CN102477153B - Copolyester composition with thermal stability - Google Patents
Copolyester composition with thermal stability Download PDFInfo
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- CN102477153B CN102477153B CN201010571375.5A CN201010571375A CN102477153B CN 102477153 B CN102477153 B CN 102477153B CN 201010571375 A CN201010571375 A CN 201010571375A CN 102477153 B CN102477153 B CN 102477153B
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Abstract
The invention relates to a copolyester composition with thermal stability. The composition comprises aliphatic-aromatic copolyester, a high-molecular chain elongation agent containing epoxy functional group, and a cocatalyst. The cocatalyst is composed of manganese carboxylate and zinc carboxylate with a weight ratio of 1:3-3:1. If the weight of the aliphatic-aromatic copolyester is considered as 100 parts, the dosage of the cocatalyst is 0.03-0.2 parts. The copolyester composition comprises good thermal stability. After a plurality times of high-temperature post-processing, the degree of thermal cracking is relatively low, and good mechanical properties are maintained.
Description
Technical field
The present invention relates to a kind of copolyesters constituent, particularly relate to a kind of copolyesters constituent with heat-resistant quality.
Background technology
Straight chain type polyester in the past, as polyethylene terephthalate (polyethylene terephthalate, abbreviation PET), polybutylene terephthalate (polybutylene terephthalate, be called for short PBT), because thering is good machinery, optics and chemically-resistant character, be widely used in various vacuum or press in empty moulded plastic products.But this kind polyester is because structure is that straight chain type and molecular weight are not high, make that melt strength is not enough and unfavorable processing particularly can't directly be applied in blown film processing or foaming processing procedure.For addressing the above problem, prior art is by adding multiple functional radical coupler (or being called the chain extension agent) mostly, and the molecular weight of straight chain type polyester and side chain are increased, and namely makes the straight chain type polyester change the branched chain type polyester into, to promote melt strength, and be beneficial to the following process application.
US 6,506,852 disclose a kind of by by after a mixture heating and melting again granulation manufacture the method for high molecular weight polyesters grain; This mixture comprises linear saturated polyester, coupler (as the compound containing bis-epoxy base or many epoxy group(ing)) and catalyst, and this catalyst is carboxylate salt, in embodiment, is to use separately respectively aluminium sodium salt or manganese acetate.Separately in US 6,841, in 106, be to use above-mentioned mixture to make foamed, the catalyst used in embodiment is respectively calcium stearate, manganese acetate or the calcium stearate/lithium stearate of independent use.Above-mentioned two patents are by promote melt strength and swelling property (degree of swelling) with coupler, and catalyst is only for accelerated reaction.
The method of above-mentioned various lifting melt strength also can't overcome in polyester high temperature process process the thermo-cracking problem that easily produces, thereby need to add in addition thermal stabilizer fully, just can allow polyester have better heat-resistant quality.Yet, after this case contriver test, find, when independent use zinc salt, as catalyst, last the obtained thermo-cracking situation of polyester after repeatedly processing is serious, more causes the physical property of follow-up goods to descend.If use separately sodium salt or manganese salt as catalyst, can be because catalysis speed can't complete reaction too slowly in short twin-screw mixer processing procedure of residence time, cause the melt strength deficiency of the branched chain type copolyesters of gained after reaction.
From the above, how to allow the reaction times shorten, and suppress the branched chain type copolyesters through the thermo-cracking phenomenon that repeatedly machining produces, take into account again the physical property (as blown film character etc.) of follow-up goods, for current industry, still have great demand.
Summary of the invention
The thermo-cracking phenomenon occurred in the multiple high temp course of processing in order to solve existing branched chain type copolyesters, take into account the speed of response of copolyesters and chain extension agent simultaneously, this case contriver is after in many ways testing, obtain the common catalyst that uses particular types and grasp its blending ratio and addition, can make the copolyesters made there is good heat-resistant quality, after multiple high temp processing, be difficult for cracking and still maintain good mechanical properties.
The object of the present invention is to provide a kind of copolyesters constituent with heat-resistant quality, it is difficult for producing the thermo-cracking phenomenon, melt strength is high and, after repeatedly processing, still can maintain good mechanical properties.
