CN103694654B - A kind of fast crystallization, high tenacity fiberglass reinforced PET composite material and preparation method thereof - Google Patents
A kind of fast crystallization, high tenacity fiberglass reinforced PET composite material and preparation method thereof Download PDFInfo
- Publication number
- CN103694654B CN103694654B CN201310694395.5A CN201310694395A CN103694654B CN 103694654 B CN103694654 B CN 103694654B CN 201310694395 A CN201310694395 A CN 201310694395A CN 103694654 B CN103694654 B CN 103694654B
- Authority
- CN
- China
- Prior art keywords
- pet
- pbt
- screw extruder
- crystallization
- twin screw
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- B29C2948/92885—Screw or gear
-
- 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
-
- 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
- B29C2948/92923—Calibration, after-treatment or cooling zone
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The present invention relates to a kind of fast crystallization, high tenacity fiberglass reinforced PET composite material, described PET composite material is composed of the following components by weight: PET100 part, reactive anti-impact modifier 5 ~ 10 parts, crystalline modified master batch 10 ~ 20 parts, 15 ~ 30 parts, glass fibre, processing aid 0.5 ~ 1 part.Present invention also offers the preparation method of PET composite material.The present invention compared with prior art, masterbatch method technology and reactive blending modification technology combine by the present invention, more effectively optimize crystal property and the toughness of PET material, obtain the mechanical property of fiberglass reinforced PET composite material, thermal characteristics and excellent size stability, processing forming is good, and in toughness, has outstanding advantage.
Description
Technical field
The present invention relates to a kind of PET composite material, be specifically related to a kind of fast crystallization, high tenacity fiberglass reinforced PET composite material and preparation method thereof.
Background technology
Polyethylene terephthalate (PET) is a kind of thermoplastic engineering plastic of semicrystalline, has excellent mechanical property, electrical property, thermotolerance etc.PET is maximum, the cheapest kind of output in thermoplastic polyester, has broad application prospects, but due to main chain rigidity larger, sub-chain motion is slow, its Tc is high, crystallization velocity slow, and shaping cycle is long, Mo Wengao, and heat-drawn wire affects greatly by crystallization.Meanwhile, notched Izod impact strength is low is limit its another defect as engineering plastics application, therefore significantly limit its application in engineering plastics field.Study on the modification mainly concentrates on and adds crystallization nucleating agent and accelerate its crystallization velocity and improve the aspect such as shock strength by blending and modifying.
The molecular weight of PET is the important factor affecting material property, the crystal property of molecular weight height material worsens, and toughness improves, both limit to a certain extent mutually, current most of research work focus mostly on simple raising PET composite material toughness or improve the crystal property of PET.On the other hand, for the improvement of PET composite material crystal property, prior art still has some limitations, as provided a kind of method being improved PET crystal property by interpolation nucleator and crystallization promoter in CN 102504500 A, improvement degree, by the restriction of material scatter, provides similar method in CN 102827462 A and CN 102040808 A.For PET this problem toughness reinforcing, current great majority work concentrates on simple method of adding toughner, toughening effect declines with the increase of toughner content after reaching certain value on the contrary, simultaneously, some work adopts the method for alloying as PET/PC alloy, adopt the cost of this kind of method material significantly to rise and the course of processing can be caused complicated, a kind of preparation method of super tough PET/PBT/PC alloy is provided in CN102061076A, the introducing of PC improves the toughness of alloy, the introducing of PBT improves crystal property to a certain extent, the method of alloying can only improve crystallinity and the toughness of PET to a certain extent, improvement degree is by the restriction of PC and PBT ratio of component, substantially increase the cost of material simultaneously.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of fast crystallization, high tenacity fiberglass reinforced PET composite material are provided.
Of the present invention again one object be that the preparation method of a kind of fast crystallization, high tenacity fiberglass reinforced PET composite material is provided.
