CN103772952B - A kind of preparation method of multi-inlay section thermal plastic copolyesters modified polycarbonate alloy - Google Patents
A kind of preparation method of multi-inlay section thermal plastic copolyesters modified polycarbonate alloy Download PDFInfo
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- CN103772952B CN103772952B CN201410034006.0A CN201410034006A CN103772952B CN 103772952 B CN103772952 B CN 103772952B CN 201410034006 A CN201410034006 A CN 201410034006A CN 103772952 B CN103772952 B CN 103772952B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/911—Cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means 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
- B29C48/40—Means 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92533—Torque
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polyesters Or Polycarbonates (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of preparation method of multi-inlay section thermal plastic copolyesters modified polycarbonate alloy, particularly relate to a kind of preparation method with the polycarbonate alloy that chemical resistance is reacted and erosion resistance, thermostability, shock resistance and geometrical dimension are stable, belong to technical field of polymer materials.Present method with PC, PBT, antioxidant and multi-block copolyesters (PBT-PTEG-PCL copolyesters) for raw material, first dry pre-treatment is carried out to PC, PBT and PBT-PTEG-PCL copolyesters, then all raw materials are weighed by certain mass percent, compound is sent in twin screw extruder and is carried out melting, plasticizing, extrude through head, draw, cool, pelletizing, obtain product after oven dry.PC/PBT alloy prepared by the present invention has higher toughness and elongation at break, can be widely used in requirement and have chemical resistance reaction and erosion resistance, thermostability, shock resistance and geometrical dimension stable product.
Description
Technical field
The present invention relates to a kind of preparation method of multi-inlay section thermal plastic copolyesters modified polycarbonate alloy, particularly relate to a kind of preparation method with the polycarbonate alloy that chemical resistance is reacted and erosion resistance, thermostability, shock resistance and geometrical dimension are stable, belong to technical field of polymer materials.
Background technology
Engineering plastic alloy utilizes the method for physical blending or chemical graft and a class novel material of the high-performance obtained, functionalization, customizations.Polyblend product can be widely used in the fields such as automobile, electronics, precision instrument, office equipment, wrapping material, material of construction.It can improve or improve the performance of existing plastics and reduce costs, and has become one of kind enlivened the most in plastics industry at present, has increased very rapid.
Polycarbonate (hereinafter referred to as PC) is one of five large general engineering plastic, and its output and consumption are only second to PA, occupy second.The alloying process of PC makes its performance more perfect and is more widely used, and the novel PC alloy of large quantities of excellent property has been put on market and has been applied.Each major company has competitively formulated new exploitation problem in the world at present, shows the bright prospects of the new PC alloy kind of exploitation.
Main PC alloy has: PC/PBT, PC/ABS, PC/PET, and wherein compatibilization techniques is the key of PC alloy research.The consistency improving polymer blending alloy by adding compatilizer is the most active method of Recent study, develops multiple high-performance, multi-functional PC alloy thus.At present to the research of PC alloy compatilizer mainly based on following a few class: the grafts of MBS, SMA, ABS, Graft Polyolefin, SAN grafting secondary amine functional groups and two-pack expanding material etc.
Polycarbonate (PC) and polybutylene terephthalate (PBT) are all the thermoplastic engineering plastics of high comprehensive performance, the blend of the two has higher mechanical strength and heat-drawn wire, and good solvent resistance, wear resistance, stress cracking resistance, dimensional stability and processing fluidity, can be used for the plate etc. of bumper, car body panel and other various apparatuses.But PC/PBT blend alloy also has some shortcomings to need to improve, and the requirement that such as notched Izod impact strength is low, intensity can not meet full-sized car component, therefore, needs to carry out toughness reinforcing and enhancing modified to it; Toughness is lower because consistency is bad for PC/PBT blend alloy simultaneously, needs to carry out capacity increasing modifying.
The existing research for the toughness reinforcing increase-volume of PC/PBT blend alloy at present, the raising further but its over-all properties is still needed.
US5484846,5546842 etc., adopts the MBS(butadiene-styrene-methylmethacrylate copolymer of nucleocapsid structure) to PBT/PC alloy, there is significant low-temperature impact modified effect, but MBS needs the amount higher (reaching 20wt%) that adds.Its reason may be do not have suitable interfacial interaction between traditional MBS and PC/PBT alloy, therefore the consistency of MBS and alloy is lower, thus limits the toughening effect of MBS.And MBS add-on too conference has a negative impact to physicals (as heat-drawn wire etc.); In MBS, undersaturated PB component also can damage the weathering resistance of material.