The present invention has the copolyesters constituent of heat-resistant quality, comprises: the macromolecular chain that an aliphatic-aromatic copolyester, contains epoxide functional groups extends agent and has catalyst altogether.Catalyst is comprised of manganese carboxylate salt and salts of carboxylic acids altogether, and the part by weight scope of manganese carboxylate salt and salts of carboxylic acids is 1: 3～3: 1, and the weight of this aliphatic-aromatic copolyester of take is 100 listed as parts by weight, and the amount ranges of this common catalyst is 0.03～0.2 weight part.
After this case contriver many experiments, learn, the catalysis that salts of carboxylic acids is reacted with the chain extension agent for copolyesters is fastest, but it not only can't suppress the thermo-cracking phenomenon that copolyesters produces after multiple high temp processing, also has on the contrary the effect of accelerating.The predicament of this conventional art, the technology obtained through the institute of joining hands by the present invention, when can effectively being overcome.
Beneficial effect of the present invention is: by using the specific catalyst altogether be comprised of manganese carboxylate salt and salts of carboxylic acids, and control consumption and the usage ratio of catalyst simultaneously, except making this aliphatic-aromatic copolyester and this chain extension agent be able to rapid reaction, and make to have outside high molten intensity via prepared copolyesters after melting blending reaction, still can make this aliphatic-aromatic copolyester in follow-up multiple high temp processing, effectively reduce the thermo-cracking phenomenon, make this aliphatic-aromatic copolyester there is good heat-resistant quality, and maintain good mechanical properties, to be suitable for being applied in blown film processing.
Embodiment
The present invention has the copolyesters constituent of heat-resistant quality, comprises macromolecular chain that an aliphatic-aromatic copolyester, contains epoxide functional groups and extends agent and catalyst altogether.Catalyst is comprised of manganese carboxylate salt and salts of carboxylic acids altogether, the part by weight scope of manganese carboxylate salt and salts of carboxylic acids is 1: 3～3: 1, and the weight of this aliphatic-aromatic copolyester of take is 100 listed as parts by weight, and the amount ranges of this common catalyst is 0.03～0.2 weight part.Being preferably 0.04～0.15 weight part, is more preferably 0.05～0.1 weight part.When the consumption of common catalyst during lower than 0.03 weight part, can't effectively accelerate reacting of this aliphatic-aromatic copolyester and chain extension agent, cause common catalyst can't bring into play the function of original accelerated reaction speed that should possess, and also can allow obtained copolyesters there is the problem of melt strength deficiency; On the contrary, when the consumption of common catalyst, during higher than 0.2 weight part, this aliphatic-aromatic copolyester may easily produce the gel phenomenon with reacting of chain extension agent because speed of reaction is too fast, and then causes the puzzlement on following process.
Preferably, the part by weight scope of manganese carboxylate salt and salts of carboxylic acids is 1: 2～2: 1.
In the manganese carboxylate described in the present invention or zinc carboxylate, refer to the carboxylate salt that contains mn ion or zine ion.The carboxylate salt can be applicable in the present invention can be, such as but not limited to, aliphatic acid salt (salt of aliphatic carboxylic acid), aromatic series hydrochlorate (salt of aromatic carboxylic acid), multi-carboxylate (salt of polycarboxylic acid) or described combination.Preferably, this carboxylate salt is to be C
1～C
18aliphatic acid salt.More preferably, this manganese carboxylate salt is to be selected from manganese acetate (manganese acetate), manganese stearate (manganese stearate) or its combination.More preferably, this salts of carboxylic acids is to be selected from zinc acetate (zinc acetate), Zinic stearas (zinc stearate) or its combination.
This aliphatic-aromatic copolyester can adopt current commercial goods or be made by known way, for example by aliphatic diacid, with aromatic diol or aromatic acid, with aliphatic diol, reacts obtained; In addition, also optional use has the copolyesters of Biodegradable.Preferably, this aliphatic-aromatic copolyester is for a unit (I) and a unit (II) carries out the polymkeric substance that copolymerization obtains, and the molar ratio scope of this unit (I) and this unit (II) is 0.1: 99.9～99.9: 0.1,
In formula (I) and (II), X
1and X
3mean respectively C
2to C
20straight chain or branched chain alkylidene group; X
2mean C
3to C
40straight chain or branched chain alkylidene group; And Ar means C
6to C
20arylidene.