For achieving the above object, the technical scheme taked of the present invention is as follows:
A fiberglass reinforced PET composite material for fast crystallization, high tenacity, it is made up of following component and content:
PET 100 parts
Reactive anti-impact modifier 5 ~ 10 parts
Crystalline modified master batch 10 ~ 20 parts
15 ~ 30 parts, glass fibre
Processing aid 0.5 ~ 1 part
The limiting viscosity of described PET is 0.75 ~ 0.85dL/g.
Described reactive anti-impact modifier is the mixture of toughner (one in EPDM-g-GMA, POE-g-MAH or LLDPE-g-MAH) and PET tackifier (one in pyromellitic acid anhydride or two oxazoline group benzene) with reactive group, and its combined weight is than being 3:2 ~ 4:1.The toughner introduced with reactive group adds on the one hand the binding ability of toughner and matrix, improve toughner dispersiveness in the base on the other hand, introducing tackifier is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Described crystalline modified master batch take PBT as matrix, and structural similitude, the consistency of one side PBT and PET are good, and another aspect PBT adds the sub-chain motion ability that can improve PET, plays a part crystallization promoter to a certain extent.Crystallization nucleating agent (one in talcum powder, nano imvite or calcium carbonate) and crystallization promoter (one in polyoxyethylene glycol PEG6000 or polyethers P1000) are dispersed component, the limiting viscosity of described PBT is 1.0dL/g, and described PBT, crystallization nucleating agent and crystallization promoter weight ratio are 6:4:1 ~ 8:4:1.Improving the crystal property of PET by adding crystalline modified master batch, compared with traditional addition manner, greatly increasing the dispersity of crystallization nucleating agent and crystallization promoter, thus improve the utilising efficiency of crystallization nucleating agent and crystallization promoter.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
For realizing above-mentioned second object, the technical scheme that the present invention takes is:
The preparation method of fiberglass reinforced PET composite material comprises the steps:
The preparation of (a) crystalline modified master batch: described PBT at 100 ~ 120 DEG C dry 5 ~ 6 hours, ratio of component takes PBT, crystallization nucleating agent and crystallization promoter as described above, and it is mixed 3 ~ 5min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrude through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200 ~ 400r/min, and each district temperature of twin screw extruder controls at 210 ~ 240 DEG C;
The drying of (b) raw material and mixing: by described PET and crystalline modified master batch at 100 ~ 120 DEG C dry 5 ~ 6 hours, ratio of component claimed to remove all the other components beyond glass fibre as described above, and mixes 3 ~ 5min in high-speed mixer;
(c) Screw Extrusion: mixed for step (b) material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200 ~ 400r/min, and each district temperature of twin screw extruder controls at 220 ~ 250 DEG C.
The limiting viscosity of described PET is 0.75 ~ 0.85dL/g, described toughner is selected from EPDM-g-GMA, one in POE-g-MAH or LLDPE-g-MAH, described PET tackifier are selected from the one in pyromellitic acid anhydride or two oxazoline group benzene, described crystallization nucleating agent is selected from talcum powder, one in nano imvite or calcium carbonate, described crystallization promoter is selected from the one in polyoxyethylene glycol PEG6000 or polyethers P1000, described glass fibre is that alkali-free is long fine, described fiberglass surfacing is through silane coupling agent process, described processing aid is terephthalic acid cyclobutanediol ester.
beneficial effect of the present invention:
1. be that matrix prepares crystalline modified master batch with PBT, compared with prior art, masterbatch method improves crystallization nucleating agent and the dispersiveness of crystallization promoter in resin matrix on the one hand, the structural similitude of PBT and PET on the other hand, but good compared with the kindliness of PET, the introducing of a small amount of PBT serves the effect of crystallization promoter.
2. PET tackifier and the composite obtained reactive anti-impact modifier of toughner with reactive group, break through traditional toughening modifying method, the method extruded by reactively blending realizes the super malleableize of PET material.
