RT | 40 | 50 | 60 | 70 | 80 | 90 | 100 | 110 |
| Dioctyl adipate two-(2-ethylhexyl adipate ester) two (n-heptyls; N-nonyl) adipate ester adipic acid diisobutyl ester adipic acid diiso decyl ester adipic acid dinonyl ester two-(tridecyl) adipate esters two-(2-ethylhexyl azelate) azelaic acid diiso decyl ester azelaic acid diisooctyl ester azelaic acid dimethyl esters azelaic acid di-n-hexyl ester diethylene glycol dibenzoate dipropylene glycol dibenzoate Macrogol 200 dibenzoate acetyl group three normal-butyl citrate acetyl triethyl citrate three normal-butyl citrate triethyl citrate two-(2-ethoxy) dimeric dibasic acid ester epoxy linseed oil epoxidised soybean oil epoxy acid 2-ethylhexyl fumaric acid dibutyl ester glycerol triacetate 2; 2; 4-trimethyl-1; The 3-pentanediol, diisobutyrate | 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 0 0 0 0 2 2 1 0 0 0 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 0 0 0 0 2 5 2 1 0 0 0 0 0 1 0 0 0 0 | 0 0 0 0 0 0 0 0 0 0 0 0 6 7 2 1 0 0 0 0 0 1 0 0 0 0 | 0 0 0 0 0 0 0 0 0 0 6 0 7 7 2 1 0 0 0 0 0 1 0 0 0 0 | 0 0 0 0 0 0 0 0 0 0 6 0 7 7 2 1 0 0 5 0 0 1 0 0 3 0 | 0 0 0 0 0 0 0 0 0 0 6 0 7 7 7 1 3 3 6 0 0 1 3 3 6 1 | 0 0 0 3 0 0 0 0 0 0 6 0 7 7 7 3 6 6 6 0 0 1 3 4 6 3 | 0 0 0 4 0 0 0 0 0 0 6 0 7 7 7 4 6 6 6 3 4 3 3 4 6 3 |
Table 1 (continuing)
| Test temperature, ℃ | RT | 40 | 50 | 60 | 70 | 80 | 90 | 100 | 110 |
| Phthalic acid di-n-butyl ester methyl laurate methyl linoleate; 75% 2-(2-ethylhexyl) maleate maleic acid di-n-butyl ester trioctyl trimellitate tri trimellitate isodecyl ester, three-(n-octyl; Positive decyl) the different nonyl ester of trimellitate tri trimellitate isopropyl myristate butyl oleate glycerin mono-fatty acid ester glycerol trioleate methyl oleate n propyl oleate oleic acid tetrahydrochysene chaff quinone isopropyl palmitate chlorinated paraffin wax hydrocarbon; 41%Cl chlorinated paraffin wax hydrocarbon; 50%Cl chlorinated paraffin wax hydrocarbon, 60%Cl diphenylphosphoric acid 2-ethylhexyl diphenylphosphoric acid isodecyl ester diphenylphosphoric acid tert-butyl-phenyl ester tricresyl phosphate-butoxy ethyl ester tributyl phosphate lindol butyl benzyl phthalate phthalic acid butyl octyl ester | 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 | 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 1 0 1 0 0 1 0 0 | 1 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 6 1 0 1 0 0 2 1 0 | 1 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 6 1 0 1 0 0 2 1 1 | 1 0 0 0 0 0 0 1 0 1 0 0 0 0 0 0 0 0 1 6 1 1 2 0 0 2 5 1 | 3 0 1 1 3 0 0 1 1 1 0 0 1 1 0 0 0 2 6 6 5 2 7 1 1 7 7 1 | 7 0 1 1 6 0 1 1 1 1 0 0 1 1 1 1 1 2 6 7 7 7 7 3 3 7 7 2 | 7 3 3 1 7 0 1 1 1 3 0 0 1 1 1 1 1 2 7 7 7 7 7 3 6 7 7 3 | 7 3 3 6 7 0 2 1 1 3 0 4 1 5 3 3 1 2 7 7 7 7 7 3 6 7 7 3 |
Table 1 (continuing)
| Test temperature, ℃ | RT | 40 | 50 | 60 | 70 | 80 | 90 | 100 | 110 |
