CN103709681A - High-toughness and high-heatproof glass fiber reinforced PBT (Polybutylece Terephthalate) composite material and preparation method thereof - Google Patents
High-toughness and high-heatproof glass fiber reinforced PBT (Polybutylece Terephthalate) composite material and preparation method thereof Download PDFInfo
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- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- B29B7/00—Mixing; Kneading
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- B29B7/00—Mixing; Kneading
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Abstract
The invention relates to a high-toughness and high-heatproof glass fiber reinforced PBT (Polybutylece Terephthalate) composite material and a preparation method thereof. The composite material is prepared from the following raw materials in parts by weight: 100 parts of PBT, 5-10 parts of reactive impact modifier, 3-5 parts of nucleating agent, 15-30 parts of glass fiber and 0.5-1 part of processing aid, wherein the reactive impact modifier is a compound of a toughening agent with reactive groups and a PBT thickening agent, and the mass ratio of the toughening agent with the reactive groups to the PBT thickening agent is (3:2)-(4:1). Compared with the prior art, the high-toughness and high-heatproof glass fiber reinforced PBT composite material has the advantages that the reactive impact modifier is prepared by compounding the PBT thickening agent and the toughening agent with the reactive groups, and the super-toughening of the PBT material is realized through reactive blending extrusion from the perspectives of a molecular chain and the external toughening of a reactive toughening agent. PBT crystal grains can be refined through the introduction of the nucleating agent, so that the toughness of the material is improved; and meanwhile, the nucleating agent plays a heterogeneous nucleation role, so that the crystallinity of PBT can be increased, and furthermore, the thermal property is greatly improved.
Description
Technical field
The present invention relates to a kind of PBT matrix material and preparation method thereof, especially relate to a kind of high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material and preparation method thereof.
Background technology
Polybutylene terephthalate (PBT) is a kind of thermoplastic engineering plastic of half hitch crystal formation, and it has good mechanical property, electrical property, thermotolerance etc., applies to widely the industries such as automobile, electronics, electrical equipment.The molecular chain kindliness of PBT is better, and crystallization is fast, compares and has excellent forming process with polyethylene terephthalate (PET).Yet PBT notched Izod impact strength is low is to limit it as engineering plastics application one large defect.
Most research work also concentrates on the elastomer blended toughness reinforcing or reactive functional groups grafting elastomerics of simple employing or the toughness reinforcing PBT matrix material of both compounds.As being provided in Chinese patent CN102002215A, a kind of composite method of dissimilar toughner improves the impact property of material, merely by adding the toughening effect that method obtains of toughner, reach after certain value the increase with toughner content on the contrary and decline, on the other hand, the introducing of a large amount of toughner makes mechanical property, the thermal characteristics of material be subject to serious impact.
Chinese patent CN103289345A has announced 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 is also that the cost of this material is higher by adding merely compatilizer, toughner, fire retardant to realize toughness reinforcing and fire-retardant effect, alloy material processed complex, and material mechanical performance and thermal characteristics need further to be improved.
Summary of the invention
Object of the present invention is exactly to provide a kind of high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material and preparation method thereof in order to overcome the defect of above-mentioned prior art existence.
Object of the present invention can be achieved through the following technical solutions:
High tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, this matrix material is made by 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 with the toughner of reactive group and the mixture of PBT tackifier, and is 3: 2～4: 1 with the toughner of reactive group and the mass ratio of PBT tackifier.Introducing has increased the binding ability of toughner and matrix on the one hand with the toughner of reactive group, improved on the other hand the dispersiveness of toughner in matrix, introducing PBT tackifier is from molecular weight level, to improve the toughness of material, by both combinations, has improved widely the impact property of material.
The described toughner with reactive group is selected from a kind of in EPDM-g-GMA, POE-g-MAH or LLDPE-g-MAH.
Described PBT tackifier are selected from a kind of in pyromellitic acid anhydride or two oxazoline group benzene.
Described nucleator is selected from a kind of 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, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, cause material embrittlement, by the introducing of nucleator, can improve the degree of crystallinity of PBT, 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 processed through silane coupling agent.
Described processing aid is terephthalic acid cyclobutanediol ester.
A preparation method for high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material, comprises the following steps:
(1) the dry and mixing of raw material: PBT is dried to 5～6 hours at 100～120 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 5～10 parts of reactive anti-impact modifiers, 3～5 parts of nucleators, 0.5～1 part of processing aid, and in high-speed mixer, mix 3～5min;
(2) Screw Extrusion: the mixed material of step (1) is joined in twin screw extruder, 15～30 parts, glass fibre is added, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, make high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material.