3. masterbatch method technology and reactive blending modification technology are combined, effectively optimize crystal property and the toughness of PET material simultaneously, obtain the mechanical property of fiberglass reinforced PET composite material, thermal characteristics and excellent size stability, processing forming is good, and in toughness, has outstanding advantage.
Embodiment
Below in conjunction with embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Embodiment 1
A fiberglass reinforced PET composite material for fast crystallization, high tenacity, it is made up of following component and content:
PET 100 parts
Reactive anti-impact modifier 5 parts
Crystalline modified master batch 10 parts
15 parts, glass fibre
Processing aid 0.5 part
The limiting viscosity of described PET is 0.75dL/g.
Described reactive anti-impact modifier is the mixture of EPDM-g-GMA and PET tackifier pyromellitic acid anhydride, and its combined weight is than being 3:2.Introduce the binding ability adding EPDM-g-GMA and matrix with toughner EPDM-g-GMA mono-aspect of reactive group, improve EPDM-g-GMA dispersiveness in the base on the other hand, introducing tackifier pyromellitic acid anhydride is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Described crystalline modified master batch take PBT as matrix, and structural similitude, the consistency of one side PBT and PET are good, and another aspect PBT adds the sub-chain motion ability that can improve PET, plays a part crystallization promoter to a certain extent.Crystallization nucleating agent talcum powder and crystallization promoter polyoxyethylene glycol PEG6000 are dispersed component, and the limiting viscosity of described PBT is 1.0dL/g, and described PBT, talcum powder and PEG6000 weight ratio are 6:4:1.Improving the crystal property of PET by adding crystalline modified master batch, compared with traditional addition manner, greatly increasing the dispersity of talcum powder and polyoxyethylene glycol PEG6000, thus improve the utilising efficiency of talcum powder and PEG6000.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.The long fibre of this surface-treated alkali-free is bought in megalith group.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
Described preparation method comprises the steps:
(1) preparation of crystalline modified master batch: described PBT at 100 DEG C dry 5 hours, ratio of component takes PBT, talcum powder and polyoxyethylene glycol PEG6000 as described above, and it is mixed 3min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrudes through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 210 DEG C;
(2) drying of raw material and mixing: by described PET and crystalline modified master batch at 100 DEG C dry 5 hours, ratio of component took all the other components except glass fibre as described above, and mixes 3min in high-speed mixer;
(3) Screw Extrusion: step (2) mixed material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 220 DEG C.
Embodiment 2
A fiberglass reinforced PET composite material for fast crystallization, high tenacity, it is made up of following component and content:
PET 100 parts
Reactive anti-impact modifier 10 parts
Crystalline modified master batch 20 parts
30 parts, glass fibre
Processing aid 1 part
The limiting viscosity of described PET is 0.85dL/g.
Described reactive anti-impact modifier is that its combined weight is than being 4:1 with the mixture in the toughner LLDPE-g-MAH of reactive group and the two oxazoline group benzene of PET tackifier.Introduce the binding ability adding LLDPE-g-MAH and matrix with toughner LLDPE-g-MAH mono-aspect of reactive group, improve LLDPE-g-MAH dispersiveness in the base on the other hand, introducing the two oxazoline group benzene of tackifier is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Described crystalline modified master batch take PBT as matrix, and structural similitude, the consistency of one side PBT and PET are good, and another aspect PBT adds the sub-chain motion ability that can improve PET, plays a part crystallization promoter to a certain extent.Crystallization nucleating agent calcium carbonate and crystallization promoter polyethers P1000 are dispersed component, and the limiting viscosity of described PBT is 1.0dL/g, and described PBT, calcium carbonate and polyethers P1000 weight ratio are 8:4:1.Improving the crystal property of PET by adding crystalline modified master batch, compared with traditional addition manner, greatly increasing the dispersity of calcium carbonate and polyethers P1000, thus improve the utilising efficiency of calcium carbonate and polyethers P1000.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
Described preparation method comprises the steps:
(1) preparation of crystalline modified master batch: described PBT at 120 DEG C dry 6 hours, ratio of component takes PBT, calcium carbonate and polyethers P1000 as described above, and it is mixed 5min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrudes through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 400r/min, and each district temperature of twin screw extruder controls at 240 DEG C;
(2) drying of raw material and mixing: by described PET and crystalline modified master batch at 120 DEG C dry 6 hours, ratio of component claimed to remove all the other components beyond glass fibre as described above, and mixes 5min in high-speed mixer;
(3) Screw Extrusion: step (2) mixed material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 400r/min, and each district temperature of twin screw extruder controls at 250 DEG C.
