CN100404581C - Alkyd resin and molded products - Google Patents
Alkyd resin and molded products Download PDFInfo
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- CN100404581C CN100404581C CNB01143533XA CN01143533A CN100404581C CN 100404581 C CN100404581 C CN 100404581C CN B01143533X A CNB01143533X A CN B01143533XA CN 01143533 A CN01143533 A CN 01143533A CN 100404581 C CN100404581 C CN 100404581C
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Abstract
The present invention discloses a polyester resin containing the monomer mixture of glycol components and dicarboxylic acid components by polymerizing, wherein the glycol components comprise 5 to 60% (molar mass) of spiro glycol (SPG) expressed by a structural formula I and 30 to 95% (molar mass) of ethylene glycol, and the dicarboxylic acid components comprise 80 to 100% (molar mass) terephthalic acid and/or the ester thereof. The polyester resin is characterized in that (1), intrinsic viscosity is from 0.4 to 1.5 dL/g; (2), melt viscosity is from 700 to 5000Pa. s; (3), molecular weight distribution is from 2.5 to 12.0; (4), glass transition temperature is 90 DEG C or higher, and an exothermic peak of crystallisation by cooling is 5 J/g or lower. The polyester resin has excellent heat resistance, transparence, mechanical performance, moulding performance and fabrication property, which can be used for producing moulding products, such as films, sheet materials, hollow vessels and foaming products.
Description
Background of invention
1. invention field
The present invention relates to a kind of vibrin, relate more specifically to a kind of vibrin that is used for film, sheet material or hollow container and a kind of moulded parts of making by this vibrin with excellent thermotolerance, the transparency, mechanical property, mouldability and manufacturing character.
2. the description of prior art
Well known, PET (polyethylene terephthalate) is a kind of polyester that industrial value is arranged, because it has excellent mechanical property such as tensile strength, elongation and Young's modulus, physicals such as thermotolerance and dimensional stability, with chemical property such as chemical resistant properties and water tolerance, and low-cost.For example, PET has been widely used in various application such as fiber, tyre cord, bottle and film.If but PET is shaped to thick sheet, i.e. plate, its high crystallization rate often causes the albefaction of plate because of crystallization in manufacturing step, thereby transparent panel can not be provided.For fear of this shortcoming, used PET by modifications such as cyclohexanedimethanols.In addition when producing the PET bottle, used expensive germanium oxide as catalyzer reducing crystallization rate, or used by a kind of modified component of copolymerization such as m-phthalic acid and cyclohexanedimethanol and the PET of modification.
But this modified PET is not too heat-resisting, so it is needing the application of high heat resistance, and for example the application in illuminatian plate, carport and the heat-resisting food product containers is limited to.
United States Patent (USP) 2945008 is open in embodiment 9 and 10, will comprise ethylene glycol and by structural formula I:
3 of expression, 9-two (1,1-dimethyl-2-hydroxyethyl)-2,4,8, the diol component (diol component) of 10-four oxaspiros [5.5] undecane (following only be called sometimes " SPG ") obtains a kind of at 180-220 ℃ of polyester that melts down with the dicarboxylic acid component's polymerization in the presence of titanium compound catalyst that comprises dimethyl terephthalate (DMT).Wherein disclosed modified PET is compared expection and is had high heat resistance with unmodified PET, because this modified PET comprises the SPG component with rigid structure.But this United States Patent (USP) does not describe performance such as limiting viscosity, molecular weight distribution, melt viscosity, mechanical characteristics and the thermotolerance of modified PET in detail.In addition, this modified PET can not stably show effective mouldability and thermotolerance or sharply descend on shock-resistance, and this depends on its chemical constitution and performance.Therefore, not necessarily a kind of actual available moulding material of this modified PET.
Japanese Patent Application Publication № 3-130425 and Japanese Patent publication № 5-69151 and 6-29396 propose, use high shrinkage continuous yarn, coating and the tackiness agent of a kind of polyester of being made by the diol component that comprises SPG as the merging filament yarn of being made up of different shrinking percentage long filaments.But in these prior aries, there is not any description about molecular weight distribution, melt viscosity and the mechanical property of this modified PET.Because this modified PET can not stably show effective thermotolerance or sharply descend not necessarily a kind of actual available moulding material of described modified PET along with its composition and performance on shock-resistance.
In addition, be very difficult to produce good foaming product, because its melt not too has elasticity and thickness by foaming a kind of linear, aromatic polyesters resin of extrusion molding such as polyethylene terephthalate.
In order to address the above problem, Japanese Patent publication № 5-15736 proposes the mixture that linear, aromatic polyesters resin and per molecule have a compound of two or more anhydride groups extrusion molding that foams, and Japanese Patent publication № 5-47575 proposition is with the mixture of linear, aromatic polyesters resin, the compound with two or more anhydride groups and the special metal compound extrusion molding that foams.In addition, Japanese Patent Application Publication № 7-33899 proposes molecular weight distribution (weight-average molecular weight/number-average molecular weight) is the polyester of the 5.0-21.0 extrusion molding that foams, and Japanese Patent Application Publication № 11-166067 proposition is 1 * 10 with Z-average molecular weight
6Or higher and branching parameter is 0.8 or the lower polyester extrusion molding that foams.
