CN103709681B - A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite and preparation method thereof - Google Patents

A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite and preparation method thereof Download PDF

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CN103709681B
CN103709681B CN201310712476.3A CN201310712476A CN103709681B CN 103709681 B CN103709681 B CN 103709681B CN 201310712476 A CN201310712476 A CN 201310712476A CN 103709681 B CN103709681 B CN 103709681B
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pbt
heat
resisting glass
toughner
parts
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CN103709681A (en
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李莉
王尹杰
朱明源
孟成铭
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Shanghai Rizhisheng New Technology Development Co Ltd
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Shanghai Rizhisheng New Technology Development Co Ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • B29B9/14Making granules characterised by structure or composition fibre-reinforced
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/58Component parts, details or accessories; Auxiliary operations
    • B29B7/72Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/74Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
    • B29B7/7461Combinations of dissimilar mixers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/80Component parts, details or accessories; Auxiliary operations
    • B29B7/88Adding charges, i.e. additives
    • B29B7/90Fillers or reinforcements, e.g. fibres
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/12Making granules characterised by structure or composition
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion 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
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/14Glass
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/30Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/46Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00Making granules
    • B29B9/02Making granules by dividing preformed material
    • B29B9/06Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/9258Velocity
    • B29C2948/9259Angular velocity
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885Screw or gear
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92819Location or phase of control
    • B29C2948/92857Extrusion unit
    • B29C2948/92876Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895Barrel or housing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02Polyesters derived from dicarboxylic acids and dihydroxy compounds

Abstract

The present invention relates to a kind of high tenacity, high-heat-resisting glass-fiber strengthens PBT composite and preparation method thereof, this matrix material is made up of the raw material of following component and weight part content: PBT100 part, reactive anti-impact modifier 5 ~ 10 parts, nucleator 3 ~ 5 parts, 15 ~ 30 parts, glass fibre, processing aid 0.5 ~ 1 part; Reactive anti-impact modifier is the mixture of toughner with reactive group and PBT tackifier, and is 3: 2 ~ 4: 1 with the toughner of reactive group and the mass ratio of PBT tackifier.Compared with prior art, the present invention adopt PBT tackifier with the composite obtained reactive anti-impact modifier of toughner of reactive group, realized the super malleableize of PBT material by the method that reactively blending is extruded from molecular chain angle and the external toughness reinforcing angle of reactive toughening agent.The present invention can make PBT grain refining by the introducing of nucleator, thus improves the toughness of material, and nucleator plays heterogeneous nucleating effect simultaneously, and it can improve the degree of crystallinity of PBT, thus greatly increases thermal characteristics.