| Two undecyl ester ricinoleic acid butyl ester three (acetyl group) ricinoleic acid glyceride acetyl group ricinoleic acid methyl ester ricinoleic acid methyl ester acetyl group ricinoleic acid n-butyl ricinoleic acid propylene glycol ester decanedioic acid dibutyl ester decanedioic acid two-(2-ethylhexyl) the ester isostearic acid isopropyl esters stearic acid n-butyl butanedioic acid diethyl ester N-ethyl o of phthalic acid dioctyl ester phthalic acid two-(2-ethylhexyl) ester phthalic acid diethyl ester phthalic acid dihexyl ester o-benzene butyl phthalate ester phthalic acid diiso decyl ester phthalic acid two different heptyl ester phthalic acid diisononyl esters phthalic acid diisooctyl ester phthalic acid dimethyl esters phthalic acid double tridecyl ester phthalic acids, the p-toluenesulfonamide | 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 | 0 0 2 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 5 | 0 0 2 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 7 | 0 0 2 0 0 0 0 0 0 7 0 0 0 0 0 0 0 0 0 0 0 0 6 7 | 0 1 6 0 2 0 0 0 1 7 0 0 0 0 0 0 0 0 0 0 0 0 6 7 | 0 1 7 1 2 0 0 0 1 7 0 0 0 0 0 0 0 0 0 0 0 0 6 7 | 0 1 7 3 6 0 0 0 2 7 0 0 0 0 0 0 0 0 0 0 0 0 6 7 | 0 1 7 3 7 1 0 0 2 7 0 0 0 0 3 3 0 0 0 0 0 7 7 7 | 3 3 7 3 7 1 0 3 3 7 0 0 3 0 4 3 4 4 3 0 0 7 7 7 |
Can observe 6 subsequently for test compound by paying close attention to when observing 7 scoring as the grading of the efficient of softening agent, the minimum temperature when observing 5 scoring is more then carried out.Consider such as cost, the factor of health and safety and so on, selection preferentially also can change.Based on above-mentioned testing sequence; preferred plasticizer comprises N-ethyl-o; the p-toluol sulfonamide; diphenylphosphoric acid 2-(ethyl hexyl) ester; diphenylphosphoric acid isodecyl ester; the tricresyl phosphate butyl ester; diphenylphosphoric acid tert-butyl-phenyl ester; lindol, clorafin hydrocarbon 50% or 60%Cl, succsinic acid diethyl ester; toxilic acid di-n-butyl ester; toxilic acid two-(2-ethylhexyl) ester, stearic acid n-butyl, acetyl triethyl citrate; triethyl citrate; three normal-butyl citrates, ethanoyl three normal-butyl citrates, Witconol 2301; fumaric acid dibutyl ester; hexanodioic acid diisobutyl ester, nonane diacid dimethyl esters, epoxy linseed oil; glyceryl monooleate; ethanoyl ricinoleic acid methyl ester, ethanoyl ricinoleic acid n-butyl, propylene glycol ricinoleate; the Macrogol 200 dibenzoate; diethylene glycol dibenzoate, dipropylene glycol dibenzoate, phthalic acid dimethyl esters; the phthalic acid diethyl ester; phthalic acid di-n-butyl ester, o-benzene butyl phthalate ester, butyl benzyl phthalate and triacetin.In the middle of preferred plasticizer, the preferred N-ethyl-o that comprises, p-toluol sulfonamide, the diphenylphosphoric acid tertiary butyl-phenylester, Tritolyl Phosphate, clorafin hydrocarbon 60%Cl, the Macrogol 200 dibenzoate, phthalic acid di-n-butyl ester, and triacetin, wherein most preferred dipropylene glycol dibenzoate, dimethyl phthalate, the dibenzoic diglycol laurate of comprising, diethyl phthalate, butyl benzyl phthalate, ethyl succinate, and triethyl citrate.