In recent years, investigated novel PC/PBT toughner both at home and abroad, as the AX8900 (ethylene-methyl acrylate-GMA multipolymer) of French A Kema company, both PTW and PT862(of du pont company are Ethylene-butyl Acrylate-methacrylic Acid Glycerin Ester Copolymer) and the KT22(ethylene-methyl acrylate-GMA multipolymer of Shenyang China Ke Tong plastic cement scientific & technical corporation) and other KT series product etc., the toughner used is ethene, the copolymer elastomer of acrylate and GMA, gather the toughness of olefinic rubber, the consistency of polyacrylic ester and PC and PBT and epoxide group and PBT hold the increasing reaction of position group (carboxyl or hydroxyl) in one, realize the increase-volume to PC/PBT blend alloy, toughness reinforcing, Be very effective.
Summary of the invention
The object of the invention is the preparation method proposing a kind of multi-block copolyesters modified polycarbonate alloy, using thermoplastic multi-block's copolyesters as properties-correcting agent, improve the consistency of the notched Izod impact strength of polyester-polycarbonate alloy and polyester, polycarbonate, obtained product can meet chemical resistance reaction and the stable application requiring of erosion resistance, thermostability, shock resistance and geometrical dimension.
The preparation method of the multi-inlay section thermal plastic copolyesters modified polycarbonate alloy that the present invention proposes, comprises the following steps:
(1) polycarbonate alloy raw materials used in the mass percent of each component be:
Polycarbonate, polybutylene terephthalate and polybutylene terephthalate-PTMG-polycaprolactone copolyesters is weighed by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials be less than 0.05%, be cooled to room temperature;
(2) weigh the first oxidation inhibitor 1 by above-mentioned mass percent, then fully mix with other components being cooled to room temperature, obtain compound;
(3) melting, plasticizing is carried out by the compound of step (2) feeding twin screw extruder, extrude through head, draw, cool, pelletizing, multi-block copolyesters modified polycarbonate alloy is obtained after oven dry, wherein the temperature in twin screw 1 ~ 5 district is respectively: 270 DEG C, 265 DEG C, 260 DEG C, 255 DEG C and 250 DEG C, engine speed is 200 revs/min, and moment of torsion is 60 ~ 70.
In above-mentioned preparation method, the preparation method of described polybutylene terephthalate-PTMG-polycaprolactone copolyesters comprises the following steps:
(1) by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, additional proportion is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1:1.8-2.0:0.1-0.2:0.1-0.2(mol ratio), the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.1 ~ 0.3%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.01% ~ 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
(2) after transesterification reaction terminates, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
(3) in reactor, nitrogen is passed into; system pressure is made to return to normal pressure; open the lower bottom valve of reactor; maintain reactor pressure at 0.3MPa; nitrogen pressure makes finished product extrude reactor mouth mould; and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle.
In above-mentioned preparation method, in the first described oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 20% ~ 30%, phosphite ester kind antioxidant 50% ~ 60%, monothioester kind antioxidant 10% ~ 20%.Wherein said Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.Described phosphite ester kind antioxidant is two octadecyl pentaerythritol diphosphites.Described thiosulfates kind antioxidant is Tyox B.