Description

A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite and preparation method thereof
Technical field
The present invention relates to a kind of PBT composite and preparation method thereof, especially relate to a kind of high tenacity, high-heat-resisting glass-fiber strengthens PBT composite and preparation method thereof.
Background technology
Polybutylene terephthalate (PBT) is a kind of thermoplastic engineering plastic of semicrystalline, and it has excellent mechanical property, electrical property, thermotolerance etc., applies to the industries such as automobile, electronics, electrical equipment widely.The molecular chain kindliness of PBT is better, and crystallization is fast, has excellent molding processibility compared with polyethylene terephthalate (PET).But PBT notched Izod impact strength is low is limit it as engineering plastics application one large defect.
Current most of research work concentrates on the elastomer blended toughness reinforcing or reactive functional groups grafted elastomeric of simple employing also or the toughness reinforcing PBT composite of both compounds.As provided a kind of composite method of dissimilar toughner in Chinese patent CN102002215A to improve the impact property of material, the simple method by adding toughner obtain after toughening effect reaches certain value and decline with the increase of toughner content on the contrary, on the other hand, the introducing of a large amount of toughner makes the mechanical property of material, thermal characteristics is subject to serious impact.
Chinese patent CN103289345A discloses a kind of high tenacity flame-retardant PBT/PC matrix material, comprises following raw material by weight: 53 ~ 65 parts of PC, 12 ~ 24 parts of PBT, 6 ~ 18 parts of fire retardant A, 5 ~ 12 parts of fire retardant B, 12 ~ 35 parts of bisphenol A polycarbonates, 3 ~ 12 parts of heat-proof modifiers, 0.6 ~ 3 part of toughner, 0.3 ~ 1 part of EMA-GMA, 0.3 ~ 1 part of antioxidant 1010,0.3 ~ 1 part of irgasfos 168,4 ~ 8 parts of MBS, 3 ~ 7 parts of compatilizer A, 2 ~ 6 parts of compatilizer B.This patent be also by adding merely compatilizer, toughner, fire retardant realize toughness reinforcing with fire-retardant effect, the cost of this material is higher, alloy material processed complex, and material mechanical performance and thermal characteristics need to be improved further.
Summary of the invention
Object of the present invention is exactly provide a kind of high tenacity, high-heat-resisting glass-fiber to strengthen PBT composite and preparation method thereof to overcome defect that above-mentioned prior art exists.
Object of the present invention can be achieved through the following technical solutions:
A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite, and this matrix material is made up of the raw material of following component and weight part content:
The limiting viscosity of described PBT is 0.9 ~ 1.05dL/g.
Described reactive anti-impact modifier is the mixture of toughner with reactive group and PBT tackifier, and is 3: 2 ~ 4: 1 with the toughner of reactive group and the mass ratio of PBT tackifier.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 PBT tackifier is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
The described toughner with reactive group is selected from the one in EPDM-g-GMA, POE-g-MAH or LLDPE-g-MAH.
Described PBT tackifier are selected from the one in pyromellitic acid anhydride or two oxazoline group benzene.
Described nucleator is selected from the one in talcum powder, nano imvite or calcium carbonate.The Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is larger, cause material embrittlement, the degree of crystallinity of PBT can be improved by the introducing of nucleator, make PBT grain refining, improve toughness and the thermal characteristics of material simultaneously.
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.
High tenacity, high-heat-resisting glass-fiber strengthen a preparation method for PBT composite, comprise the following steps:
(1) drying of raw material and mixing: by PBT at 100 ~ 120 DEG C dry 5 ~ 6 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 5 ~ 10 parts, nucleator 3 ~ 5 parts, processing aid 0.5 ~ 1 part, and mix 3 ~ 5min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in twin screw extruder, 15 ~ 30 parts, glass fibre is added, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, obtained high tenacity, high-heat-resisting glass-fiber strengthen PBT composite.
The rotating speed of twin screw extruder is 200 ~ 400r/min, and each district temperature of twin screw extruder controls at 210 ~ 230 DEG C.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) PBT tackifier and the composite obtained reactive anti-impact modifier of toughner with reactive group, break through traditional toughening modifying method, realized the super malleableize of PBT material from molecular chain angle and the external toughness reinforcing angle of reactive toughening agent by the method that reactively blending is extruded.
(2) Chain Flexibility of PBT is large, and therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is larger, cause material embrittlement, PBT grain refining can be made by the introducing of nucleator, thus improve the toughness of material.On the other hand, nucleator plays heterogeneous nucleating effect, and it can improve the degree of crystallinity of PBT, thus greatly increases thermal characteristics.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.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 kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite, are made up of the raw material of following component and weight part content:
Wherein, the limiting viscosity of PBT is 0.9dL/g.
Reactive anti-impact modifier is the mixture of toughner EPDM-g-GMA with reactive group and PBT tackifier pyromellitic acid anhydride, and its combined weight ratio is 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 pyromellitic acid anhydride is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Nucleator is talcum powder, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is comparatively large, causes material embrittlement, can be improved the degree of crystallinity of PBT by talcous introducing, make PBT grain refining, improve toughness and the thermal characteristics of material simultaneously.
Glass fibre is that alkali-free is long fine, and fiberglass surfacing is through silane coupling agent process.
Processing aid is terephthalic acid cyclobutanediol ester.
Above-mentioned high tenacity, high-heat-resisting glass-fiber strengthen the preparation method of PBT composite, comprise the steps:
(1) drying of raw material and mixing: by PBT at 100 DEG C dry 5 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 5 parts, nucleator 3 parts, processing aid 0.5 part, and mix 3min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, 15 parts, 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 210 DEG C.
Embodiment 2
A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite, and this matrix material is made up of the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.05dL/g.
Reactive anti-impact modifier is the toughner LLDPE-g-MAH with reactive group and the mixture of PBT tackifier pair oxazoline group benzene, and its combined weight ratio is 4: 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.
Nucleator is calcium carbonate, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is comparatively large, causes material embrittlement, can be improved the degree of crystallinity of PBT by the introducing of calcium carbonate, make PBT grain refining, improve toughness and the thermal characteristics of material simultaneously.
