CN102093673B - Polyester having thermal ageing resistant performance and production method thereof - Google Patents

Polyester having thermal ageing resistant performance and production method thereof Download PDF

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Publication number
CN102093673B
CN102093673B CN2011100200856A CN201110020085A CN102093673B CN 102093673 B CN102093673 B CN 102093673B CN 2011100200856 A CN2011100200856 A CN 2011100200856A CN 201110020085 A CN201110020085 A CN 201110020085A CN 102093673 B CN102093673 B CN 102093673B
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polyester
oxidation inhibitor
resistant
agent
glass
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CN102093673A (en
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马宝海
陈哲
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Dongguan Dongxiang Plastic Co ltd
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NANTONG CITY DONGFANG PLASTIC CO Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885Screw or gear

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses polyester having thermal ageing resistant performance, which comprises a thermoplastic polyester, a flexibilizer, antioxygen, a heat stabilizer, a filler and other assistant. The product has high thermal ageing resistant performance and high flame-retarding performance.

Description

Polyester and working method thereof with resistant to thermal aging performance
Technical field
The present invention relates to a kind of polyester and working method thereof.
Background technology
Strengthening fire-retardant (not fire-retardant) polyester and be widely used in electronics, electrical equipment and automobile industry because of its favorable mechanical performance and electric property, is the employed ideal material of component of these industries.As everyone knows, plastics are a kind of relatively materials of easy ageing, and in use, the quality of plastic part and work-ing life and plastic ageing have confidential relation, and in the time of aging the generation, its performance can degenerate gradually, until final forfeiture use value.Plastic ageing mainly shows as following several kinds of forms, as chap, be clamminess, harden, soften, efflorescence, variable color, mildew etc.In the middle of daily life, strengthen fire-retardant (not fire-retardant) polyester material because heat and the effect of oxygen to work-ing life of material playing critical effect, so prevent that plastic degradation that heat, oxygen association response are caused from just becoming and are even more important.
Strengthen flame retardant polyester and can be used for electronic connector, air-conditioning terminal strip, breaker protector, rly., electrical condenser, coil rack, telephone socket, safety box, contactor, potentiometer, tuner shell, junctor, transmitter, automobile ignition coil, fans, electriciron parts, micromachine case etc. in electronics, electrical apparatus industry and automobile industry; Reinforced polyester can be used for collision bumper, wiper, automobile handle, car light framework or the like in automobile industry; These fields are to all there being working life of material certain requirement; The aging resistance of material is good more; The working life that means material is long more; In the middle of U.S. UL product certification system, proposed the RTI index, i.e. relatively hot ageing index is that the simulation material is at a certain temperature through the degradation degree of the action material of overheated and oxygen.Its index default value of polyester (PBT) is 75 ℃, reaches as high as 140 ℃ through the RTI value that promotes back polyester (PBT).Its method is that the plastic material high temperature (150 ℃-200 ℃) with different temperature points in the middle of the baking oven of fixed temperature and humidity after the sample preparation toasts experiment; In for some time, take out the variation of its intensity of test; Experiment can be at short notice as was inferred the changing value of material property after 10 years in 1 year with interior method with mathematics; The RTI value is high more, and the stability to aging of illustrative material is good more, and each item performance index of material descend slowly more.
Summary of the invention
The object of the present invention is to provide a kind of resistance to thermooxidation good, the polyester with resistant to thermal aging performance and the working method thereof that can prolong the work-ing life of material.
Technical solution of the present invention is:
A kind of polyester with resistant to thermal aging performance is characterized in that: in parts by weight, comprise following component:
130 parts of thermoplastic polyesters
Toughner 0-60 part
Oxidation inhibitor 0.05-3.0 part
Thermo-stabilizer 0.05-6.0 part
Weighting agent 0-300 part
Other auxiliary agent 0-12 part.
Spendable in the present invention exemplary polyester comprises; But be not limited in the middle of the polyethylene terephthalate (PET), poly terephthalic acid 1,4 butanediol ester (PBT), PEN (PEN), PBN (PBN), polytrimethylene terephthalate (PPT) one or more.
Spendable in the present invention toughner is ethene and ethene copolymer (including but not limited to LLDPE, LDPE, HDPE, POE, ethylene-methyl acrylate (EMA), ethylene-ethyl acrylate (EEA), ethylene-butyl acrylate (EBA), ethylene-vinyl acetate (EVA)); Vinyl grafting body (maleic anhydride graft or acrylic acid-grafted; Include but not limited to POE-g-MAH, PE-g-MAH, ethylene-propylene maleic anhydride grafts or the like); Ethylene-acrylate-SY-Monomer G (includes but not limited to EMA-GMA; EEA-GMA, one or more among the EBA-GMA).