In above-mentioned preparation method, in the second described oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 40% ~ 60%, phosphite ester kind antioxidant 40% ~ 60%.Described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.Described phosphite ester kind antioxidant is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
The preparation method of the multi-inlay section thermal plastic copolyesters modified polycarbonate alloy that the present invention proposes, its advantage is: multi-inlay section thermal plastic copolyesters modified polycarbonate alloy prepared by the inventive method, by hard section and the soft section of multi-block copolyesters formed, wherein soft section provides elasticity and flexibility, hard section provides intensity and rigidity, forms the structure of microphase-separated; Wherein soft section is low-molecular-weight PTMEG-PCL multipolymer dibasic alcohol, and hard section is then made up of PBT.PBT-PETG-PCL copolyesters has snappiness due to it, can be used for carrying out blending and modifying to improve the toughness of polymkeric substance to polymkeric substance.The second-order transition temperature of polytetrahydrofuran is very low (-86 DEG C), and polycaprolactone (PCL) and PC have good consistency.Polytetrahydrofuran and polycaprolactone, all have excellent mechanical property.Polybutylene terephthalate-PTMG-polycaprolactone copolyesters thermoplastic polyester elastomer is not only containing polybutylene terephthalate but also containing polycaprolactone, not only good with polycarbonate, polybutylene terephthalate consistency, and polycarbonate and polybutylene terephthalate system are had to the effect of good solubilizing agent, the consistency of polycarbonate and polybutylene terephthalate can be improved.Due to polybutylene terephthalate-PTMG-polycaprolactone copolyesters thermoplastic polyester elastomer and PBT consistency good, itself and PBT are blended, obviously can improve notched Izod impact strength and the elongation at break of PBT.
Multi-inlay section thermal plastic copolyesters modified polycarbonate alloy prepared by the inventive method, both the characteristic having maintained former TPEE turn increases the segment compatible with PC, therefore for PC/PBT alloy, both improve the interface performance that blending extrudant mechanical property which in turn improves alloy.
Embodiment
The preparation method of the multi-inlay section thermal plastic copolyesters modified polycarbonate alloy that the present invention proposes, comprises the following steps:
(1) polycarbonate alloy raw materials used in the mass percent of each component be:
Polycarbonate, polybutylene terephthalate and polybutylene terephthalate-PTMG-polycaprolactone copolyesters is weighed by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials be less than 0.05%, be cooled to room temperature;
(2) weigh the first oxidation inhibitor 1 by above-mentioned mass percent, then fully mix with other components being cooled to room temperature, obtain compound;
(3) melting, plasticizing is carried out by the compound of step (2) feeding twin screw extruder, extrude through head, draw, cool, pelletizing, multi-block copolyesters modified polycarbonate alloy is obtained after oven dry, wherein the temperature in twin screw 1 ~ 5 district is respectively: 270 DEG C, 265 DEG C, 260 DEG C, 255 DEG C and 250 DEG C, engine speed is 200 revs/min, and moment of torsion is 60 ~ 70.
In above-mentioned preparation method, the preparation method of described polybutylene terephthalate-PTMG-polycaprolactone copolyesters comprises the following steps:
(1) by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, additional proportion is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1:1.8-2.0:0.1-0.2:0.1-0.2(mol ratio), the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.1 ~ 0.3%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.01% ~ 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
(2) after transesterification reaction terminates, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
(3) in reactor, nitrogen is passed into; system pressure is made to return to normal pressure; open the lower bottom valve of reactor; maintain reactor pressure at 0.3MPa; nitrogen pressure makes finished product extrude reactor mouth mould; and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle.
In above-mentioned preparation method, in the first described oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 20% ~ 30%, phosphite ester kind antioxidant 50% ~ 60%, monothioester kind antioxidant 10% ~ 20%.Wherein said Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).Described phosphite ester kind antioxidant is two octadecyl pentaerythritol diphosphites (oxidation inhibitor 619).Described thiosulfates kind antioxidant is Tyox B (DLTP).
In above-mentioned preparation method, in the second described oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 40% ~ 60%, phosphite ester kind antioxidant 40% ~ 60%.Described Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010).Described phosphite ester kind antioxidant is two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites (oxidation inhibitor 627A).
Below introduce the embodiment of the inventive method:
Embodiment 1: prepare polybutylene terephthalate-PTMG-polycaprolactone copolyesters.
(1) by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, additional proportion is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1/1.8/0.1/0.1, the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.2%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
(2) after transesterification reaction terminates, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
(3) in reactor, nitrogen is passed into; system pressure is made to return to normal pressure; open the lower bottom valve of reactor; maintain reactor pressure at 0.3MPa; nitrogen pressure makes finished product extrude reactor mouth mould; and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle.
Embodiment 2: prepare polybutylene terephthalate-PTMG-polycaprolactone copolyesters
(1) by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, additional proportion is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1/1.8/0.15/0.1, the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.2%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
(2) after transesterification reaction terminates, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
(3) in reactor, nitrogen is passed into; system pressure is made to return to normal pressure; open the lower bottom valve of reactor; maintain reactor pressure at 0.3MPa; nitrogen pressure makes finished product extrude reactor mouth mould; and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle.