Preferably, the weight average molecular weight scope of this aliphatic-aromatic copolyester is 30,000～50,000, and fusing point is between 50 ℃～200 ℃.
Preferably, this aliphatic-aromatic copolyester is to be selected from butyleneglycol adipic acid ester-terephthalic acid ester copolyesters (butylene glycol adipate-terephthalate copolymer, commercial goods is as the commodity of Far East New Era Company
the commodity of BASF AG
the commodity of IREChemicals company
8000 or the commodity of Eastman Chemicals company
deng), (butylene glycol succinate-terephthalate copolymer, commercial goods is as the commodity of E.I.Du Pont Company for butyleneglycol succinate-terephthalic acid ester copolyesters
deng), tetramethyl-adipic acid ester-terephthalic acid ester copolyesters (tetramethyladipate-terephthalate copolymer) or these combination.In concrete example of the present invention, this aliphatic-aromatic copolyester is butyleneglycol adipic acid ester-terephthalic acid ester copolyesters.
The weight of this aliphatic-aromatic copolyester of take is 100 listed as parts by weight, and the amount ranges of this chain extension agent is 0.3～2.0 weight part, is preferably 0.4～1.5 weight part, is more preferably 0.5～1.0 weight part.When the addition of this chain extension agent, during lower than 0.3 weight part, the copolyesters obtained easily can't carry out blown film processing (blown film) because melt strength is not enough.On the contrary, when the addition of this chain extension agent, during higher than 2.0 weight part, easily occur excessively crosslinked in reaction process and then produce gel (gel), causing filter net jam and make processing be difficult for.
This chain extension agent is mainly the chain extension agent that contains epoxide functional groups.Preferably, this chain extension agent is that the acrylate monomer and the auxiliary monomer that have epoxide functional groups by least one carry out polymerization and make, and this auxiliary monomer is to be selected from acrylic ester monomer, styrenic monomers, or this both combination.In the preparation process of this chain extension agent, this polyreaction is preferably and begins to carry out under the agent existence together, this initiator can be any applicable reagent, for example Diisopropyl azodicarboxylate [2,2 '-azobis (2-methylpropionitrile), AIBN], benzoyl peroxide (benzyl peroxide, BPO).
This acrylic ester monomer with epoxide functional groups can be, such as but not limited to, glycidyl methacrylate (glycidyl methacrylate, GMA) or glycidyl acrylate (glycidyl acrylate).
In this auxiliary monomer, this acrylic ester monomer can be, such as but not limited to, methyl methacrylate (methyl methacrylate, MMA), β-dimethyl-aminoethylmethacrylate (ethyl methacrylate, EMA), n-BMA (n-butyl methacrylate, n-BMA), Tert-butyl Methacrylate (tert-butyl methacrylate, t-BMA), isobornyl methacrylate (isobornyl methacrylate, IBMA), trifluoroethyl methacrylate (trifluoroethyl methacrylate), methyl acrylate (methyl acrylate, MA), butyl acrylate (butyl acrylate, BA), lauryl acrylate (lauryl acrylate, LA), octadecyl acrylate (stearyl acrylate, SA), methacrylic acid benzene methyl (benzyl methacrylate, BzMA), methacrylic acid-2-ethyl phenoxy (2-phenoxy ethyl methacrylate) or vinylformic acid-2-ethyl phenoxy (phenoxy ethyl acrylate).
This styrenic monomers can be, such as but not limited to, vinylbenzene (styrene, ST), arteries and veins-vinyl toluene, p-methylstyrene, three-butylstyrene or Vinyl toluene.
Preferably, in the chain extension agent, this amount ranges with acrylate monomer of epoxide functional groups is 30～50wt%, and the amount ranges of this auxiliary monomer is 70～50wt%.
Preferably, the weight average molecular weight of this chain extension agent is 5,000～20,000, and epoxy equivalent (weight) is between between 200～500g/eq.