By the above method evaluation and be found to be those plasticizer compounds that used AAPE has the significant quantity softening agent and all be shown in Table 2, wherein plasticizer compounds is compatible plasticizer and lists according to the descending of validity.Solubleness also can be used by Michael M.Coleman, John E.Graf and Paul C.Painter are at their books, the solubility parameter of describing among the SpecificInteractions and the Miscibility of of Polymer Blends predicts that solubility values belongs to the various softening agent in this test.Solubility values can belong to 10.17 the terephthalic acid by 45mol%, the 55mol% hexanodioic acid and the AAPE of the copolyesters formed of 100mol% butyleneglycol basically.In one embodiment, solubility values can belong at 8.17-12.17 (cal/cc)
1/2The solubility values scope in compatible plasticizer of the present invention.
With the contrast of the solubility values of each softening agent, by Coleman and other people evaluation suggestion: if solvent/softening agent is at 2 (cal/cc) for experimental data
1/2Add or deduct within the scope of the value that belongs to polymkeric substance, then this solvent/softening agent on certain level with polymer-compatible.In addition, the value of softening agent solubility values and AAPE copolyesters is approaching more, and is then compatible more.Yet solubility parameter is not absolute, because have many power to work when two molecules are met, especially compare this softening agent/solvent with the macromole of polymkeric substance be extremely little and say that simply also having some is not other material of the material of naming purely.For example, for dibenzoic acid dipropylene glycol ester, the material of industrial preparation comprises the dipropylene glycol mono benzoate of various levels, dipropylene glycol dibenzoate and its mono benzoate and the potentiality of a plurality of polypropylene glycol groups.In addition, use by the shortcoming of the works that people such as Coleman release is, some softening agent contain end group such as hydroxyl and metal ion and central element group such as phosphorus, sulphur and other potential central element, they are not easy to be represented by mathematical expression, because lack the data of contributing about various solubleness in their works.Therefore, need experimental data to come in the thinner potentiality that disclose plasticizing efficiency of measuring.
Table 2
| Test temperature (℃) | δ (cal/cc) 1/2 | 40 | 50 | 60 | 70 | 80 | 90 | 100 | 110 |
| N-ethyl o; P-toluenesulfonamide dipropylene glycol dibenzoate phthalic acid dimethyl esters diethylene glycol phthalate ester diphenylphosphoric acid tert-butyl-phenyl ester lindol phthalic acid diethyl ester butyl benzyl phthalate chlorinated paraffin wax hydrocarbon, 60%Cl diphenylphosphoric acid 2-ethylhexyl diphenylphosphoric acid isodecyl ester Macrogol 200 dibenzoate phthalic acid di-n-butyl ester | A B 10.4 10.3 A A 10 10.1 A A A 10.1 9.5 | 5 5 | 7 5 6 | 7 7 7 6 6 | 7 7 7 7 6 5 6 | 7 7 7 7 7 7 7 7 6 5 | 7 7 7 7 7 7 7 7 7 7 7 7 7 | 7 7 7 7 7 7 7 7 7 7 7 7 7 | 7 7 7 7 7 7 7 7 7 7 7 7 7 |
Table 2 (continuing)
| Test temperature (℃) | δ (cal/cc) 1/2 | 40 | 50 | 60 | 70 | 80 | 90 | 100 | 110 |
| Butanedioic acid diethyl ester chlorinated paraffin wax hydrocarbon, 50%Cl maleic acid di-n-butyl ester o-benzene butyl phthalate ester stearic acid n-butyl azelaic acid dimethyl esters citric acid triethyl group ester glycerol triacetate acetyl triethyl citrate citric acid three n-butyl tricresyl phosphate butyl ester maleic acids two-(2-ethylhexyl) ester oil acid methyl esters fumaric acid dibutyl ester adipic acid diisobutyl ester acetyl group three normal-butyl citrate epoxy linseed oil glycerin mono-fatty acid ester acetyl group methyl ricinoleate acetyl group ricinoleic acid n-butyl ricinoleic acid propylene glycol esters | 9.2 A 8.9 9.2 8.2 9 A A A A A 8.7 B 8.9 8.6 A B B 8.7 8.6 A | 6 | 6 6 | 6 6 6 5 | 6 6 6 6 6 6 6 | 7 7 7 7 7 6 6 6 6 6 6 4 | 7 7 7 7 7 6 6 6 6 6 6 6 5 4 4 4 4 4 4 4 4 |
A=contains people such as Coleman do not provide solubility constant in their works element (element).