Embodiment 3
A fiberglass reinforced PET composite material for fast crystallization, high tenacity, it is made up of following component and content:
PET 100 parts
Reactive anti-impact modifier 8 parts
Crystalline modified master batch 15 parts
20 parts, glass fibre
Processing aid 0.7 part
The limiting viscosity of described PET is 0.8dL/g.
Described reactive anti-impact modifier is the mixture of toughner POE-g-MAH with reactive group and PET tackifier pyromellitic acid anhydride, and its combined weight is 3:1.Introduce the binding ability adding POE-g-MAH and matrix with toughner POE-g-MAH mono-aspect of reactive group, improve POE-g-MAH dispersiveness in the base on the other hand, introducing pyromellitic acid anhydride is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Described crystalline modified master batch take PBT as matrix, and structural similitude, the consistency of one side PBT and PET are good, and another aspect PBT adds the sub-chain motion ability that can improve PET, plays a part crystallization promoter to a certain extent.Crystallization nucleating agent nano imvite and crystallization promoter polyoxyethylene glycol PEG6000 are dispersed component, and the limiting viscosity of described PBT is 1.0dL/g, and described PBT, nano imvite and polyoxyethylene glycol PEG6000 weight ratio are 6:4:1 ~ 8:4:1.Improving the crystal property of PET by adding crystalline modified master batch, compared with traditional addition manner, greatly increasing the dispersity of nano imvite and polyoxyethylene glycol PEG6000, thus improve the utilising efficiency of nano imvite and polyoxyethylene glycol PEG6000.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
Described preparation method comprises the steps:
(1) preparation of crystalline modified master batch: described PBT at 110 DEG C dry 6 hours, ratio of component takes PBT, nano imvite and polyoxyethylene glycol PEG6000 as described above, and it is mixed 4min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrudes through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 300r/min, and each district temperature of twin screw extruder controls at 225 DEG C;
(2) drying of raw material and mixing: by described PET and crystalline modified master batch at 110 DEG C dry 5 hours, ratio of component claimed to remove all the other components beyond glass fibre as described above, and mixes 4min in high-speed mixer;
(3) Screw Extrusion: step (2) mixed material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 300r/min, and each district temperature of twin screw extruder controls at 240 DEG C.
Embodiment 4
A fiberglass reinforced PET composite material for fast crystallization, high tenacity, it is made up of following component and content:
PET 100 parts
Reactive anti-impact modifier 6 parts
Crystalline modified master batch 12 parts
30 parts, glass fibre
Processing aid 0.5 part
The limiting viscosity of described PET is 0.75dL/g.