In any aforesaid method, polyfunctional carboxylic acids acid anhydride or multifunctional glycidyl compound are added vibrin.If this polyfunctional compound adds in producing the vibrin process, products therefrom becomes three-dimensional, therefore is difficult to take out from reaction vessel product.Therefore, the branching aromatic copolyesters resin that adds the polyfunctional compound or obtain in must extrusion molding step process afterwards by this polyfunctional compound of copolymerization and linear polyester resin.
Japanese Patent Application Publication № 8-231751 discloses a kind of foaming product of being made by aromatic polyester resin, and this vibrin use comprises the diol component of cyclohexanedimethanol and ethylene glycol and makes.In the method, crystallization in the foam process process can postpone by using the aromatic polyester resin of being made by two kinds of diol components, and the gained foaming product has heat-insulating property, high shock-absorbing capacity and the good recovery ability of uniformly thin closed pore, high blowing ratio, excellence like this.But this foaming product is still not enough on thermotolerance and physical strength.
In addition, Japanese Patent Application Publication № 11-147969 discloses a kind of foaming product of being made by aromatic polyester resin, and this vibrin uses and comprises 2, the dicarboxylic acid component of 6-naphthalic acid and terephthalic acid and making.In the production of this foaming product, if increase by 2, the amount of 6-naphthalic acid is to improve thermotolerance, because the increase of crystallization rate is difficult to produce satisfactorily the foaming product with high closed cell content.
The invention summary
Consider the problems referred to above of the prior art, an object of the present invention is to provide a kind of vibrin that is used for film, sheet material or hollow container with excellent thermotolerance, the transparency, mechanical property, mouldability and manufacturing character.Even another object of the present invention provide a kind of even without produce with any branching agent also have high melt viscosity and also at short notice polymerization also further have low limiting viscosity, that is, be used to produce the vibrin of the various excellent properties of foaming product.
The inventor has been found that thermotolerance, the transparency, mechanical property and the manufacturing character that has excellence by the copolyesters that uses limited amount specific glycol comonomer to make and to have specific soltion viscosity, melt viscosity and a molecular weight distribution after the above-mentioned purpose in further investigation.The inventor finds that also this copolyesters particularly suitable makes to produce the material of foaming product.
Like this, the invention provides and a kind ofly comprise the vibrin that diol component and dicarboxylic acid component's monomer mixture is made by polymerization, wherein said diol component comprises the glycol of being represented by structural formula I (SPG) of 5-60% mole:
With the ethylene glycol of 30-95% mole, described dicarboxylic acid component comprises terephthalic acid and/or its ester of 80-100% mole, and described vibrin satisfies following (1)-(4) that require:
(1) limiting viscosity of measuring in 6/4 (quality) mixed solvent at phenol/sym.-tetrachloroethane under 25 ℃ is 0.4-1.5dL/g;
(2) be 700-5000Pas in the melt viscosity of under 100/ second shearing rate, measuring under 240 ℃;
(3) molecular weight distribution is 2.5-12.0; With
(4) by determine with dsc method the time, second-order transition temperature is 90 ℃ or higher, and the crystallisation by cooling exothermic peak is 5J/g or lower.
The present invention also provides a kind of moulded parts of being made by this vibrin.
Detailed Description Of The Invention
Vibrin of the present invention is made by the monomer mixture that polymerization comprises diol component (diol component) and dicarboxylic acid component, wherein said diol component comprises the SPG that is represented by structural formula I of 5-60% mole and the ethylene glycol of 30-95% mole, and described dicarboxylic acid component comprises terephthalic acid and/or its ester of 80-100% mole.The example of terephthalate comprises dimethyl terephthalate (DMT), diethyl terephthalate, terephthalic acid dipropyl, terephthalic acid diisopropyl ester, dibutyl terephthalate, terephthalic acid dicyclohexyl ester etc.By using the SPG that is represented by structural formula I in the above scope, the gained vibrin has excellent thermotolerance, solvent resistance, the transparency, mouldability, mechanical property and manufacturing character simultaneously.
Preferably, vibrin of the present invention is made by the monomer mixture that polymerization comprises diol component and dicarboxylic acid component, wherein said diol component comprises the SPG that is represented by structural formula I of 20-40% mole and the ethylene glycol of 50-80% mole, and described dicarboxylic acid component comprises terephthalic acid and/or its ester of 95-100% mole.By in above-mentioned scope, regulating diol component and dicarboxylic acid component's content, can further improve thermotolerance and mechanical property.
The vibrin that is specially adapted to produce foaming product is made by the monomer mixture that polymerization comprises diol component and dicarboxylic acid component, wherein said diol component comprises the SPG that is represented by structural formula I of 15-60% mole and the ethylene glycol of 40-85% mole, and described dicarboxylic acid component comprises terephthalic acid and/or its ester of 90-100% mole.