Glass fibre is that alkali-free is long fine, and fiberglass surfacing is through silane coupling agent process.
Processing aid is terephthalic acid cyclobutanediol ester.
Above-mentioned high tenacity, high-heat-resisting glass-fiber strengthen the preparation method of PBT composite, comprise the steps:
(1) drying of raw material and mixing: by PBT at 120 DEG C dry 6 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 10 parts, nucleator 5 parts, processing aid 1 part, and mix 5min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, 30 parts, 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 230 DEG C.
Embodiment 3
A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite, and this matrix material is made up of the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is the mixture of toughner POE-g-MAH with reactive group and PBT tackifier pyromellitic acid anhydride, and its combined weight ratio 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.
Nucleator is nano imvite, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is comparatively large, causes material embrittlement, can be improved the degree of crystallinity of PBT by the introducing of nano imvite, make PBT grain refining, improve toughness and the thermal characteristics of material simultaneously.
Glass fibre is that alkali-free is long fine, and fiberglass surfacing is through silane coupling agent process.
Processing aid is terephthalic acid cyclobutanediol ester.
Above-mentioned high tenacity, high-heat-resisting glass-fiber strengthen the preparation method of PBT composite, comprise the steps:
(1) drying of raw material and mixing: by PBT at 110 DEG C dry 5.5 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 7 parts, nucleator 4 parts, processing aid 0.7 part, and mix 4min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, 20 parts, 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 225 DEG C.
Embodiment 4
A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite, and this matrix material is made up of the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is the toughner EPDM-g-GMA with reactive group and the mixture of PBT tackifier pair oxazoline group benzene, and its combined weight ratio is 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.
Nucleator is talcum powder, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is comparatively large, causes material embrittlement, can be improved the degree of crystallinity of PBT by talcous introducing, make PBT grain refining, improve toughness and the thermal characteristics of material simultaneously.
Glass fibre is that alkali-free is long fine, and fiberglass surfacing is through silane coupling agent process.
Processing aid is terephthalic acid cyclobutanediol ester.
Above-mentioned high tenacity, high-heat-resisting glass-fiber strengthen the preparation method of PBT composite, comprise the steps:
(1) drying of raw material and mixing: by PBT at 100 DEG C dry 6 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 6 parts, nucleator 4 parts, processing aid 0.7 part, and mix 5min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, 30 parts, 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 230 DEG C.
Embodiment 5
A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite, and this matrix material is made up of the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is the toughner POE-g-MAH with reactive group and the mixture of PBT tackifier pair oxazoline group benzene, and its combined weight ratio is 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 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.
Nucleator is nano imvite, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is comparatively large, causes material embrittlement, can be improved the degree of crystallinity of PBT by the introducing of nano imvite, make PBT grain refining, improve toughness and the thermal characteristics of material simultaneously.
Glass fibre is that alkali-free is long fine, and fiberglass surfacing is through silane coupling agent process.
Processing aid is terephthalic acid cyclobutanediol ester.
Above-mentioned high tenacity, high-heat-resisting glass-fiber strengthen the preparation method of PBT composite, comprise the steps:
(1) drying of raw material and mixing: by PBT at 100 DEG C dry 6 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 8 parts, nucleator 4 parts, processing aid 0.8 part, and mix 5min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, 30 parts, 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 230 DEG C.
Embodiment 6
A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite, and this matrix material is made up of the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is the mixture of toughner LLDPE-g-MAH with reactive group and PBT tackifier pyromellitic acid anhydride, and its combined weight ratio is 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 pyromellitic acid anhydride is the toughness improving material from molecular weight levels, is greatly increased the impact property of material by both combinations.
Nucleator is calcium carbonate, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, but its high temperature nucleation capability is not good, and homogeneous nucleation gained spherocrystal is comparatively large, causes material embrittlement, can be improved the degree of crystallinity of PBT by the introducing of calcium carbonate, make PBT grain refining, improve toughness and the thermal characteristics of material simultaneously.
Glass fibre is that alkali-free is long fine, and fiberglass surfacing is through silane coupling agent process.
Processing aid is terephthalic acid cyclobutanediol ester.
Above-mentioned high tenacity, high-heat-resisting glass-fiber strengthen the preparation method of PBT composite, comprise the steps:
(1) drying of raw material and mixing: by PBT at 100 DEG C dry 5 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 9 parts, nucleator 4 parts, processing aid 0.8 part, and mix 4min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, 30 parts, 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 230 DEG C.
Comparative example
A kind of fiber glass reinforced PBT matrix material, this matrix material is made up of the raw material of following component and weight part content: PBT100 part, composite toughing agent 10 parts, 5 parts, calcium carbonate, 30 parts, glass fibre, processing aid 1 part.
The limiting viscosity of PBT is 1.05dL/g.
Composite toughing agent is the mixture of LLDPE and LLDPE-g-MAH, and its compositely proportional is 4: 1.
Glass fibre is that alkali-free is long fine, and fiberglass surfacing is through silane coupling agent process.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of fiber glass reinforced PBT matrix material comprises the steps:
(1) drying of raw material and mixing: by PBT at 120 DEG C dry 6 hours, get the raw materials ready according to following component and weight part content: PBT100 part, composite toughing agent 10 parts, 5 parts, calcium carbonate, processing aid 1 part, and mix 5min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in the hopper of twin screw extruder, 30 parts, 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 230 DEG C.
The performance of the PBT composite that above-described embodiment 1 ~ embodiment 6 and comparative example obtain is as shown in table 1.
The performance synopsis of table 1, PBT composite
Be 30 weight part fiber glass reinforced PBT matrix materials in embodiment 2 and comparative example, from above-mentioned data, compared with conventional modification technology resulting materials, the toughness of the PBT composite that the inventive method obtains and thermal characteristics are improved all greatly.