In copolyesters constituent of the present invention, need depending on processing procedure or range of application, can add in addition the reagent such as appropriate tinting material, static inhibitor, fireproofing agent, whipping agent, anti-UV tranquilizer, antiskid agent, fluidizer, inorganic filler, antioxidant and/or lubricant.Preferably, the weight of this aliphatic-aromatic copolyester of take is 100 listed as parts by weight, and the interpolation weight range of this reagent is 0～30 weight part.
Copolyesters constituent of the present invention can adopt traditional method, via single screw rod or twin-screw extruder, carries out being squeezed into pencil after melting blending reaction, then forms granular upgrading copolyesterester grain by the tablets press cutting.
The prepared copolyesters constituent of the present invention can use various processing modes to make the goods of various forms according to subsequent applications, for example blown film processing or foaming processing.
The present invention will be described further with regard to following examples, but will be appreciated that, this embodiment is only for illustrating use, and should not be interpreted as restriction of the invention process.
[chemical] following examples will be used following chemical:
1. aliphatic-aromatic copolyester: (Far East New Era Company is manufactured, trade(brand)name to use butyleneglycol adipic acid ester-terephthalic acid ester copolyesters
120 ℃ of fusing points, glass tansition temperature-33 ℃).
This aliphatic-aromatic copolyester need be under 80 ℃ before experiment dry 8 hours, moisture content need≤200ppm.
2. contain the chain extension agent of epoxide functional groups: by glycidyl methacrylate, vinylbenzene and methyl methacrylate, under hot initiator Diisopropyl azodicarboxylate and toluene existence, reacted, detailed preparation process is as described below.
3. catalyst: embodiment is used respectively manganese acetate (purchased from Showa company, call MnAc in the following text) with zinc acetate (purchased from Aldrich company, call ZnAc in the following text) combination, manganese stearate (purchased from MP Biomedicals company, call Mn St in the following text) and the combination of the combination of zinc acetate or manganese acetate and Zinic stearas (purchased from high patina work company, calling ZnSt in the following text).Comparative example is used sodium stearate (purchased from Acros company, call NaSt in the following text), sodium-acetate is (purchased from Showa company, call NaAc in the following text), ionic polymer sodium salt is (purchased from Honeywell company, call Na-ionomer in the following text), zinc oxide (purchased from island for a long time the chemistry, call ZnO in the following text).
4. other additive: inorganic talcum powder (purchased from Taiwan Jia get Li company, model P2000).
<preparation example > the preparation macromolecular chain that contains epoxide functional groups extends agent
Adopt Raolical polymerizable, using respectively toluene and Diisopropyl azodicarboxylate as solvent and initiator, using vinylbenzene, methyl methacrylate and the glycidyl methacrylate monomer as polymerization.
The synthetic three kinds of macromolecular chains that contain epoxide functional groups of the present invention extend agent A, B and C, and the ratio of monomer and initiator is listed in table one in detail.At first after monomer being mixed according to the tabular ratio, add Diisopropyl azodicarboxylate, after being stirred to dissolving fully, splash in the glass reaction groove of five liters that contains toluene with base runoff.Temperature of reaction is controlled at 85 ± 5 ℃, and question response, after two hours, with except desolventizing, obtains the macromolecular chain that the contains epoxide functional groups prolongation agent of a white powder shape by the product vacuum drying.
According to ASTM D 1652 standard methods, respectively above-mentioned prepared chain extension agent A, B and C are measured to epoxy equivalent (weight), and with gel permeation chromatography instrument (GPC) sense weight molecular-weight average, number average molecular weight and vergence (PDI), finally re-use elementary errors scanning calorimeter analyser (DSC) and detect the glass tansition temperature, result arranges in table one.
Table one
A. consumption be take the monomer gross weight as 100 listed as parts by weight.
<embodiment 1～4 >
By the butyleneglycol adipic acid ester with Biodegradable matter of 100 weight parts-terephthalic acid ester copolyesters (Far East New Era Company, trade(brand)name
), the macromolecular chain that obtains of the above-mentioned preparation example of the 0.65 weight part common catalyst that extends agent A and 0.065 weight part (selects catalyst kind and regulation and control part by weight according to following table two, directly two kinds of catalyst being mixed to institute obtains) after even the mixing, utilize HAAKE to mould spectrometer and be controlled under 200 ℃, rotating speed 50rpm condition, melting blending 20 minutes, to obtain respectively the copolyesters constituent of embodiment 1～4.In melting blending process, utilize and mould spectrometer in every torque value (unit is Newton meter, below is denoted as " Nm ") of measuring described copolyesters constituent in 0.5 minute, acquired results is as following table two.When torque value is higher, mean that the melt strength of copolyesters constituent is stronger.That is to say, between aliphatic-aromatic copolyester and macromolecular chain prolongation agent, level of response is higher.