Described reactive anti-impact modifier is the mixture with the toughner EPDM-g-GMA of reactive group and the two oxazoline group benzene of PET tackifier, and its combined weight is than being 2:1.Introduce the binding ability adding EPDM-g-GMA and matrix with toughner EPDM-g-GMA mono-aspect of reactive group, improve EPDM-g-GMA dispersiveness in the base on the other hand, introducing two oxazoline group benzene is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Described crystalline modified master batch take PBT as matrix, and structural similitude, the consistency of one side PBT and PET are good, and another aspect PBT adds the sub-chain motion ability that can improve PET, plays a part crystallization promoter to a certain extent.Crystallization nucleating agent talcum powder and crystallization promoter polyethers P1000 are dispersed component, and the limiting viscosity of described PBT is 1.0dL/g, and described PBT, talcum powder and polyethers P1000 weight ratio are 7:4:1.Improving the crystal property of PET by adding crystalline modified master batch, compared with traditional addition manner, greatly increasing the dispersity of talcum powder and polyethers P1000, thus improve the utilising efficiency of talcum powder and polyethers P1000.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
Described preparation method comprises the steps:
(1) preparation of crystalline modified master batch: described PBT at 100 DEG C dry 6 hours, ratio of component takes PBT, talcum powder and polyethers P1000 as described above, and it is mixed 3min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrudes through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 210 DEG C;
(2) drying of raw material and mixing: by described PET and crystalline modified master batch at 100 DEG C dry 6 hours, ratio of component claimed to remove all the other components beyond glass fibre as described above, and mixes 3min in high-speed mixer;
(3) Screw Extrusion: step (2) mixed material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 250 DEG C.
Embodiment 5
A fiberglass reinforced PET composite material for fast crystallization, high tenacity, it is made up of following component and content:
PET 100 parts
Reactive anti-impact modifier 8 parts
Crystalline modified master batch 14 parts
30 parts, glass fibre
Processing aid 0.8 part
The limiting viscosity of described PET is 0.8dL/g.
Described reactive anti-impact modifier is the mixture with the toughner POE-g-MAH of reactive group and the two oxazoline group benzene of PET tackifier, and its combined weight is than being 2:1.Introduce the binding ability adding POE-g-MAH and matrix with toughner POE-g-MAH mono-aspect of reactive group, improve POE-g-MAH dispersiveness in the base on the other hand, introducing two oxazoline group benzene is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Described crystalline modified master batch take PBT as matrix, and structural similitude, the consistency of one side PBT and PET are good, and another aspect PBT adds the sub-chain motion ability that can improve PET, plays a part crystallization promoter to a certain extent.Crystallization nucleating agent nano imvite and crystallization promoter polyethers P1000 are dispersed component, and the limiting viscosity of described PBT is 1.0dL/g, and described PBT, nano imvite and polyethers P1000 weight ratio are 6:4:1.Improving the crystal property of PET by adding crystalline modified master batch, compared with traditional addition manner, greatly increasing the dispersity of nano imvite and polyethers P1000, thus improve the utilising efficiency of nano imvite and polyethers P1000.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
Described preparation method comprises the steps:
(1) preparation of crystalline modified master batch: described PBT at 100 DEG C dry 5 hours, ratio of component takes PBT, nano imvite and polyethers P1000 as described above, and it is mixed 3min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrudes through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 210 DEG C;
(2) drying of raw material and mixing: by described PET and crystalline modified master batch at 100 DEG C dry 5 hours, ratio of component claimed to remove all the other components beyond glass fibre as described above, and mixes 3min in high-speed mixer;
(3) Screw Extrusion: step (2) mixed material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 240 DEG C.
Embodiment 6
A fiberglass reinforced PET composite material for fast crystallization, high tenacity, it is made up of following component and content:
PET 100 parts
Reactive anti-impact modifier 8 parts
Crystalline modified master batch 16 parts
30 parts, glass fibre
Processing aid 0.8 part
The limiting viscosity of described PET is 0.8dL/g.