Spendable in the present invention primary antioxidant is a phenolic antioxidant, includes but not limited to that the antioxidant 1010 chemical name is that four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, oxidation inhibitor 245 chemical names are the two β of triglycol-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester, and oxidation inhibitor 1098 chemical names are N, N '-hexa-methylene two (3; 5-di-t-butyl-4-hydroxybenzene propionic acid amide), oxidation inhibitor 1790 chemical names are 1,3,5-(three (the 4-tertiary butyl-3-hydroxyl-2,6-dimethyl benzene methyl)-1; 3,5-triazine-2,4,6-(1H, 3H; 5H)-and triketone, the antioxidant 3114 chemical name is 1,3,5-(three (3; The 5-di-tert-butyl-4-hydroxyl benzyl)-1,3,5-triazines-2,4; 6-(1H, 3H, 5H)-and triketone, the antioxidant 330 chemical name is 1.3.5-trimethylammonium-2.4.6-three (3.5-di-tert-butyl-4-hydroxyl benzyl) benzene; Oxidation inhibitor 1024 chemical names are 1,2-two (3, the 5-di-tert-butyl-hydroxy phenyl) propionyl, oxidation inhibitor BRUGGOLEN H12.
Spendable in the present invention assisted class oxidation inhibitor is phosphite ester kind antioxidant.Oxidation inhibitor 626 chemical names are two (3, the 5-di-tert-butyl-phenyl) pentaerythritol diphosphites, and oxidation inhibitor 627/627A is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Oxidation inhibitor P-EPQ chemical name be four (2, the 4-di-tert-butyl-phenyl) 4,4 '-the xenyl bis-phosphite; Oxidation inhibitor 168 chemical names are three (2,4 di-t-butyl) phosphorous acid ester, oxidation inhibitor S9228 chemical name two (2; 4-two cruel bases) pentaerythritol diphosphites, oxidation inhibitor BRUGGOLEN H12.。
Spendable in the present invention thermo-stabilizer is thioesters type thermal stabilizing agent such as DLTDP chemical name 3,3 '-Tyox B, DSTDP chemical name 3,3 '-thio-2 acid ester in February acyl, two 14 esters of DMTDP chemical name thio-2 acid.
Spendable in the present invention filling modifying agent includes but not limited to one or more in spun glass, glass microballon, thomel, wollastonite, clay, zeolite, quartz, zeyssatite, silit, silicon oxide, mica, kaolin, calcium sulfate, permanent white, lime carbonate, talcum powder, Calucium Silicate powder, zinc oxide, zinc sulphide, the whisker etc.
Spendable in the present invention other auxiliary agent includes but not limited to one or more in lubricant, anti-dripping agent (tetrafluoroethylene, i.e. 4F), static inhibitor, the tinting material etc.
Described polyester with resistant to thermal aging performance also comprises following components in part by weight:
Main flame retardant 12-65 part
Fire retarding synergist 4-22 part;
Spendable in the present invention main flame retardant is that bromination epoxy, TDE (are called for short DBDPE, molecular formula C 14H 4Br 10), bromination gathers carbon, brominated polyphenylene, brominated polystyrene, three (tribromophenoxy) triazine (molecular formula C 21H 6Br 9N 3O 3), two tetrabromo phthalimide (the molecular formula C of ethylene 18H 4O 4N 2Br 8), gather in the bromination pentabromobenzyl ester one or more.
Spendable in the present invention fire retarding synergist is the compound of Antimony Trioxide: 99.5Min, sodium antimonate, antimony peroxide, antimony organic class, in the hydration zinc borate one or more.
Described polyester with resistant to thermal aging performance in parts by weight, comprises following component:
100 parts of polybutylene terephthalates
Polyethylene terephthalate 0-20 part
Main flame retardant 14-48 part
Fire retarding synergist 5-17 part
Toughner 1-16 part
Oxidation inhibitor 0.05-1.0 part
Thermo-stabilizer 0.05-2.0 part
Weighting agent 0-115 part
Other auxiliary agent 0.05-4.0 part;
Spendable in the present invention exemplary polyester comprises polybutylene terephthalate, is called for short PBT, and its density is 1.31-1.35g/cm 3, viscosity is 0.7-1.2dl/g, melt temperature 220-230 ℃.Polyethylene terephthalate is called for short PET, and its specific density is 1.38g/cm 3
Spendable in the present invention main flame retardant is that bromination is gathered a kind of in carbon (like the BC-58 of U.S. Chemtura Corporation) and the brominated polystyrene (like the FR621 of U.S. Albemarle Corporation) or two kinds.
Spendable in the present invention fire retarding synergist is an Antimony Trioxide: 99.5Min.
Spendable in the present invention toughner is LLDPE (linear low density polyethylene) or DUPONT company 4170 (EBA-GMA).。
Spendable in the present invention oxidation inhibitor is the blend of primary antioxidant and assisted class oxidation inhibitor, and trade name is the oxidation inhibitor BRUGGOLENH12 that BRUGGEMANN CHEMICAL company produces.
Spendable in the present invention thermo-stabilizer is a DSTDP chemical name 3,3 '-thio-2 acid ester in February acyl.
Spendable in the present invention glass fiber diameter is the 5-20 micron, and the glass through compound silane coupling agent is handled only refers to short glass fiber, like U.S. PPG company 3786 short fibers.
Toughner can be to use DUPONT company 4170 or PT862 separately, or with LLDPE and DUPONT company 4170 or the composite use of PT862.
Spendable in the present invention other auxiliary agent includes but not limited to lubricant (calcium stearate, montanate, illiteracy dawn ester, pentaerythritol ester, OPE etc.) anti-dripping agent (tetrafluoroethylene; Be 4F), in static inhibitor (polyvalent alcohol, polyol ester such as Zerol, non-ionic antistatic agents such as sorbitan mono fatty acid ester), tinting material (pigment, dyestuff, white dyes etc.) etc. one or more.
A kind of working method with polyester of resistant to thermal aging performance; It is characterized in that: with thermoplastic polyester, toughner, oxidation inhibitor, thermo-stabilizer, other auxiliary agent set of dispense ratio by weight; After in the high speed blender, mixing; Send in the main feeding in the twin screw extruder, the glass/glass fiber adds in the side direction feeding subsequently, through extrude, cooling, pelletizing, drying, packing and process.
When in the high speed blender, mixing, also add main flame retardant and fire retarding synergist is mixed together.