In the present invention, the dicarboxylic acid component can comprise 20% mole or the lower dicarboxylic acid except terephthalic acid and/or its ester.The example that can be used for the dicarboxylic acid except terephthalic acid of the present invention comprises m-phthalic acid, phthalic acid, 2-methyl terephthalic acid, naphthalic acid, biphenyl dicarboxylic acid, the naphthane dioctyl phthalate, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, the dodecane dioctyl phthalate, cyclohexane cyclohexanedimethanodibasic, the perhydronaphthalene dioctyl phthalate, the norbornane dioctyl phthalate, the tristane dioctyl phthalate, five rings decane dioctyl phthalate, the isophorone dioctyl phthalate, 3,9-two (2-propyloic)-2,4,8,10-four oxaspiros [5.5] undecane, 1,2, the 4-benzenetricarboxylic acid, 1,3, the 5-benzenetricarboxylic acid, pyromellitic acid, and tricarballylic acid, but be not limited thereto.
In addition in the present invention, diol component can comprise 10% mole or the lower glycol except SPG shown in the structural formula I and ethylene glycol.The example of this glycol includes, but is not limited to aliphatic diol as 1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, glycol ether, triglycol, propylene glycol and neopentyl glycol; Polyalkylene glycol such as polyoxyethylene glycol, polypropylene glycol and polytetramethylene glycol; Trivalent or more multivalent polyol such as glycerine, TriMethylolPropane(TMP) and tetramethylolmethane; Alicyclic diol is as 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-perhydronaphthalene dimethanol, 1,3-perhydronaphthalene dimethanol, 1,4-perhydronaphthalene dimethanol, 1,5-perhydronaphthalene dimethanol, 1,6-perhydronaphthalene dimethanol, 2,7-perhydronaphthalene dimethanol, naphthane dimethanol, norbornane dimethanol, tristane dimethanol, 5-methylol-5-ethyl-2-(1,1-dimethyl-2-hydroxyethyl)-1,3-diox and five rings decane dimethanol; Bis-phenol is as 4,4 '-(1-methyl ethylidene) bis-phenol, methylene radical bis-phenol (Bisphenol F), 4,4 '-cyclohexylidene bis-phenol (bisphenol Z) and 4, the oxyalkylene affixture of 4 '-alkylsulfonyl bis-phenol (bisphenol S); And aromatic dihydroxy compound such as Resorcinol, Resorcinol, 4,4 '-dihydroxybiphenyl, 4,4 '-dihydroxy diphenyl ether and 4, the oxyalkylene affixture of 4 '-dihydroxybiphenyl benzophenone.
Vibrin of the present invention can be made by any suitable currently known methods, is not particularly limited.For example, this vibrin can be made by transesterification reaction or direct esterification reaction, can carry out in melt polymerization method or solution polymerization process.As transesterification catalyzer, catalyst for esterification reaction, etherification reaction inhibitor, polymerisation catalysts, various stablizer such as thermo-stabilizer and photostabilizer and polyreaction properties-correcting agent, use known in the art those.The example of transesterification catalyzer comprises the compound of manganese, cobalt, zinc, titanium and calcium.The example of catalyst for esterification reaction comprises the compound of manganese, cobalt, zinc, titanium and calcium.The example of etherification reaction inhibitor comprises amine compound.
The example of polycondensation catalyst comprises the compound of germanium, antimony, tin and titanium.The example of thermo-stabilizer comprises multiple phosphorus compound such as phosphoric acid, phosphorous acid and phenyl-phosphonic acid.In addition, various additives such as photostabilizer, static inhibitor, lubricant, antioxidant and releasing agent can be used for producing vibrin.
SPG can add in any stage of producing vibrin.For example, SPG can add after esterification or transesterification reaction are finished.In the direct esterification reaction method, water can be used for keeping the stable of slurry state.
In the present invention, the performance of vibrin is measured by the following method.
(1) limiting viscosity (IV)
Limiting viscosity is used the Abbe viscometer, is measuring in 6/4 (quality) mixed solvent at phenol and sym.-tetrachloroethane under 25 ℃ the steady temperature.
(2) melt viscosity
Melt viscosity is used the Capirograph 1C that derives from Toyo Seiki Co.Ltd., measures under the following conditions.
Measure temperature: 240 ℃;
Warm up time: 1 minute
Nozzle diameter: 1 millimeter
Nozzle length: 10 millimeters
Shearing rate: 100/ second
(3) molecular weight distribution (Mw/Mn)
Metering facility: the gel permeation chromatography (GPC) " Shodex-11 " that derives from Showa Denko Co.Ltd.