B=contains the mixture of material retained owing to the efficient of the production of main plasticizer.
The present invention describes in detail with reference to preferred embodiment particularly, still, should be appreciated that, can carry out some changes and improvements within the spirit and scope of the present invention.
Claims (49)
1. polymer composition, it comprises:
(A) second-order transition temperature is lower than about 10 ℃ and copolyesters composed of the following components:
(1) diacid residues comprises about 1-65mol% aromatic dicarboxylic acid residue; Contain the aliphatic dicarboxylic acid residue of 4-14 the carbon atom of having an appointment with being selected from of the about 35mol% of 99-and contain non-aromatics dicarboxylic acid residue in cycloaliphatic dicarboxylic acid's residue of 5-15 the carbon atom of having an appointment; Wherein total mol% of diacid residues equals 100mol%; With
(2) diol residue, it is selected from one or more aliphatic diols that contain 2-8 the carbon atom of having an appointment, and contains the polyalkylene ether of 2-8 the carbon atom of having an appointment and contains the cycloaliphatic diol of 4-12 the carbon atom of having an appointment; Wherein total mol% of diol residue equals 100mol%; With
(B) one or more compatible plasticizers of plasticising significant quantity.
2. the polymer composition of claim 1 comprises being selected from sour residue, pure residue, benzoates, phthalate, one or more softening agent in phosphoric acid ester or the isophthalic ester class.
3. the polymer composition of claim 2, wherein said sour residue comprise and are selected from phthalic acid, hexanodioic acid, trimellitic acid, phenylformic acid, nonane diacid, terephthalic acid, m-phthalic acid, butyric acid, pentanedioic acid, one or more residues in citric acid or the phosphoric acid.
4. the polymer composition of claim 2 wherein should comprise the aliphatics that contains 1 to 20 carbon atom by the alcohol residue, cyclic aliphatic, or one or more residues in the aromatic alcohol.
5. the polymer composition of claim 4 wherein should the alcohol residue comprises being selected from methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, Stearyl alcohol, lauryl alcohol, phenol, benzylalcohol, quinhydrones, catechol, Resorcinol, ethylene glycol, dimethyltrimethylene glycol, one or more residues in 1,4 cyclohexane dimethanol or the glycol ether.
6. the polymer composition of claim 1; wherein said one or more softening agent are selected from N-ethyl-o; the p-toluol sulfonamide; diphenylphosphoric acid 2-(ethyl hexyl) ester; diphenylphosphoric acid isodecyl ester; tributyl phosphate, diphenylphosphoric acid tert-butyl-phenyl ester, lindol; clorafin hydrocarbon (60% chlorine); clorafin hydrocarbon (50% chlorine), ethyl succinate, toxilic acid di-n-butyl ester; toxilic acid two-(2-ethylhexyl) ester; the stearic acid n-butyl, CitroflexA-2, triethyl citrate; citric acid three-n-butyl; ethanoyl three-normal-butyl citrate, Witconol 2301, dibutyl fumarate; diisobutyl adipate; dimethyl azelate, epoxy linseed oil, glyceryl monooleate; the ethanoyl methyl ricinoleate; ethanoyl ricinoleic acid n-butyl, ricinoleic acid propylene glycol ester, Macrogol 200 dibenzoate; dibenzoic diglycol laurate; dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate; phthalic acid di-n-butyl ester; diisobutyl phthalate, butyl benzyl phthalate, or triacetin.