The length-to-diameter ratio of twin screw extruder screw rod is 25-50: 1, and the screw rod design temperature is 180-245 ℃, screw speed is set at 200-600 rev/min.
The present invention has following several characteristics
1, has excellent resistant to thermal aging performance.
Can still keep later the over half of starting material mechanical property and electrical property, long service life, ageing-resistant performance excellence the work-ing life of the utilization polyester material that the present invention produced in 10 years.Realize that in the present invention this function mainly is through the following aspects:
(I) synergy of primary antioxidant, auxiliary antioxidant and thermo-stabilizer.Primary antioxidant and auxiliary antioxidant provide the ageing-resistant performance of material under normal temps, can eliminate the radical that material is in use produced rapidly, long-acting good stability, and material thermostable effect has at high temperature been strengthened in the utilization of thermo-stabilizer DSTP.
(II) selection of resin and glass.The present invention has selected to have the vibrin than low terminal carboxy content≤20meq/kg, has alleviated because of the too high Degradation to material of content of carboxyl end group, has protected matrix resin.Having selected is main short fiber product with PPG3786, and the content of treating compound and long fibre have significantly differently in the short fiber, and its bonding properties with base resin is better, and difficult generation is worn out in the middle of the life-time service process.
(III) interpolation of a small amount of polyethylene terephthalate (PET) and permanent white.Add a spot of polyethylene terephthalate (PET) and permanent white the stability to aging of material body has been played strengthening effect.
2, has good flame retardancy.The flame retardant rating of the utilization enhancing flame-retardant polyester material that the present invention produced is a 0.4mm UL94V-0 level.Can make the thick product of 0.4mm reach fire-retardant requirement, use this material can prepare aging-resistant electronics thin-walled, high temperature resistant, electric equipment products.
Below in conjunction with embodiment the present invention is described further.
Embodiment
With thermoplastic polyester, toughner, oxidation inhibitor, thermo-stabilizer, other auxiliary agent set of dispense ratio by weight; After in the high speed blender, mixing; Send in the main feeding in the twin screw extruder; The glass/glass fiber adds in the side direction feeding subsequently, through extrude, cooling, pelletizing, drying, packing and process.
When in the high speed blender, mixing, also main flame retardant can be added and fire retarding synergist is mixed together.
The length-to-diameter ratio of twin screw extruder screw rod is 25-50: 1, and the screw rod design temperature is 180-245 ℃, screw speed is set at 200-600 rev/min.
Each amounts of components of specific embodiment 1-6 and comparative example is seen table (consumption is a weight part in the table).
Figure BDA0000044169250000081
Figure BDA0000044169250000082
Figure BDA0000044169250000091
Experimental technique:
Plastic pellet is processed the batten that to survey tensile strength, electric breakdown strength, simple beam unnotched impact strength; Every six roots of sensation batten is one group; Measure initial value earlier, then with all battens in the baking oven of fixed temperature and humidity, keep the consistence of temperature all in the baking oven;, oven temperature carries out the relatively hot weathering test under being 200 ℃ condition then, regularly the changing value of (about about 15 days) test material each item performance index.
The product test performance is as shown in the table:
Figure BDA0000044169250000092
Figure BDA0000044169250000101
Figure BDA0000044169250000102
Figure BDA0000044169250000111
Figure BDA0000044169250000112
The product test performance is as shown in the table:
Figure BDA0000044169250000113
Figure BDA0000044169250000121
Consumption of the foregoing description and component can change, as:
In parts by weight, comprise following component:
130 parts of thermoplastic polyesters
Toughner 0-60 part (example 1,30,60)
Oxidation inhibitor 0.05-3.0 part (example 0.1,2,3)
Thermo-stabilizer 0.05-6.0 part (example 0.1,3,6)
Weighting agent 0-300 part (example 1,150,300)
Other auxiliary agent 0-12 part (example 1,6,12).
Said thermoplastic polyester is one or more in polyethylene terephthalate, poly terephthalic acid 1,4 butanediol ester, PEN, PBN, the polytrimethylene terephthalate;
Said toughner is one or more in ethene, ethene copolymer, vinyl grafting body, the ethylene-acrylate-SY-Monomer G;
Described oxidation inhibitor comprises primary antioxidant, auxiliary antioxidant; Primary antioxidant is a phenolic antioxidant; Auxiliary antioxidant is a phosphite ester kind antioxidant;
Said thermo-stabilizer is the thioesters type thermal stabilizing agent.
Filling modifying agent is one or more in spun glass, glass microballon, thomel, wollastonite, clay, zeolite, quartz, zeyssatite, silit, silicon oxide, mica, kaolin, calcium sulfate, permanent white, lime carbonate, talcum powder, Calucium Silicate powder, zinc oxide, zinc sulphide, the whisker;
Other auxiliary agent is one or more in lubricant, anti-dripping agent, static inhibitor, the tinting material.
Also can comprise following components in part by weight:
Main flame retardant 12-65 part (example 15,30,60)
Fire retarding synergist 4-22 part (example 5,15,22);
Said main flame retardant is that bromination epoxy, TDE, bromination gather carbon, brominated polyphenylene, brominated polystyrene, three (tribromophenoxy) triazine, the two tetrabromo phthalimides of ethylene, gather in the bromination pentabromobenzyl ester one or more.
Fire retarding synergist is the compound of Antimony Trioxide: 99.5Min, sodium antimonate, antimony peroxide, antimony organic class, in the hydration zinc borate one or more.