Solvent: 2 mmoles in hexafluoro-2-propyl alcohol/rise sodium trifluoroacetate
Sample solution concentration: about 0.05% weight
Detector: refractive index detector (RI)
Proofread and correct: polymethylmethacrylate (PMMA) standard substance
(4) drop weight test
Metering facility: the drop-testing machine that derives from Parker Corporation
Envrionment conditions: 25 ℃ and 60 ± 20% relative humidity
The shape of weight: the snaphead of 20 mm dias
The speed of falling: 10 meter per seconds
Striking energy: 300 joules
The energy that absorbs when weight penetrates test sample is measured according to ASTM D3029 in the above conditions.The result that use records, the breaking tenacity of dropping hammer is calculated by following formula:
Breaking tenacity=(absorbing energy)/(thickness of test sample) drops hammer
(5) second-order transition temperature and crystallisation by cooling exothermic peak
Use derives from the DSC/TA-50WS of Shimadzu company, be placed on about 10 milligrams of sample polymer in the unsealed aluminum container and in the stream of nitrogen gas of flow velocity 30 ml/min with the heating of 20 ℃/minute temperature rise rate, measure second-order transition temperature (Tg).The center temperature of the discontinuity zone of baseline on the DSC curve, promptly specific heat is reduced to the temperature of a half as Tg.After measuring Tg, sample polymer kept 1 minute down at 280 ℃, then with 10 ℃/minute temperature drop rate cooling.Crystallisation by cooling exothermic peak (following only be called " Δ Hc ") is determined as the area of the exothermic peak that occurs in process of cooling.
The limiting viscosity of vibrin of the present invention is 0.4-1.5dL/g, preferred 0.5-1.0dL/g, more preferably 0.6-0.8dL/g.If limiting viscosity is 0.4dL/g or higher, the gained moulded parts has excellent intensity, is 1.5dL/g or lower and work as limiting viscosity, and this vibrin has excellent mouldability.
Vibrin of the present invention is 700-5000Pas in the melt viscosity of measuring under 100/ second shearing rate under 240 ℃.If melt viscosity is in above-mentioned scope, this vibrin has excellent mouldability.
The molecular weight distribution of vibrin of the present invention is 2.5-12.0.If molecular weight distribution is in above-mentioned scope, this vibrin has excellent mouldability.Molecular weight distribution is meant the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn).By the add-on of suitable selection SPG and molecular weight, polymeric reaction temperature and the additive of feed in raw material timing, this polyester, molecular weight distribution can be regulated in the scope of 2.5-12.0.
The shock strength of vibrin of the present invention is expressed as the breaking tenacity of dropping hammer.When the weight that has 20 mm dia snapheads by falling vertically was applied to 300 joules of striking energys on the polyester sheet of being made by this vibrin, the breaking tenacity of dropping hammer was 10kJ/m or higher.Breaking tenacity is 10kJ/m or higher if drop hammer, and the gained moulded parts has actual effectively shock strength.
When measuring according to differential scanning calorimetry (DSC), the second-order transition temperature of vibrin of the present invention is that 90 ℃ or higher and crystallisation by cooling exothermic peak are 5J/g or lower.If second-order transition temperature is 90 ℃ or higher, this vibrin has actual effectively thermotolerance.In addition when the crystallisation by cooling exothermic peak be 5J/g or when lower, this vibrin has the excellent transparency, mouldability and manufacturing character.
Vibrin of the present invention is shaped to the moulded products that requires to have high transparent, is non-stretching or slight tensile list-or multi-layer sheet by T die head extrusion molding or the type of being co-extruded for example, can be made into stretched film or the deep drawn container that slightly stretches; With make the thin-walled hollow container that body thickness is the 0.1-2 millimeter by non-stretching direct blowing or stretch-blow method.
The sheet material that derives from vibrin of the present invention can be used for various application.In material of construction was used, sheet material can be used as outer material as being used for the illuminatian plate of vending machine, show cabinet, outdoor signboard and carport; The outer cover that is used for various industrial machines; Windshield; With factory's division plate.Application on household electrical appliance comprises forth screen plate, the directing plate backlight of electric light outer cover, projection TV and is used for the header board of game station.In food applications, this sheet material can be used as the lid of the lunch box that need carry out pasteurization or disinfectant transparent vessel, heat-resisting transparent drinking glasses, food disc and need reheat.In addition, the vibrin sheet material is applicable to the folding transparent vessel of making and transparent box, bubble shape cover and at the exported product of ocean long period transportation.The sheet material or the hollow container that derive from vibrin of the present invention also can be for example as packing or lappings.
Foaming product of the present invention was by making the foaming structure stabilization polyester resin foamed and subsequently.The foaming method of vibrin is not particularly limited, and mainly is impregnated with the resin of whipping agent by heating, or is undertaken by whipping agent is mediated in the molten resin.This vibrin can be by foam-in-mould method or the foaming extrusion molding extrusion molding that foams, but is not limited to this." foam-in-mould " be meant a kind of with resin expanded one-tenth bead and subsequently the heating under in mould the caked method of molding.