<comparative example 1～7 >
The preparation of catalyst comparative example 1～4 and test process are identical with embodiment 1～4, and difference is in not using catalyst or using single catalyst (selecting please according to following table two of catalyst), and test result arranges equally in following table two.
The preparation of catalyst comparative example 5～7 and test process are identical with embodiment 1～4, and difference is in the common catalyst that uses the different sorts collocation or the common catalyst (selecting please according to following table two of catalyst) of Different Weight ratio, and test result arranges equally in following table two.
Table two
As shown in Table 2, comparative example 1 is under the situation of not adding catalyst, torque value is lower than 1Nm, show that copolyesters and the macromolecular chain with epoxide functional groups extend the agent sluggish, and maximum torque value is too low, the melt strength deficiency, hence one can see that is necessary to add a catalyst and shortens its reaction times in this reaction.Comparative example 2～4 adds single catalyst, can within the short period of time, arrive maximum torque value though add ZnSt in comparative example 4, but along with the time increases, torque value is more and more lower, confirm as background technology Duan Suoti, after long-time processing, not only ZnSt the heat-resistant quality at high temperature of copolyesters constituent can't be provided, can accelerate on the contrary the thermo-cracking speed of copolyesters constituent.From comparative example 5 results, the common catalyst catalytic effect that contains MnSt and NaSt is not good, and the time that reaches maximum torque value is 9.5 minutes, and the maximum torque value is lower slightly.Though the maximum torque value of comparative example 5 can reach 1.6Nm, its needed time is oversize, is unfavorable for procedure for processing.If embodiment 3 is compared with comparative example 7, need equally within 5 minutes, reach maximum torque value, but the maximum torque value of comparative example 7 is far below embodiment 3.If embodiment 4 is compared with comparative example 6, though both all can reach the torque value of 1.3Nm, required time of embodiment 4 is far below the time of comparative example 6.Result by embodiment 1～4 can be learnt, the scope of torque maximum value is 1.30～2.30Nm, reaching torque maximum value required time is 2.7～5.0 minutes, and increase in time, more than torque value still can maintain 1Nm, proof the present invention uses manganese carboxylate salt and salts of carboxylic acids as common catalyst, not only can accelerated reaction, and the copolyesters of gained is along with the reaction times increases, still maintain good torque value, the common catalyst ratio of the MnAc used with embodiment 1 again: ZnAc (1: 1) has the most excellent character.
<embodiment 5～7 and comparative example 8 >
The preparation process of embodiment 5～7 and comparative example 8 and condition are identical with embodiment 1, difference be in: change chain extension agent and the consumption of catalyst altogether according to following table three, finally obtain respectively the copolyesters constituent of embodiment 5～7 and comparative example 8.
According to the test process of embodiment 1, utilize respectively and mould spectrometer to embodiment 5～7 and comparative example 8 measurement torque values equally, observe the gel state simultaneously, experimental result is converged whole in table three.
Table three
By known in table three, in comparative example 8, altogether lower than 0.3 weight part, maximum torque value is too low, shows that chain extension poor effect and viscosity promote not obvious lower than 0.03 weight part and chain extension agent consumption for the catalyst consumption; In comparative example 9, altogether the catalyst consumption higher than 2.0 weight parts, has the gel phenomenon to produce higher than 0.2 weight part and chain extension agent consumption, causes the difficulty in processing.Based on the following process application demand, when common catalyst consumption is controlled at 0.065 weight part and chain extension agent consumption and is controlled at 0.65 weight part, the most applicable procedure for processing that is applied to twin-screw extruder of the character of its copolyesters.