7. the polymer composition of claim 6, wherein said softening agent is selected from N-ethyl-o, the p-toluol sulfonamide; diphenylphosphoric acid 2-(ethyl hexyl) ester, diphenylphosphoric acid isodecyl ester, tributyl phosphate; diphenylphosphoric acid tert-butyl-phenyl ester, lindol, clorafin hydrocarbon (60% chlorine); clorafin hydrocarbon (50% chlorine); ethyl succinate, n-butyl maleate, toxilic acid two-(2-ethylhexyl) ester; the stearic acid n-butyl; CitroflexA-2, triethyl citrate, citric acid three-n-butyl; dimethyl azelate; the Macrogol 200 dibenzoate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester; dimethyl phthalate; diethyl phthalate, phthalic acid di-n-butyl ester, diisobutyl phthalate; butyl benzyl phthalate, or triacetin.
8. the polymer composition of claim 7, wherein said one or more softening agent are selected from N-ethyl-o, p-toluol sulfonamide, diphenylphosphoric acid 2-(ethyl hexyl) ester, diphenylphosphoric acid isodecyl ester, diphenylphosphoric acid tert-butyl-phenyl ester, lindol, clorafin hydrocarbon (60% chlorine), clorafin hydrocarbon (50% chlorine), ethyl succinate, n-butyl maleate, stearic acid n-butyl, the Macrogol 200 dibenzoate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate, phthalic acid di-n-butyl ester, diisobutyl phthalate, or butyl benzyl phthalate.
9. the polymer composition of claim 8, wherein said one or more softening agent are to be selected from N-ethyl-o, the p-toluol sulfonamide, diphenylphosphoric acid 2-(ethyl hexyl) ester, diphenylphosphoric acid isodecyl ester, diphenylphosphoric acid tert-butyl-phenyl ester, Tritolyl Phosphate, clorafin hydrocarbon (60% chlorine), Macrogol 200 dibenzoate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate, phthalic acid di-n-butyl ester, or butyl benzyl phthalate.
10. the polymer composition of claim 9, wherein said one or more softening agent are to be selected from N-ethyl-o, the p-toluol sulfonamide, diphenylphosphoric acid tert-butyl-phenyl ester, Tritolyl Phosphate, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, dimethyl phthalate, diethyl phthalate, or butyl benzyl phthalate.
11. the polymer composition of claim 10, wherein said one or more softening agent are to be selected from N-ethyl-o, p-toluol sulfonamide, dibenzoic diglycol laurate, dibenzoic acid dipropylene glycol ester, or dimethyl phthalate.
12. the polymer composition of claim 11, wherein this softening agent comprises dibenzoic diglycol laurate.
13. according to the polymer composition of claim 1, wherein polyester (A) comprises and is selected from terephthalic acid, m-phthalic acid, or the diacid residues in their mixture.
14. according to the polymer composition of claim 1, wherein polyester (A) comprises the terephthalic acid residue of about 25-65mol%.
15. according to the polymer composition of claim 14, wherein polyester (A) comprises the terephthalic acid residue of about 35-65mol%.
16. according to the polymer composition of claim 15, wherein polyester (A) comprises the terephthalic acid residue of about 40-60mol%.
17. according to the polymer composition of claim 1, wherein non-aromatics dicarboxylic acid residue select oneself diacid, pentanedioic acid or their mixture.
18. according to the polymer composition of claim 17, wherein polyester (A) comprises the diacid of selecting oneself of about 75-35mol%, pentanedioic acid, or the non-aromatic dicarboxylic acid in their mixture.
19. according to the polymer composition of claim 18, wherein polyester (A) comprises the diacid of selecting oneself of about 65-35mol%, pentanedioic acid, or the non-aromatic dicarboxylic acid in their mixture.
20. according to the polymer composition of claim 19, wherein this polyester (A) comprises the diacid of selecting oneself of about 40-60mol%, pentanedioic acid, or the non-aromatic dicarboxylic acid in the binding substances of its two or more diol residue.