Embodiment 3: prepare polybutylene terephthalate-PTMG-polycaprolactone copolyesters
(1) by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, additional proportion is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1/1.8/0.15/0.15, the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.2%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
(2) after transesterification reaction terminates, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
(3) in reactor, nitrogen is passed into; system pressure is made to return to normal pressure; open the lower bottom valve of reactor; maintain reactor pressure at 0.3MPa; nitrogen pressure makes finished product extrude reactor mouth mould; and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle.
Embodiment 4: prepare polybutylene terephthalate-PTMG-polycaprolactone copolyesters
(1) by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, additional proportion is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1/1.8/0.0.2/0.15, the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.2%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
(2) after transesterification reaction terminates, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
(3) in reactor, nitrogen is passed into; system pressure is made to return to normal pressure; open the lower bottom valve of reactor; maintain reactor pressure at 0.3MPa; nitrogen pressure makes finished product extrude reactor mouth mould; and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle.
Embodiment 5: prepare polybutylene terephthalate-PTMG-polycaprolactone copolyesters
(1) by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, additional proportion is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1/1.8/0.2/0.2, the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.2%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
(2) after transesterification reaction terminates, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
(3) in reactor, nitrogen is passed into; system pressure is made to return to normal pressure; open the lower bottom valve of reactor; maintain reactor pressure at 0.3MPa; nitrogen pressure makes finished product extrude reactor mouth mould; and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle.
Embodiment 6: prepare multi-block copolyesters modified polycarbonate alloy:
(1) polycarbonate alloy raw materials used in the mass percent of each component be:
Polycarbonate, polybutylene terephthalate and polybutylene terephthalate-PTMG-polycaprolactone copolyesters is weighed by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials be less than 0.05%, be cooled to room temperature;
(2) weigh the first oxidation inhibitor 1 by above-mentioned mass percent, then fully mix with other components being cooled to room temperature, obtain compound;
(3) melting, plasticizing is carried out by the compound of step (2) feeding twin screw extruder, extrude through head, draw, cool, pelletizing, multi-block copolyesters modified polycarbonate alloy is obtained after oven dry, wherein the temperature in twin screw 1 ~ 5 district is respectively: 270 DEG C, 265 DEG C, 260 DEG C, 255 DEG C and 250 DEG C, engine speed is 200 revs/min, and moment of torsion is 60 ~ 70.
Embodiment 7: prepare multi-block copolyesters modified polycarbonate alloy
(1) polycarbonate alloy raw materials used in the mass percent of each component be:
Polycarbonate, polybutylene terephthalate and polybutylene terephthalate-PTMG-polycaprolactone copolyesters is weighed by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials be less than 0.05%, be cooled to room temperature;
(2) weigh the first oxidation inhibitor 1 by above-mentioned mass percent, then fully mix with other components being cooled to room temperature, obtain compound;
(3) melting, plasticizing is carried out by the compound of step (2) feeding twin screw extruder, extrude through head, draw, cool, pelletizing, multi-block copolyesters modified polycarbonate alloy is obtained after oven dry, wherein the temperature in twin screw 1 ~ 5 district is respectively: 270 DEG C, 265 DEG C, 260 DEG C, 255 DEG C and 250 DEG C, engine speed is 200 revs/min, and moment of torsion is 60 ~ 70.
Embodiment 8: prepare multi-inlay section thermal plastic copolyesters modified polycarbonate alloy.
Polycarbonate alloy raw materials used in the mass percent of each component be:
Its preparation method comprises the following steps:
(1). weigh PC, PBT, PBT-PTMEG-PCL copolyesters by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials all below 0.05%, be then cooled to room temperature;
(2). weigh composite antioxidant by above-mentioned per-cent, then fully mix with the various resins being cooled to room temperature;
(3). the compound that step (2) obtained is sent in twin screw extruder and is carried out melting, plasticizing, extrudes, draws, cools, pelletizing through head, obtains product after oven dry, wherein each district of twin screw (1st ~ 5 district) temperature is respectively: 270 DEG C, 265 DEG C, 260 DEG C 255 DEG C, 250 DEG C; Engine speed 200 revs/min, moment of torsion is 60 ~ 70.
Embodiment 9: prepare multi-inlay section thermal plastic copolyesters modified polycarbonate alloy.