Preferably, foaming product of the present invention mixes whipping agent by this resin of fusing under High Temperature High Pressure with molten resin, then molten resin is extruded into the low pressure area that is used to foam and makes.The example of whipping agent comprises rare gas element, saturated aliphatic hydrocarbon, aromatic hydrocarbons, halohydrocarbon, ether and ketone.These whipping agents can be separately or two or more be used in combination.The object lesson of whipping agent comprises carbon dioxide, nitrogen, methane, ethane, normal butane, iso-pentane, neopentane, normal hexane, 2-methylpentane, 3-methylpentane; 2; 2-dimethylbutane, 2; 3-dimethylbutane, methyl cyclopropane, ethyl tetramethylene, 1; 1,2-trimethylammonium cyclopropane, benzene, Trichloromonofluoromethane, Refrigerant R 113, dichloro tetrafluoro ethane, dme, cellosolvo, acetone, ethyl methyl ketone and ethanoyl ketone.The consumption of whipping agent is the 1-20 weight part based on 100 weight part vibrin.If the amount of whipping agent is lower than 1 weight part, polyester resin foamed deficiency causes cost-performance bad and foaming product is adiabatic bad.If the amount of whipping agent surpasses 20 weight parts, may can not get stable sealing gland at the die head place, cause producing bad foaming product.
In general, extruded plastic foam is by mixing whipping agent with molten resin, then molten resin is cooled to the temperature of resin viscosity when reaching the suitable level that foams and carries out.Therefore need be under high rotation speed fully this vibrin of melt-kneaded and whipping agent.In addition, in order to improve cooling efficiency, this kneading product is preferably extruded under low screw rod speed of rotation, will shear heating like this and be controlled to low as far as possible.If melt-kneaded that is used for foaming and cooling are carried out at same forcing machine, this forcing machine need cool off to guarantee enough resins under low screw rod speed of rotation in operation.As a result, it is not enough that the melt-kneaded of vibrin and whipping agent often becomes, thereby foam bad and the production rate variance because of low extrusion capacity causes.Therefore in the present invention, the melt-kneaded of molten polyester resin and whipping agent and will be resin extruded preferably in corresponding one or more forcing machines, separating and carry out to foam cooling before distinguishing of low pressure.The configuration or the kind of forcing machine are not particularly limited.
When production foaming product of the present invention, vibrin can add suitable additive, and for example nucleator such as talcum, linking agent are as from aggressiveness, the mineral filler that comprises fiber, fire retardant, static inhibitor, antioxidant and tinting material.
The thickness of the foaming product of the present invention that is obtained by above technology is preferably the 0.2-7 millimeter.If thickness is lower than 0.2 millimeter, heat insulating ability, buffering efficient and physical strength may be not enough.If thickness surpasses 7 millimeters, making character such as thermoforming and bag may be bad.
The present invention is by following examples more detailed description.But should be noted that following examples are illustrative, have no intention to limit the invention to this.
In the following Examples and Comparative Examples, dimethyl terephthalate (DMT) abbreviates " DMT ", 2 as, the 6-naphthalene diformic acid dimethyl ester is that " NDCM ", pyromellitic acid are that " PMDA ", ethylene glycol are that " EG ", neopentyl glycol are " NPG ", 1, the 4-cyclohexanedimethanol is " CHDM " and 3,9-two (1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-four oxaspiros [5.5] undecane is " SPG ".
Embodiment 1
(1) production of resin
The mixture of 13313 gram (69 moles) DMT, 7191 gram (116 moles) EG and 2294 gram (7.5 moles) SPG being heated to 200 ℃ under the nitrogen atmosphere in the presence of based on 0.03 mole of four hydration manganous acetate of 100 moles of DMT, is carried out transesterification reaction.
The distillation amount of methyl alcohol reach 90% or higher after, in reaction mixture, add stoichiometric quantity respectively based on 0.01 mole of weisspiessglanz (III) and the 0.06 mole of phosphoric acid triphenylmethyl methacrylate (following only be called " TPP ") of 100 moles of DMT.Temperature raises gradually and pressure descends gradually, finally reaches 280 ℃ and 0.1kPa or lower to carry out polyreaction.Polyreaction stops when reaction product reaches predetermined melt viscosity, obtains a kind of unitary polyester of SPG that comprises 9% mole (SPG9) amount like this.The content of SPG unit in this polymkeric substance passes through
1H-NMR (400 megahertz) measures.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 1.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 2.
Embodiment 2
(1) production of resin
According to the same way as of embodiment 1, prepare by the diol component that comprises 20% mole of SPG unit and 80% mole of ethylene glycol unit and comprise the polyester that the dicarboxylic acid component of 100% mole of terephthalic acid units (SPG20) forms.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 1.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 2.
Embodiment 3
(1) production of resin
According to the same way as of embodiment 1, prepare by the diol component that comprises 50% mole of SPG unit and 50% mole of ethylene glycol unit and comprise the polyester that the dicarboxylic acid component of 100% mole of terephthalic acid units (SPG50) forms.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 1.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 2.
Embodiment 4
(1) production of resin
According to the same way as of embodiment 1, prepare by the diol component that comprises 5% mole of SPG unit and 95% mole of ethylene glycol unit and comprise 90% mole of terephthalic acid units and polyester that the dicarboxylic acid component of 10% mole of naphthalic acid unit (SPG5N10) forms.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 1.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 2.