Described reactive anti-impact modifier is the mixture with the toughner LLDPE-g-MAH of reactive group and the two oxazoline group benzene of PET tackifier, and its combined weight is than being 2:1.Introduce the binding ability adding LLDPE-g-MAH and matrix with toughner LLDPE-g-MAH mono-aspect of reactive group, improve LLDPE-g-MAH dispersiveness in the base on the other hand, introducing two oxazoline group benzene is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Described crystalline modified master batch take PBT as matrix, and structural similitude, the consistency of one side PBT and PET are good, and another aspect PBT adds the sub-chain motion ability that can improve PET, plays a part crystallization promoter to a certain extent.Crystallization nucleating agent calcium carbonate and crystallization promoter polyoxyethylene glycol PEG6000 are dispersed component, and the limiting viscosity of described PBT is 1.0dL/g, and described PBT, calcium carbonate and polyoxyethylene glycol PEG6000 weight ratio are 6:4:1.Improving the crystal property of PET by adding crystalline modified master batch, compared with traditional addition manner, greatly increasing the dispersity of calcium carbonate and polyoxyethylene glycol PEG6000, thus improve the utilising efficiency of calcium carbonate and polyoxyethylene glycol PEG6000.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
Described preparation method comprises the steps:
(1) preparation of crystalline modified master batch: described PBT at 100 DEG C dry 6 hours, ratio of component takes PBT, calcium carbonate and polyoxyethylene glycol PEG6000 as described above, and it is mixed 5min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrudes through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 210 DEG C;
(2) drying of raw material and mixing: by described PET and crystalline modified master batch at 100 DEG C dry 5 hours, ratio of component claimed to remove all the other components beyond glass fibre as described above, and mixes 5min in high-speed mixer;
(3) Screw Extrusion: step (2) mixed material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200r/min, and each district temperature of twin screw extruder controls at 240 DEG C.
Comparative example
PET 100 parts
Toughner LLDPE-g-GMA 10 parts
4 parts, calcium carbonate
Polyethers P1000 1.5 parts
30 parts, glass fibre
Processing aid 0.5 part
The limiting viscosity of described PET is 0.85dL/g.
Described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
Described processing aid is terephthalic acid cyclobutanediol ester, and it is the cyclic oligomer of PBT, can not affect the mechanical property of material after interpolation, but can improve the mobility of material greatly, improve Drawing abillity and crystallinity.
Described preparation method comprises the steps:
(1) drying of raw material and mixing: by described PET at 120 DEG C dry 6 hours, ratio of component claimed to remove all the other components beyond glass fibre as described above, and mixes 5min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 400r/min, and each district temperature of twin screw extruder controls at 250 DEG C.
Performance synopsis
Embodiment 2 and comparative example are 30 fiberglass reinforced PET composite material, and from above-mentioned data relatively, obtain material compared with routine techniques resulting materials by masterbatch method technology and reactive blending modification technology combined together, its toughness and crystal property improve all greatly.
Claims (5)
1. fast crystallization, a high tenacity fiberglass reinforced PET composite material, it is characterized in that, this material is made up of following component and content: PET 100 parts;
Reactive anti-impact modifier 5 ~ 10 parts;
Crystalline modified master batch 10 ~ 20 parts;
15 ~ 30 parts, glass fibre;
Processing aid 0.5 ~ 1 part;
Described reactive anti-impact modifier is the mixture of toughner with reactive group and PET tackifier, and its combined weight is than being 3:2 ~ 4:1; Described crystalline modified master batch take PBT as matrix, and crystallization nucleating agent and crystallization promoter are dispersed component, and the limiting viscosity of described PBT is 1.0dL/g, and described PBT, crystallization nucleating agent and crystallization promoter weight ratio are 6:4:1 ~ 8:4:1; Described toughner is selected from the one in EPDM-g-GMA, POE-g-MAH or LLDPE-g-MAH, and described PET tackifier are selected from the one in pyromellitic acid anhydride or two oxazoline group benzene; Described crystallization nucleating agent is selected from the one in talcum powder, nano imvite or calcium carbonate, and described crystallization promoter is selected from the one in polyoxyethylene glycol PEG6000 or polyethers P1000; Described processing aid is terephthalic acid cyclobutanediol ester.
2. fiberglass reinforced PET composite material according to claim 1, is characterized in that, the limiting viscosity of described PET is 0.75 ~ 0.85dL/g.