Polycarbonate alloy raw materials used in the mass percent of each component be:
Its preparation method comprises the following steps:
(1). weigh PC, PBT, PBT-PTMEG-PCL copolyesters by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials all below 0.05%, be then cooled to room temperature;
(2). weigh composite antioxidant by above-mentioned per-cent, then fully mix with the various resins being cooled to room temperature;
(3). the compound that step (2) obtained is sent in twin screw extruder and is carried out melting, plasticizing, extrudes, draws, cools, pelletizing through head, obtains product after oven dry, wherein each district of twin screw (1st ~ 5 district) temperature is respectively: 270 DEG C, 265 DEG C, 260 DEG C 255 DEG C, 250 DEG C; Engine speed 200 revs/min, moment of torsion is 60 ~ 70.
Embodiment 10: prepare multi-inlay section thermal plastic copolyesters modified polycarbonate alloy.
Polycarbonate alloy raw materials used in the mass percent of each component be:
Its preparation method comprises the following steps:
(1) PC, PBT, PBT-PTMEG-PCL copolyesters is weighed by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials all below 0.05%, be then cooled to room temperature;
(2) weigh composite antioxidant by above-mentioned per-cent, then fully mix with the various resins being cooled to room temperature;
(3) compound that step (2) obtained is sent in twin screw extruder and is carried out melting, plasticizing, extrudes, draws, cools, pelletizing through head, obtains product after oven dry, wherein each district of twin screw (1st ~ 5 district) temperature is respectively: 270 DEG C, 265 DEG C, 260 DEG C 255 DEG C, 250 DEG C; Engine speed 200 revs/min, moment of torsion is 60 ~ 70.
Comparative example
Comparative example: prepare polycarbonate alloy.
Polycarbonate alloy raw materials used in the mass percent of each component be:
Polycarbonate (PC) 71.9%
Polybutylene terephthalate (PBT) 27.6%
First oxidation inhibitor 0.5%
Its preparation method comprises the following steps:
(1) PC, PBT is weighed by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials all below 0.05%, be then cooled to room temperature;
(2) weigh composite antioxidant by above-mentioned per-cent, then fully mix with the various resins being cooled to room temperature;
(3) compound that step (2) obtained is sent in twin screw extruder and is carried out melting, plasticizing, extrudes, draws, cools, pelletizing through head, obtains product after oven dry, wherein each district of twin screw (1st ~ 5 district) temperature is respectively: 270 DEG C, 265 DEG C, 260 DEG C 255 DEG C, 250 DEG C; Engine speed 200 revs/min, moment of torsion is 60 ~ 70.
The raw material sources used in the embodiment of the present invention is as follows:
Polycarbonate, produced by Shanghai Bayer company, product type is 2850;
Polybutylene terephthalate, produced by Changchun, Taiwan chemical industrial company, product type is 1100-211M;
In first oxidation inhibitor, the antioxidant 1010 that Hinered phenols antioxidant provides for Co., Ltd in Ciba, the oxidation inhibitor 619 that phosphite ester kind antioxidant provides for GE company of the U.S., the anti-oxidant DLTP that thiosulfates kind antioxidant provides for Ningbo gold Hai Yabao company limited.
In second oxidation inhibitor, the antioxidant 1010 that Hinered phenols antioxidant provides for Co., Ltd in Ciba, the oxidation inhibitor 627A that phosphite ester kind antioxidant provides for Compton Co., Ltd of the U.S.,
PTMG, produced by PTG company of Korea S, product type is PTMEG-1000,
Polycaprolactone, produced by company limited of Britain of Sweden, product type is capa
tA7201A.
Table 1. multi-block copolyesters modified polycarbonate alloy product performance test results
As can be seen from the table, the multi-block copolyesters (PBT-PTMEG-PCL) utilizing the present invention to prepare is as the compatibilization and toughening agent of PC/PBT alloy, and effectively improve the processing fluidity of alloy, improve the toughness of material, normal temperature notch shock is strong
Degree improves 4 ~ 5 times, and along with the increase of content of soft segmer in copolyesters, elongation at break increases substantially.