<embodiment 8 > preparation of copolyesters grain
Carry out melting blending granulation with twin-screw extruder: the main feed chute that the copolyesterester grain of 100 weight parts is positioned over to twin screw extruder machine; be dry mixed the chain extension agent A of uniform 0.65 weight part and the common catalyst of 0.065 weight part and be placed in secondary feed chute; charging in varing proportions; be squeezed into pencil after the melting blending; and be cut into particle with tablets press, make the copolyesterester grain.Imposing a condition as screw rod long-width ratio L/D=36 of twin-screw extruder, screw speed 50rpm, the temperature distribution of screw rod is 140 ℃, 160 ℃, 180 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃, 200 ℃ of die head (die) temperature, 205 ℃ of material melt temperatures.
<embodiment 9 > preparation of film bag
twin shaft processing for the first time
Utilize equally twin-screw extruder, 100kg butyleneglycol adipic acid ester-terephthalic acid ester copolyesters is placed in to main feeding cylinder groove, and, by after 0.65kg chain extension agent A and abundant stirring of the common catalyst (manganese acetate that is 3: 1 by part by weight and zinc acetate mixing gained) of 0.065kg, pour in secondary head tank groove.Then separately be fed in twin-screw extruder, granulation after making butyleneglycol adipic acid ester-terephthalic acid ester copolyesters and chain extension agent and being total to catalyst melting blending, carry out twin shaft processing for the first time.The main head tank groove input speed of twin-screw extruder is 40kg/hr, and secondary head tank groove input speed is 0.286kg/hr.Prepared branched chain type copolyesters is dried to weighing and obtain 95kg, productive rate is 95%.Recycling solution solvent viscosity ratio analyser is measured solution solvent viscosity ratio (Relatively Viscosity is called for short RV), and utilizes the acid value analyser to measure acid value, and test result is converged whole in table four.Solution solvent viscosity ratio is higher represents that molecular weight is larger; The acid value value is proportional to the quantity of the carboxyl of copolyesters, represents that when acid value is higher the degree of this copolyesters high temperature chain rupture (thermo-cracking) is larger, and heat-resistant quality is not good.
twin shaft processing for the second time
The 95kg branched chain type copolyesters of above-mentioned gained is placed in to the main head tank groove of twin-screw extruder, the 5kg talcum powder is placed in secondary head tank groove, carries out the processing for the second time of branched chain type copolyesters, finally obtains a blending thing.The main head tank groove input speed of twin-screw extruder is 40kg/hr, and secondary head tank groove input speed is 2kg/hr, and increases the 120mesh filter screen in order to impurity screening in the die head place of twin-screw extruder.Then the blending thing obtained after processing is for the second time dried, and weighing obtains 95kg, and productive rate is 95%, with regard to solution solvent viscosity ratio (RV) and acid value, is measured equally, and test result is converged whole in table four.
single shaft processing (blown film processing) for the third time
The blending thing 50kg of above-mentioned gained is placed in to the head tank groove of single screw rod inflation film manufacturing machine, is fed into single screw rod inflation film manufacturing machine.Utilize single screw rod inflation film manufacturing machine to be expressed to ring-like die head place after the complete melting of material, and appropriate blow stretch under blowfilm shaping, obtain the film bag of thickness 20～25 μ m.The input speed of single screw rod inflation film manufacturing machine is 40kg/hr, screw rod long-width ratio L/D=32, and screw speed 25rpm, the temperature distribution of screw rod is 160 ℃, 170,170 ℃, die head temperature 170, the material melt temperature is 150 ℃.With regard to solution solvent viscosity ratio and acid value, tested equally, test result is converged whole in table four, in addition, utilizes the Instron tensiometer to measure the mechanical properties of film bag, and test result is converged whole in table five.
<embodiment 10～11 >
The preparation process of embodiment 10～11, preparation condition and test process are identical with embodiment 9, and it is to change according to following table four that difference is in the part by weight of selected common catalyst kind and catalyst.Similarly, through for the first time, after twin shaft processing for the second time and single shaft processing for the third time, the solution solvent viscosity ratio of gained and acid value test result are converged wholely in table four, and in addition, the mechanical properties test result of film bag is converged whole in table five.
<comparative example 10～12 >
The preparation process of comparative example 10～12, preparation condition and test process are identical with embodiment 9, and difference is in not using and be total to catalyst or use single catalyst.Similarly, through for the first time, after twin shaft processing for the second time and single shaft processing for the third time, the solution solvent viscosity ratio of gained and acid value test result are converged wholely in table four, and in addition, the mechanical properties test result of film bag is converged whole in table five.