Claims (3)

1. polyester with resistant to thermal aging performance is characterized in that: in parts by weight, comprise following component:
Polyester is polybutylene terephthalate or polyethylene terephthalate; Polybutylene terephthalate density is 1.31-1.35g/cm 3, viscosity is 0.9-1.1dl/g, melt temperature 220-230 ℃, and content of carboxyl end group≤20 meq/kg; The specific density of polyester polyethylene terephthalate is 1.38g/cm 3
Main flame retardant is that bromination is gathered a kind of in carbon, the brominated polystyrene or two kinds;
Fire retarding synergist is an Antimony Trioxide: 99.5Min;
Toughner is LLDPE;
Oxidation inhibitor is the blend of primary antioxidant and assisted class oxidation inhibitor;
Thermo-stabilizer is DSTDP;
Weighting agent is a spun glass, and glass fiber diameter is the 5-20 micron, is the glass of handling through compound silane coupling agent, is short glass fiber.
2. the polyester with resistant to thermal aging performance according to claim 1 is characterized in that: other auxiliary agent is one or more in lubricant, anti-dripping agent, static inhibitor, the tinting material.
3. described working method of claim 1 with polyester of resistant to thermal aging performance; It is characterized in that: with thermoplastic polyester, toughner, oxidation inhibitor, thermo-stabilizer, other auxiliary agent set of dispense ratio by weight; After in the high speed blender, mixing; Send in the main feeding in the twin screw extruder, spun glass adds in the side direction feeding subsequently, through extrude, cooling, pelletizing, drying, packing and process; When in the high speed blender, mixing, also add main flame retardant and fire retarding synergist is mixed together; The length-to-diameter ratio of twin screw extruder screw rod is 25-50:1, and the screw rod design temperature is 180-245 ℃, and screw speed is set at 200-600 rev/min.
CN2011100200856A 2011-01-18 2011-01-18 Polyester having thermal ageing resistant performance and production method thereof Expired - Fee Related CN102093673B (en)

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CN113502564A (en) * 2021-06-07 2021-10-15 苏州海晨塑胶有限公司 Flame-retardant anti-dripping polyester material

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