Injection-molded item and sheet material are assessed in accordance with the following methods.
1. the assessment of injection-molded item
(1) tensile property
Measure according to ASTM D638.
(2) flexural property
Measure according to ASTM D790.
(3) deflection temperature under load
Measure under the stress in bending of 451kPa according to ASTM D648.
(4) falling weight impact test
Metering facility: the drop-testing machine that derives from Parker company
Envrionment conditions: 25 ℃ and 60 ± 20% relative humidity
The shape of weight: the snaphead of 20 mm dias
The speed of falling: 10 meter per seconds
Striking energy: 300 joules
The energy that absorbs when weight penetrates test sample is measured according to ASTM D3029 in the above conditions.The result that use records, the breaking tenacity of dropping hammer is calculated by following formula:
Breaking tenacity=(absorbing energy)/(thickness of test sample) drops hammer
2. the assessment of sheet material
(1) mouldability
Molding sheet material is cut into the square test sample of 100 millimeters long (extruding direction) * 100 mm wides (width).Measure the thickness of test sample at 10 points choosing arbitrarily.If standard deviation uniform thickness 5% within, mouldability is decided to be " good ", if surpass 5% then be " bad ".In addition, the resin that is not easy to be extruded into sheet material also is decided to be " bad ".
(2) thermotolerance
Sheet material is cut into the square test sample of 100 millimeters long (extruding direction) * 100 mm wides (width).Test sample was heated 30 minutes in stove at 85 ℃.On length and width, shrink and all surpass 10% test sample and aspect thermotolerance, be decided to be " bad ".
(3) falling weight impact test
Metering facility: the drop-testing machine that derives from Parker company
Envrionment conditions: 25 ℃ and 60 ± 20% relative humidity
The shape of weight: the snaphead of 20 mm dias
Shock of a fall speed: 10 meter per seconds
Striking energy: 300 joules
The energy that absorbs when weight penetrates test sample is measured according to ASTM D3029 in the above conditions.The result that use records, the breaking tenacity of dropping hammer is calculated by following formula:
Breaking tenacity=(absorbing energy)/(thickness of test sample) drops hammer
Evaluation criteria
A: greater than 40kJ/m
B：10-40kJ/m
C: less than 10kJ/m
(4) die-cut quality
Stamping machine: TORC-PAC PRESS
Die-cut diameter: 19 millimeters
Blade: Thomson blade
Die-cut test is carried out in the above conditions, according to the die-cut quality character of every kind of test sample of following criterion evaluation:
A: die-cut fully, but on the cutting surface, do not have burr
B: can be die-cut, but on the cutting surface, have burr
C: can not be die-cut
Table 1
Table 2
Comparative Examples 1
(1) production of resin
According to the same way as of embodiment 1, prepare by the diol component that comprises 3% mole of SPG unit and 97% mole of ethylene glycol unit and comprise the polyester that the dicarboxylic acid component of 100% mole of terephthalic acid units (SPG3) forms.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 3.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 4.
Comparative Examples 2
(1) vibrin
Use derives from the PETG (PET of 33% mole of cyclohexanedimethanol modification) of Eastman Kodak Company as vibrin.
(2) preparation of injection-molded item
The vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition of this polyester; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 3.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 4.
Comparative Examples 3
(1) production of resin
According to the same way as of embodiment 1, prepare by the diol component that comprises 45% mole of SPG unit and 55% mole of ethylene glycol unit and comprise the polyester that the dicarboxylic acid component of 100% mole of terephthalic acid units (SPG45) forms.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 3.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 4.
Comparative Examples 4
(1) production of resin
According to the same way as of embodiment 1, prepare by the diol component that comprises 70% mole of SPG unit and 30% mole of ethylene glycol unit and comprise the polyester that the dicarboxylic acid component of 100% mole of terephthalic acid units (SPG70) forms.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 3.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 4.
Comparative Examples 5
(1) production of resin
According to the same way as of embodiment 1, prepare by the diol component that comprises 10% mole of SPG unit and 90% mole of ethylene glycol unit and comprise the polyester that the dicarboxylic acid component of 100% mole of terephthalic acid units (SPG10) forms.
(2) preparation of injection-molded item
The polyester that so obtains vacuum-drying and under predetermined condition, use screw injection molding machine (screw diameter: 32 millimeters φ under predetermined condition; Mold clamping pressure: 9.8kN) carry out injection moulding, prepare the test sample of 3.2 mm thick.The measuring result of the various performances of this injection moulding test sample provides in table 3.
(3) preparation of sheet material
With polyester in vacuum-drying under the predetermined condition and under predetermined condition, extrude sheet material into about 0.8 mm thick.Test result provides in table 4.
Table 3
Table 4
Embodiment 5-6 and Comparative Examples 6-9
(1) Ping production
Corresponding resin mold shown in table 5 and 6 is moulded bottle.