Table four
Table five
B. " NA " means because can't recording by blown film.
In table four, utilize solution solvent viscosity ratio (RV) and acid value to observe the heat-resistant quality of copolyesters, can cause molecular weight and molecular weight when the copolyesters chain rupture, and the terminal carboxyl(group) quantity of copolyesters can increase, so the situation of utilizing the RV observed molecular weight to descend, when the lower molecular weight of RV less.The situation of more utilizing in addition the mensuration of acid value to observe its chain rupture, when acid value promotes, represent that the terminal carboxyl(group) quantity of copolyesters is more, namely the chain rupture situation of copolyesters is more serious, therefore, when RV descend or (with) acid value is while uprising, and represents that the heat-resistant quality of its copolyesters is not good.
From the result of table four and table five, comparative example 10, because do not add catalyst, causes solution solvent viscosity ratio lower (lower than 1.80) and acid value higher, and, along with the increase of processing number of times, the numerical value of acid value is more and more higher, shows that heat-resistant quality is relatively not good.Comparative example 11 is used single catalyst, although can obtain good solution solvent viscosity ratio, along with the increase of processing number of times, the numerical value of acid value more and more higher (by 40.2, being increased to 63.1), after being presented at multiple high temp processing, it is not good that the heat-resistant quality meeting becomes.It is that 4: 1 catalytic effects are not good that comparative example 12 is used MnAc and ZnAc to be total to the catalyst ratio, causes solution solvent viscosity ratio lower (only having 2.00).Review embodiment 9～11, in three processing, all can obtain good solution solvent viscosity ratio and lower acid value (all lower than 60.8), prove that copolyesters constituent of the present invention has good heat-resistant quality really, and, after multiple high temp processing, be difficult for producing the thermo-cracking phenomenon.
Result by comparative example 10 can find, when not adding catalyst, the copolyesters constituent is because of the not enough blowfilm shaping smoothly of melt strength; The result of the result of embodiment 9～11 and comparative example 11～12 is compared, can find that comparative example 11 is because being used single catalyst, cause the mechanical properties of film bag all lower than embodiment 9～11, comparative example 12 is 4: 1 because MnAc/ZnAc is total to the catalyst ratio, catalytic effect is not good, cause solution solvent viscosity ratio lower, the mechanical properties of film bag is also all lower than embodiment 9～11.Physical property proves that the prepared film bag of copolyesters of the present invention, after multiple high temp processing, still has good mechanical properties, except can match in excellence or beauty general with plastics PE, even than PE physical properties excellent.
In sum, the present invention has the copolyesters constituent of heat-resistant quality by adding the common catalyst that contains manganese carboxylate salt and salts of carboxylic acids and suitably controlling consumption and the part by weight of catalyst altogether, the macromolecular chain that not only allows aliphatic-aromatic copolyester contain epoxide functional groups with this fast extends agent and reacts, make prepared copolyesters can not produce the thermo-cracking phenomenon simultaneously after the processing of follow-up multiple high temp, and follow-uply can make a kind of goods (as the film bag) with good mechanical properties.
Be as described above, for preferred embodiment of the present invention, when not limiting scope of the invention process with this, the simple equivalence of namely doing according to the present patent application the scope of the claims and invention description content changes and modifies, and all still remains within the scope of the patent.
Claims (13)
1. the copolyesters constituent with heat-resistant quality is characterized in that: this copolyesters constituent comprises the macromolecular chain that an aliphatic-aromatic copolyester, contains epoxide functional groups and extends agent, and catalyst altogether; Catalyst is comprised of manganese carboxylate salt and salts of carboxylic acids altogether, the part by weight scope of manganese carboxylate salt and salts of carboxylic acids is 1: 3～3: 1, and the weight of this aliphatic-aromatic copolyester of take is 100 listed as parts by weight, and the amount ranges of this common catalyst is 0.03～0.2 weight part.
2. the copolyesters constituent with heat-resistant quality as claimed in claim 1, it is characterized in that: this manganese carboxylate salt is C
1～C
18aliphatic carboxylic acid manganese salt.