Claims (8)

1. high tenacity, high-heat-resisting glass-fiber strengthen a PBT composite, and it is characterized in that, this matrix material is made up of the raw material of following component and weight part content:
Described reactive anti-impact modifier is the mixture of toughner with reactive group and PBT tackifier, and is 3:2 ~ 4:1 with the toughner of reactive group and the mass ratio of PBT tackifier;
Described processing aid is terephthalic acid cyclobutanediol ester.
2. a kind of high tenacity according to claim 1, high-heat-resisting glass-fiber strengthen PBT composite, and it is characterized in that, the limiting viscosity of described PBT is 0.9 ~ 1.05dL/g.
3. a kind of high tenacity according to claim 1, high-heat-resisting glass-fiber strengthen PBT composite, and it is characterized in that, the described toughner with reactive group is selected from the one in EPDM-g-GMA, POE-g-MAH or LLDPE-g-MAH.
4. a kind of high tenacity according to claim 1, high-heat-resisting glass-fiber strengthen PBT composite, and it is characterized in that, described PBT tackifier are selected from the one in pyromellitic acid anhydride or two oxazoline group benzene.
5. a kind of high tenacity according to claim 1, high-heat-resisting glass-fiber strengthen PBT composite, and it is characterized in that, described nucleator is selected from the one in talcum powder, nano imvite or calcium carbonate.
6. a kind of high tenacity according to claim 1, high-heat-resisting glass-fiber strengthen PBT composite, it is characterized in that, described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is through silane coupling agent process.
7. the high tenacity as described in as arbitrary in claim 1 ~ 6, high-heat-resisting glass-fiber strengthen a preparation method for PBT composite, and it is characterized in that, the method comprises the following steps:
(1) drying of raw material and mixing: by PBT at 100 ~ 120 DEG C dry 5 ~ 6 hours, get the raw materials ready according to following component and weight part content: PBT100 part, reactive anti-impact modifier 5 ~ 10 parts, nucleator 3 ~ 5 parts, processing aid 0.5 ~ 1 part, and mix 3 ~ 5min in high-speed mixer;
(2) Screw Extrusion: step (1) mixed material is joined in twin screw extruder, 15 ~ 30 parts, glass fibre is added, extrude through melt blending, tie rod, through water-cooled, drying, pelletizing, obtained high tenacity, high-heat-resisting glass-fiber strengthen PBT composite.
8. the preparation method of a kind of high tenacity according to claim 7, high-heat-resisting glass-fiber enhancing PBT composite, it is characterized in that, the rotating speed of twin screw extruder is 200 ~ 400r/min, and each district temperature of twin screw extruder controls at 210 ~ 230 DEG C.
CN201310712476.3A 2013-12-20 2013-12-20 A kind of high tenacity, high-heat-resisting glass-fiber strengthen PBT composite and preparation method thereof Expired - Fee Related CN103709681B (en)

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CN107573652A (en) * 2017-07-28 2018-01-12 扬州金森光电材料有限公司 Short glass fiber is modified the technique that method prepares optical cable loose tube high intensity PBT
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