Condition of moulding
Premolding: 30 grams
Injection moulding machine: the M200 bottle that derives from Meiki Seisakusho Co.Ltd.: 300 milliliters of capacity; Pressure resistant type; At the bottom of the petal
Blow moulding machine: the LB-01 that derives from Krupp Corpoplast Maschinenbau GmbH is in Comparative Examples 6, and service performance viscosity is the polyethylene terephthalate (deriving from the RT543 of Nippon Unipet Co.Ltd.) of 0.75dL/g.
The blowing of every kind of resin is according to following criterion evaluation:
Well: essentially no irregular thickness
Bad: irregular along peripheral direction thickness
(2) drop test
The bottle that is filled with water is kept spending the night down at 5 ℃, utilize gravity to drop then, the bottom is (vertically dropping) downwards.Each sample carries out drop test with 15 bottles, then according to following criterion evaluation:
Well: do not change
Bad: as the crack to occur or leak
(3) hot water filling test
The bottle placement that will be filled with 85 ± 1 ℃ of hot water is spent the night, and assesses according to the maintenance situation of height and capacity according to following standard then:
Highly keep:
Well: 99% or higher
Bad: as to be lower than 99%
Capacity keeps:
Well: 98.5% or higher
Bad: as to be lower than 98.5%
The result provides in table 5 and 6.
Table 5
Table 6
Embodiment 7-8 and Comparative Examples 10-13
(1) extrusion molding of sheet material
To generate vibrin according to the corresponding mole polycondensation shown in table 7 and 8 as dicarboxylic acid component's DMT, DMT-NDCM mixture or DMT-PMDA mixture with as EG, SPG-EG mixture, CHDM-EG mixture or the NPG-EG mixture of diol component.Then, 0.05 weight part talcum is added in the 100 weight part vibrin as nucleator.The measurement of gained resin is fed to first forcing machine that is used for melt-kneaded, heats therein then, melts and mediate.Then, will be fed in the forcing machine under pressure with amount as the Trimethylmethane of whipping agent, then with this mixture melt-kneaded based on 10 weight parts of 100 weight part vibrin.This melt-kneaded product is fed in second forcing machine, and the end at forcing machine pushes through an annular die head under the temperature shown in table 7 and 8 then.This extrudes the tubulose foaming product and stretches on the refrigerative core rod being used for, and obtains foam sheet along extruding the direction cutting then.The mouldability of foam sheet and the performance of resin provide in table 7 and 8.Polymer properties is measured by the following method.In Comparative Examples 13, the difficulty because having formed three-dimensional polymer (gelling) is extruded in foaming.
(2) thermal test
Foam sheet is cut into the square test sample of 100 millimeters long (extruding direction) * 100 mm wides (width).Test sample was heated 30 minutes in stove under 85 ℃.On length and width, shrink and all surpass 10% test sample and aspect thermotolerance, be decided to be " bad ".
(3) foam structure
The foam sheet that obtains in embodiment and Comparative Examples respectively is cut into the square sheets of 25 millimeters long and 25 mm wides, but does not change thickness.20 square sheets are piled up on thickness direction, obtain a kind of sample that is used to measure closed cell content (%).At first, the apparent volume Va of this sample (centimetre
3) measure by outside dimension.Then, according to ASTM D2856, measure this sample by the air specific weight bottle actual volume Vx(centimetre
3).According to gained Va and Vx, calculate open cell content Fo (%) by following formula:
Fo＝(Va-Vx)/Va×100。
Closed cell content Fc (%) is calculated by following formula:
Fc＝100-Fo。
According to following criterion evaluation foam structure:
A: even and very tiny abscess and closed cell content Fc are 85% or higher
B: even and tiny abscess and closed cell content Fc are 80% or higher but be lower than 85%
C: uneven a little abscess and closed cell content Fc are 50% or higher but be lower than 80%
Two kinds of foam sheets that obtain in embodiment 7 and 8 all have high closed cell content, therefore can successfully be shaped to the good dish of corner angleization by vacuum moulding.The result provides in table 7 and 8.
Table 7
Table 8
Vibrin of the present invention has excellent thermotolerance, the transparency, mechanical property, mouldability and manufacturing character, therefore is suitable for the raw material of making film, sheet material, hollow container and foaming product.Industrial packaging material for food, material of construction or the analogue of making by vibrin of the present invention of can be used as of moulded parts.
Claims (8)
1. one kind comprises the vibrin that diol component and dicarboxylic acid component's monomer mixture is made by polymerization in the presence of at least a polycondensation catalyst that is selected from germanium, antimony and tin, and wherein said diol component comprises the spiroglycol of being represented by structural formula I of 5-60% mole
With the ethylene glycol of 30-95% mole, described dicarboxylic acid component comprises terephthalic acid and/or its ester of 80-100% mole, and described vibrin satisfies following (1)-(4) that require:
(1) limiting viscosity of measuring in 6/4 quality mixed solvent at phenol/sym.-tetrachloroethane under 25 ℃ is 0.4-1.5dL/g;
(2) be 700-5000Pas in the melt viscosity of under 100/ second shearing rate, measuring under 240 ℃;
(3) molecular weight distribution is 2.5-12.0; With
(4) when measuring by Differential Scanning Calorimeter, second-order transition temperature is 90 ℃ or higher, and the crystallisation by cooling exothermic peak is 0-5J/g.