3. the copolyesters constituent with heat-resistant quality as claimed in claim 2 is characterized in that: this manganese carboxylate salt is to be selected from the group that manganese acetate and manganese stearate form.
4. the copolyesters constituent with heat-resistant quality as claimed in claim 1, it is characterized in that: this salts of carboxylic acids is C
1～C
18the aliphatic carboxylic acid zinc salt.
5. the copolyesters constituent with heat-resistant quality as claimed in claim 4 is characterized in that: this salts of carboxylic acids is to be selected from the group that zinc acetate and Zinic stearas form.
6. the copolyesters constituent with heat-resistant quality as claimed in claim 1, it is characterized in that: this aliphatic-aromatic copolyester is to carry out for a unit (I) and a unit (II) polymkeric substance that copolymerization obtains, and this unit (I) is 0.1: 99.9～99.9: 0.1 with the molar ratio scope of this unit (II)
7. the copolyesters constituent with heat-resistant quality as claimed in claim 1, it is characterized in that: this aliphatic-aromatic copolyester is to be selected from butyleneglycol adipic acid ester-terephthalic acid ester copolyesters, butyleneglycol succinate-terephthalic acid ester copolyesters, tetramethyl-adipic acid ester-terephthalic acid ester copolyesters or its combination.
8. the copolyesters constituent with heat-resistant quality as claimed in claim 1, it is characterized in that: the weight average molecular weight scope of this aliphatic-aromatic copolyester is 30,000～50,000.
9. the copolyesters constituent with heat-resistant quality as claimed in claim 1 is characterized in that: the weight of this aliphatic-aromatic copolyester of take is 100 listed as parts by weight, and the amount ranges that this macromolecular chain extends agent is 0.3～2.0 weight part.
10. the copolyesters constituent with heat-resistant quality as claimed in claim 1 is characterized in that: the weight average molecular weight scope that this macromolecular chain extends agent is 5,000～20,000.
11. have the copolyesters constituent of heat-resistant quality as claimed in claim 1, it is characterized in that: the epoxy equivalent (weight) scope that this macromolecular chain extends agent is 200～500g/eq.
The copolyesters constituent that there is heat-resistant quality 12. as claimed in claim 1, it is characterized in that: it is that acrylate monomer and an auxiliary monomer that has epoxide functional groups by least one carries out polymerization and make that this macromolecular chain extends agent, and this auxiliary monomer is to be selected from styrenic monomers.
13. have the copolyesters constituent of heat-resistant quality as claimed in claim 12, it is characterized in that: this amount ranges with acrylate monomer of epoxide functional groups is 30～50wt%, and the amount ranges of this auxiliary monomer is 70～50wt%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010571375.5A CN102477153B (en) | 2010-11-23 | 2010-11-23 | Copolyester composition with thermal stability |
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| CN201010571375.5A CN102477153B (en) | 2010-11-23 | 2010-11-23 | Copolyester composition with thermal stability |
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| CN102477153A CN102477153A (en) | 2012-05-30 |
| CN102477153B true CN102477153B (en) | 2014-01-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106700032B (en) * | 2015-11-13 | 2019-03-19 | 上纬企业股份有限公司 | Branch-like thermoplastic composite and preparation method thereof |
| CN115637023B (en) * | 2021-07-19 | 2023-07-07 | 广东祥利科技集团有限公司 | Biodegradable blown film |
| CN114456666B (en) * | 2022-03-30 | 2022-10-28 | 北京化工大学 | High-temperature-resistant water-based gloss oil, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6506852B2 (en) * | 1997-04-02 | 2003-01-14 | Djk Techno Science Laboratories, Inc. | Polyester resin and process for producing molded product thereof |
| WO2000020491A1 (en) * | 1998-10-02 | 2000-04-13 | Djk Techno Science Laboratories Inc. | Foamed polyester resin molding and process for producing the same |
| US8258239B2 (en) * | 2007-07-01 | 2012-09-04 | Ftex, Incorporated | Production method of polyethylene terephthalate graft copolymerized resin and molded product thereof |
| KR101543489B1 (en) * | 2008-04-15 | 2015-08-10 | 바스프 에스이 | Method for the continuous production of biodegradable polyesters |
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