3. fiberglass reinforced PET composite material according to claim 1, is characterized in that, described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
4. a preparation method for the fiberglass reinforced PET composite material as described in as arbitrary in claim 1-3, it is characterized in that, the method comprises the steps:
The preparation of (a) crystalline modified master batch: described PBT at 100 ~ 120 DEG C dry 5 ~ 6 hours, takes PBT, crystallization nucleating agent and crystallization promoter according to ratio of component according to claim 1, and it is mixed 3 ~ 5min in high-speed mixer; The material mixed is thrown in twin screw extruder, extrude through melt blending, tie rod, namely obtain crystalline modified master batch through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200 ~ 400r/min, and each district temperature of twin screw extruder controls at 210 ~ 240 DEG C;
The drying of (b) raw material and mixing: by described PET and crystalline modified master batch at 100 ~ 120 DEG C dry 5 ~ 6 hours, take all the other components except glass fibre according to ratio of component according to claim 1, and mix 3 ~ 5min in high-speed mixer;
(c) Screw Extrusion: mixed for step (b) material is joined in the hopper of twin screw extruder, glass fibre is added from glass fiber opening, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, the rotating speed of twin screw extruder is 200 ~ 400r/min, and each district temperature of twin screw extruder controls at 220 ~ 250 DEG C.
5. preparation method according to claim 4, it is characterized in that, the limiting viscosity of described PET is 0.75 ~ 0.85dL/g, described toughner is selected from EPDM-g-GMA, one in POE-g-MAH or LLDPE-g-MAH, described PET tackifier are selected from the one in pyromellitic acid anhydride or two oxazoline group benzene, described crystallization nucleating agent is selected from talcum powder, one in nano imvite or calcium carbonate, described crystallization promoter is selected from the one in polyoxyethylene glycol PEG6000 or polyethers P1000, described glass fibre is that alkali-free is long fine, described fiberglass surfacing is through silane coupling agent process, described processing aid is terephthalic acid cyclobutanediol ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694395.5A CN103694654B (en) | 2013-12-18 | 2013-12-18 | A kind of fast crystallization, high tenacity fiberglass reinforced PET composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310694395.5A CN103694654B (en) | 2013-12-18 | 2013-12-18 | A kind of fast crystallization, high tenacity fiberglass reinforced PET composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103694654A CN103694654A (en) | 2014-04-02 |
| CN103694654B true CN103694654B (en) | 2015-08-26 |
Family
ID=50356330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310694395.5A Active CN103694654B (en) | 2013-12-18 | 2013-12-18 | A kind of fast crystallization, high tenacity fiberglass reinforced PET composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103694654B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI823663B (en) * | 2022-11-04 | 2023-11-21 | 南亞塑膠工業股份有限公司 | Polyethylene terephthalate composite material containing glass fiber and method for manufacturing the same |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107849339B (en) * | 2015-07-22 | 2019-03-19 | 胜技高分子株式会社 | The manufacturing method of polybutylene terephthalate (PBT) resin combination and the manufacturing method of polybutylene terephthalate (PBT) resin-formed body |
| CN108299804A (en) * | 2017-12-25 | 2018-07-20 | 福建华塑新材料有限公司 | A kind of preparation method of high strength and modulus fiber glass reinforced PBT composite material |
| CN113956620A (en) * | 2021-07-27 | 2022-01-21 | 黄山鑫赢再生资源有限公司 | Preparation method of high-viscosity recycled PET plastic particles |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101280095A (en) * | 2008-05-20 | 2008-10-08 | 上海大学 | Glass fiber reinforced polyethylene glycol terephthalate composite material and preparation thereof |
| CN102134378B (en) * | 2010-01-21 | 2013-05-15 | 顾红军 | Polyester composite material with controllable crystallinity for sheet material |