2. according to the vibrin of claim 1, wherein said diol component comprises the spiroglycol of being represented by structural formula I of 20-40% mole and the ethylene glycol of 50-80% mole.
3. according to the vibrin of claim 1, wherein said dicarboxylic acid component comprises terephthalic acid and/or its ester of 95-100% mole.
4. according to the vibrin of claim 1, wherein said diol component comprises the spiroglycol of being represented by structural formula I of 15-60% mole and the ethylene glycol of 40-85% mole.
5. according to the vibrin of claim 1, it is made into polyester film or sheet material, when the semisphere weight by one 20 mm dia that falls vertically was applied to 300 joules of striking energys on described polyester film or the sheet material, the breaking tenacity of dropping hammer of described polyester film or sheet material was 10kJ/m or higher.
6. according to the vibrin of claim 1, it is made into hollow container.
7. method of producing the expanded polyester sheet material comprises:
Will according to the vibrin of claim 4 in the presence of whipping agent in forcing machine melt-kneaded, wherein foaming agent consumption is the 1-20 weight part, based on the vibrin of 100 weight parts; Then
Extrude this vibrin.
8. expanded polyester sheet material, the thickness of wherein said sheet material is that 0.2-7 millimeter and closed cell content are at least 50%, wherein said vibrin is made by the monomer mixture that comprises diol component and dicarboxylic acid component by polymerization in the presence of at least a polycondensation catalyst that is selected from germanium, antimony and tin, and wherein said diol component comprises the spiroglycol of being represented by structural formula I of 5-60% mole
With the ethylene glycol of 30-95% mole, described dicarboxylic acid component comprises terephthalic acid and/or its ester of 80-100% mole, and described vibrin satisfies following (1)-(4) that require:
(1) limiting viscosity of measuring in 6/4 quality mixed solvent at phenol/sym.-tetrachloroethane under 25 ℃ is 0.4-1.5dL/g;
(2) be 700-5000Pas in the melt viscosity of under 100/ second shearing rate, measuring under 240 ℃;
(3) molecular weight distribution is 2.5-12.0; With
(4) when measuring by Differential Scanning Calorimeter, second-order transition temperature is 90 ℃ or higher, and the crystallisation by cooling exothermic peak is 0-5J/g.
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| CNB01143533XA CN100404581C (en) | 2001-12-12 | 2001-12-12 | Alkyd resin and molded products |
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| CNB01143533XA CN100404581C (en) | 2001-12-12 | 2001-12-12 | Alkyd resin and molded products |
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| CN100404581C true CN100404581C (en) | 2008-07-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7935399B2 (en) * | 2004-09-02 | 2011-05-03 | Grupo Petrotemex, S.A. De C.V. | Low melting polyester polymers |
| JP2012017456A (en) * | 2010-06-11 | 2012-01-26 | Fujifilm Corp | Polyester film and method for producing the same, back sheet for solar cell, and solar cell module |
| JP5517842B2 (en) * | 2010-08-31 | 2014-06-11 | 株式会社ジェイエスピー | Method for producing extruded polycarbonate resin foam and extruded polycarbonate resin foam |
| TWI423999B (en) * | 2011-11-25 | 2014-01-21 | Ind Tech Res Inst | Amorphous copolyesters and flexible substrates and optical films utilizing the same |
| JP6654151B2 (en) * | 2015-01-26 | 2020-02-26 | リケンテクノス株式会社 | Production method of resin panels |
| WO2017097630A1 (en) * | 2015-12-08 | 2017-06-15 | Sabic Global Technologies B.V. | Translucent laser weldable thermoplastic compositions and laser-welded products |
| CN109694468A (en) * | 2017-10-24 | 2019-04-30 | 中国石化仪征化纤有限责任公司 | The preparation method of high heat resistance bottle modified poly ester |
| CN109694467A (en) * | 2017-10-24 | 2019-04-30 | 中国石油化工集团公司 | The heat resistance modified method of PBT |
| CN110437429A (en) * | 2018-05-02 | 2019-11-12 | 中国石油化工股份有限公司 | A kind of preparation method of modified poly ester and preparation method thereof and its film |
| CH715228A1 (en) * | 2018-08-02 | 2020-02-14 | Alpla Werke Alwin Lehner Gmbh & Co Kg | Preform made of polyester. |
| CN111072940B (en) * | 2019-11-28 | 2021-09-28 | 中国科学院宁波材料技术与工程研究所 | Copolyester based on spiro ethylene glycol and preparation method and product thereof |
| CN111072935A (en) * | 2019-12-18 | 2020-04-28 | 浙江恒澜科技有限公司 | Heat-resistant biodegradable polyester and preparation method thereof |
| KR20230069199A (en) * | 2020-11-24 | 2023-05-18 | 킨테 머티리얼즈 사이언스 앤드 테크놀로지 컴퍼니 리미티드 | Water-based polyester copolymer, manufacturing method and application thereof |
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