21. according to the polymer composition of claim 1, wherein the diol residue of polyester (A) is to be selected from ethylene glycol, glycol ether, propylene glycol, 1, ammediol, 2,2-dimethyl-1, ammediol, 1,3 butylene glycol, 1, the 4-butyleneglycol, 1,5-pentanediol, 1, the 6-hexylene glycol, polyoxyethylene glycol, glycol ether, 2,2,4-trimethylammonium-1,6-hexylene glycol, thiodiethanol, 1, the 3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol, 2,2,4,4-tetramethyl--1,3-tetramethylene glycol, the binding substances of triglycol and Tetraglycol 99 or these two or more diol residue.
22. according to the polymer composition of claim 1, wherein the diol residue of polyester (A) mainly is made up of the aliphatic diol residue.
23. according to the polymer composition of claim 22, wherein polyester (A) comprises and is selected from 1,4-butyleneglycol, 1, ammediol, ethylene glycol, 1,6-hexylene glycol, glycol ether, the glycol in the binding substances of 1,4 cyclohexane dimethanol or these two or more diol residue.
24. according to the polymer composition of claim 22, wherein polyester (A) comprises and is selected from 1,4-butyleneglycol, ethylene glycol, the glycol in the binding substances of 1,4 cyclohexane dimethanol or these two or more diol residue.
25. according to the polymer composition of claim 24, wherein the diol residue of polyester (A) comprises 1, the 4-butyleneglycol.
26. according to the polymer composition of claim 25, wherein polyester (A) comprises diol residue, this diol residue further comprises 1 of about 80-100mol%, the 4-butyleneglycol; Wherein total mol% of diol residue equals 100mol%.
27. according to the polymer composition of claim 1, wherein the diacid of polyester (A) and diol residue mainly are made up of following:
(1) comprises the terephthalic acid residue of about 25-65mol% and the aromatic dicarboxylic acid residue of the non-aromatics dicarboxylic acid residue of the about 35mol% of 75-; With
(2) diol residue of forming by aliphatic diol.
28. according to the polymer composition of claim 27, wherein the diacid of polyester (A) and diol residue mainly are made up of following:
(1) aromatic dicarboxylic acid residue, it comprises the hexanodioic acid residue of terephthalic acid residue and the about 35mol% of 75-of about 25-65mol%, pentanedioic acid residue, or the binding substances of hexanodioic acid residue and pentanedioic acid residue; With
(2) by 1, the diol residue that the 4-butyleneglycol is formed.
29. according to the polymer composition of claim 28, wherein the diacid of polyester (A) and diol residue mainly are made up of following:
(1) aromatic dicarboxylic acid residue, it comprises the hexanodioic acid residue of terephthalic acid residue and the about 35mol% of 65-of about 35-65mol%, pentanedioic acid residue, or the binding substances of hexanodioic acid residue and pentanedioic acid residue; With
(2) by 1, the diol residue that the 4-butyleneglycol is formed.
30. according to the polymer composition of claim 29, wherein the diacid of polyester (A) and diol residue mainly are made up of following:
(1) aromatic dicarboxylic acid residue, it comprises the hexanodioic acid residue of terephthalic acid residue and the about 40mol% of 60-of about 40-60mol%, pentanedioic acid residue, or the binding substances of hexanodioic acid residue and pentanedioic acid residue; With
(2) by 1, the diol residue that the 4-butyleneglycol is formed.
31. polymer composition according to claim 1, wherein polyester (A) has the limiting viscosity (I.V.) of about 0.4-2.0dL/g, descends to measure at 25 ℃ by the solvent of being made up of 60wt% phenol and 40wt% tetrachloroethane that uses 0.50 gram polymkeric substance/every l00ml.
32. polymer composition according to claim 1, wherein the overall weight percent of this softening agent is that the weight percentage of about 5-40 weight percentage and polyester (A) is about 95-60 weight percentage, and wherein the overall weight percent of this softening agent and polyester (A) equals 100 weight percentage.
33. polymer composition according to claim 32, wherein the overall weight percent of this softening agent is that the weight percentage of about 5-20 weight percentage and polyester (A) is about 80-95 weight percentage, and wherein the overall weight percent of this softening agent and polyester (A) equals 100 weight percentage.