| CN102020833B (en) * | 2011-01-18 | 2012-10-03 | 南通市东方塑胶有限公司 | Reinforced flame retardant polyester with high molding rate and fluidity and production method thereof |
| CN102816414B (en) * | 2012-04-09 | 2014-04-30 | 青岛海尔新材料研发有限公司 | High heat-resistant fire-retardant reinforced polyethylene terephthalate (PET) composition and preparation method thereof |
-
2013
- 2013-12-18 CN CN201310694395.5A patent/CN103694654B/en active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI823663B (en) * | 2022-11-04 | 2023-11-21 | 南亞塑膠工業股份有限公司 | Polyethylene terephthalate composite material containing glass fiber and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103694654A (en) | 2014-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101580632B (en) | High-gloss high-performance fiber glass reinforced PBT material and preparation method thereof | |
| CN104231567B (en) | A kind of degradable, rapid-result type PET/PBS Alloy And Preparation Method | |
| CN101580636B (en) | Warpage resistance nylon 6 composite material for vehicle air conditioning air door and preparation method thereof | |
| CN105153654A (en) | Fiber-reinforced polyester composition and preparation method thereof | |
| CN103694654B (en) | A kind of fast crystallization, high tenacity fiberglass reinforced PET composite material and preparation method thereof | |
| CN103382297B (en) | Fine REINFORCED PET/polyester alloy of a kind of low warpage carbon and preparation method thereof | |
| CN101195708B (en) | Reinforcing heat-resisting nylon composite material and method for producing the same | |
| CN103709681B (en) | A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite and preparation method thereof | |
| CN103467977A (en) | Low temperature resistant anti-impact nylon 6 composite for snowboard and preparation method of composite | |
| CN103694564A (en) | PP/PMMA (polypropylene/polymethyl methacrylate) alloy material and preparation method thereof | |
| CN103554667A (en) | Method for enhancing polypropylene composition by recycling waste CFRP (carbon fiber reinforced plastic) powder and manufacture method | |
| CN102061076A (en) | Super-tough PC (polycarbonate)/PBT (Polybutylece Terephthalate)/PET (Polyethylene Glycol Terephthalate) alloy and preparation method thereof | |
| CN103524871A (en) | Fibrilia-reinforced polypropylene as well as preparation method thereof | |
| CN102321354A (en) | A kind of plasticizing polylactic acid/composite polyethylene material and preparation method thereof | |
| CN103709688A (en) | PBS (polybuthylenesuccinate) fully biodegradable material as well as preparation method and application thereof | |
| CN105073889A (en) | Composition of reinforced polyalkylene terephthalate, preparation and use thereof | |
| CN106189126A (en) | A kind of high heat distortion temperature low molding cycle flame-retardant strengthening polythylene terephthalate (PET) material and preparation method | |
| CN105086452A (en) | Halogen-free flame-retardant polyphenylene sulfide composite material and preparation method thereof | |
| CN107501921A (en) | A kind of composition of modified fiberglass reinforced PA 6 and preparation method thereof | |
| CN108047503A (en) | A kind of PBAT polyester compositions and preparation method thereof and nucleating agent used | |
| CN103788589A (en) | Glass fiber-reinforced polyethylene terephthalate composite material and preparation method thereof | |
| CN103724948A (en) | Polyethylene terephthalate composite material and preparation method for same | |
| CN104356589A (en) | Carbon fiber reinforced friction-resistant polyoxymethylene (POM) composite material and preparation method thereof | |
| CN105623210A (en) | High-rigidity and low-warpage biodegradable polylactic acid engineering plastic and preparation method and application thereof | |
| CN101525478A (en) | Polytrimethylene terephthalate/Poly-butylene terephthalate alloy material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161226 Address after: 201107 Shanghai, Minhang District Ji Gao Road, building 1399, No. 1 Patentee after: SHANGHAI RIZHISHENG TECHNOLOGY CO., LTD. Address before: 201109 Shanghai city Minhang District humin Road No. 3078 Patentee before: Shanghai Sunny Company |