Claims (4)
1. a preparation method for multi-inlay section thermal plastic copolyesters modified polycarbonate alloy, is characterized in that the method comprises the following steps:
(1) polycarbonate alloy raw materials used in the mass percent of each component be:
Polycarbonate, polybutylene terephthalate and polybutylene terephthalate-PTMG-polycaprolactone copolyesters is weighed by above-mentioned mass percent, and at 120 DEG C dry 2 hours, make the water ratio of above-mentioned raw materials be less than 0.05%, be cooled to room temperature;
(2) weigh the first oxidation inhibitor by above-mentioned mass percent, then fully mix with other components being cooled to room temperature, obtain compound;
(3) melting, plasticizing is carried out by the compound of step (2) feeding twin screw extruder, extrude through head, draw, cool, pelletizing, multi-block copolyesters modified polycarbonate alloy is obtained after oven dry, wherein the temperature in twin screw 1 ~ 5 district is respectively: 270 DEG C, 265 DEG C, 260 DEG C, 255 DEG C and 250 DEG C, engine speed is 200 revs/min, and moment of torsion is 60 ~ 70;
The preparation method of wherein said polybutylene terephthalate-PTMG-polycaprolactone copolyesters comprises the following steps:
A () is by the dimethyl terephthalate (DMT) after metering, 1, 4-butyleneglycol, PTMG, polycaprolactone joins in polymerization reaction kettle, the mol ratio added is: dimethyl terephthalate (DMT): 1, 4-butyleneglycol: PTMG: polycaprolactone=1:1.8-2.0:0.1-0.2:0.1-0.2, the number-average molecular weight of PTMG is 1000, the number-average molecular weight of polycaprolactone (PCL) is 1000, 150 DEG C are heated in nitrogen atmosphere, stirring 15 minutes is continued again after stirring and dissolving, then in reactor, catalyzer tetrabutyl titanate and the second oxidation inhibitor is added, the ratio added is: the mass percent that tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.1 ~ 0.3%, the mass percent that second oxidation inhibitor accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.01% ~ 0.03%, transesterification reaction is carried out under the protection of nitrogen, transesterification reaction temperature is 200 ~ 230 DEG C, the transesterification reaction time is 100-200 minute, the top temperature of reactor top splitter is at 65 ~ 70 DEG C, remove the small molecules product that transesterification reaction is formed,
B () transesterification reaction terminates after, add catalyzer tetrabutyl titanate, additional proportion is: the mass percent that catalyzer tetrabutyl titanate accounts for polybutylene terephthalate-PTMG-polycaprolactone copolyesters finished product is 0.5%, temperature is risen to 250-260 DEG C, vacuumize, in two hours, make the vacuum tightness of system reach 70Pa, react while stirring, the reaction times is 2-3 hour;
C () passes into nitrogen in reactor, system pressure is made to return to normal pressure, open the lower bottom valve of reactor, maintain reactor pressure at 0.3MPa, nitrogen pressure makes finished product extrude reactor mouth mould, and pulling into material strip, material strip uses dicing machine pelletizing after water cooling, obtains polybutylene terephthalate-PTMG-polycaprolactone copolyesters particle;
In the first wherein said oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 20% ~ 30%, phosphite ester kind antioxidant 50% ~ 60%, monothioester kind antioxidant 10% ~ 20%;
In the second wherein said oxidation inhibitor, the weight percent of each component is: Hinered phenols antioxidant 40% ~ 60%, phosphite ester kind antioxidant 40% ~ 60%.
2. preparation method as claimed in claim 1, is characterized in that wherein said Hinered phenols antioxidant is four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester.
3. preparation method as claimed in claim 1, it is characterized in that the phosphite ester kind antioxidant in the first wherein said oxidation inhibitor is two octadecyl pentaerythritol diphosphites, phosphite ester kind antioxidant in second oxidation inhibitor is two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
4. preparation method as claimed in claim 1, is characterized in that wherein said thiosulfates kind antioxidant is Tyox B.
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| CN103122135A (en) * | 2013-01-31 | 2013-05-29 | 深圳市亚塑科技有限公司 | PC-PBT (polycarbonate-polybutylene terephthalate) hybrid alloy and preparation method thereof |
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| CN103122135A (en) * | 2013-01-31 | 2013-05-29 | 深圳市亚塑科技有限公司 | PC-PBT (polycarbonate-polybutylene terephthalate) hybrid alloy and preparation method thereof |
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