34. polymer composition according to claim 33, wherein this polyester (A) comprises component (C), this component (C) further comprises one or more phosphorus catalyst quenchers, and it can provide the element phosphor concentration of about 0-0.5 weight percentage, based on component (A) and weight (B).
35. the polymer composition of claim 1, wherein polyester (A) comprises one or more branching agents, accounts for about 10.0 weight percentage of about 0.01-of the gross weight of polyester (A).
36. the polymer composition of claim 35, it contains one or more branching agents, accounts for about 5 weight percentage of about 0.05-of the gross weight of polyester (A).
37. the polymer composition of claim 36, wherein this branching agent comprises having 3 or 3 above carboxyl substituents, hydroxyl substituent, or monomeric one or more residues of their bonded.
38. the polymer composition of claim 37, wherein this branching agent comprises one or more residues of following material: trimellitic acid 1,2-anhydride, 1,2,4,5-pyromellitic acid dianhydride, glycerine, Sorbitol Powder, 1,2,6-hexane triol, tetramethylolmethane, trimethylolethane, or 1,3, the 5-benzenetricarboxylic acid.
39. the polymer composition of claim 1, it comprises the fire retardant of the about 40wt% of about 5-, based on the gross weight of described polymer composition.
40. the polymer composition of claim 39, it comprises one or more fire retardants that are selected from the inferior phosphorio compound.
41. the polymer composition of claim 40, it comprises one or more monoesters of phosphoric acid, diester, or three esters.
42. make the method for film or sheet material or moulded parts, comprise the polymer composition of claim 1 is extruded or calendering or step of injection molding.
43. comprise film or sheet material or moulded parts according to the polymer composition of claim 1.
44. according to film or the sheet material or the moulded parts of claim 42, wherein this film or sheet material are by extruding or rolling process production.
45. comprise moulded parts according to the polymer composition of claim 1.
46. the polymer composition of claim 1, wherein the solubleness of this softening agent adds or deducts 2 (cal/cc) in the solubility values of polyester itself
1/2Within the scope.
47. the polymer composition of claim 46, wherein the solubleness of this softening agent is to add or deduct 1.5 (cal/cc) in the solubility values of polyester itself
1/2Scope within.
48. the polymer composition of claim 47, wherein the solubleness of this softening agent is to add or deduct 1 (cal/cc) in the solubility values of polyester itself
1/2Scope within.
49. the polymer composition of claim 1, wherein polyester (A) is the terephthalic acid residue who comprises 45mol%, the hexanodioic acid of 55mol% is also basically by 100mol%1, and the copolyesters that the 4-butyleneglycol is formed and the solubleness of wherein said softening agent are at 8.17-12.17 (cal/cc)
1/2The solubility values scope within.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US53165803P | 2003-12-22 | 2003-12-22 | |
| US60/531,658 | 2003-12-22 | ||
| US10/998,910 | 2004-11-29 |
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| CN1898311A true CN1898311A (en) | 2007-01-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200480038408 Pending CN1898311A (en) | 2003-12-22 | 2004-12-17 | Polyester compositions |
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| CN (1) | CN1898311A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731758A (en) * | 2012-03-13 | 2012-10-17 | 蓝海永乐（江苏）新材料有限公司 | Foamable flame-retarding polyester capable of being used for supercritical CO2 and preparation method and application thereof |
| CN109071926A (en) * | 2016-04-25 | 2018-12-21 | 花王株式会社 | Polyester resin forming composition for damping material |
-
2004
- 2004-12-17 CN CN 200480038408 patent/CN1898311A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731758A (en) * | 2012-03-13 | 2012-10-17 | 蓝海永乐（江苏）新材料有限公司 | Foamable flame-retarding polyester capable of being used for supercritical CO2 and preparation method and application thereof |
| CN109071926A (en) * | 2016-04-25 | 2018-12-21 | 花王株式会社 | Polyester resin forming composition for damping material |
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