The rotating speed of twin screw extruder is 200～400r/min, and twin screw extruder Ge district temperature is controlled at 210～230 ℃.
Compared with prior art, the present invention has the following advantages and beneficial effect:
(1) PBT tackifier with the toughner of reactive group is composite, make reactive anti-impact modifier, break through traditional toughening modifying method, the method for extruding by reactively blending from molecular chain angle and the external toughness reinforcing angle of reactive toughening agent realizes the super malleableize of PBT material.
(2) Chain Flexibility of PBT is large, so the low-temperature epitaxy ability of crystal grain is better, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, cause material embrittlement, the introducing by nucleator can make PBT grain refining, thereby improves the toughness of material.On the other hand, nucleator plays heterogeneous nucleating effect, and it can improve the degree of crystallinity of PBT, thereby has improved widely thermal characteristics.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
High tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, by the raw material of following component and weight part content, made:
Wherein, the limiting viscosity of PBT is 0.9dL/g.
Reactive anti-impact modifier is that its compound weight ratio is 3: 2 with the toughner EPDM-g-GMA of reactive group and the mixture of PBT tackifier pyromellitic acid anhydride.Introducing has increased the binding ability of EPDM-g-GMA and matrix on the one hand with the toughner EPDM-g-GMA of reactive group, improved on the other hand the dispersiveness of EPDM-g-GMA in matrix, introducing pyromellitic acid anhydride is from molecular weight level, to improve the toughness of material, by both combinations, has improved widely the impact property of material.
Nucleator is talcum powder, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, causes material embrittlement, by talcous introducing, can improve the degree of crystallinity of PBT, 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 processed through silane coupling agent.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of above-mentioned high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material, comprises the steps:
(1) the dry and mixing of raw material: PBT is dried to 5 hours at 100 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 5 parts of reactive anti-impact modifiers, 3 parts of nucleators, 0.5 part of processing aid, and in high-speed mixer, mix 3min;
(2) Screw Extrusion: the mixed material of step (1) is joined in the hopper of twin screw extruder, 15 parts, glass fibre is added from glass fiber opening, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, the rotating speed of twin screw extruder is 200r/min, and twin screw extruder Ge district temperature is controlled at 210 ℃.
Embodiment 2
High tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, this matrix material is made by the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.05dL/g.
Reactive anti-impact modifier is that its compound weight ratio is 4: 1 with the mixture of the toughner LLDPE-g-MAH of reactive group and the two oxazoline group benzene of PBT tackifier.Introducing has increased the binding ability of LLDPE-g-MAH and matrix on the one hand with the toughner LLDPE-g-MAH of reactive group, improved on the other hand the dispersiveness of LLDPE-g-MAH in matrix, introducing two oxazoline group benzene is from molecular weight level, to improve the toughness of material, by both combinations, has improved widely the impact property of material.
Nucleator is calcium carbonate, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, causes material embrittlement, by the introducing of calcium carbonate, can improve the degree of crystallinity of PBT, 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 processed through silane coupling agent.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of above-mentioned high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material, comprises the steps:
(1) the dry and mixing of raw material: PBT is dried to 6 hours at 120 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 10 parts of reactive anti-impact modifiers, 5 parts of nucleators, 1 part of processing aid, and in high-speed mixer, mix 5min;
(2) Screw Extrusion: the mixed material of step (1) is joined in the hopper of twin screw extruder, 30 parts, glass fibre is added from glass fiber opening, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, the rotating speed of twin screw extruder is 400r/min, and twin screw extruder Ge district temperature is controlled at 230 ℃.
Embodiment 3
High tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, this matrix material is made by the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is that its compound weight ratio is 3: 1 with the toughner POE-g-MAH of reactive group and the mixture of PBT tackifier pyromellitic acid anhydride.Introducing has increased the binding ability of POE-g-MAH and matrix on the one hand with the toughner POE-g-MAH of reactive group, improved on the other hand the dispersiveness of POE-g-MAH in matrix, introducing pyromellitic acid anhydride is from molecular weight level, to improve the toughness of material, by both combinations, has improved widely the impact property of material.
Nucleator is nano imvite, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, causes material embrittlement, by the introducing of nano imvite, can improve the degree of crystallinity of PBT, 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 processed through silane coupling agent.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of above-mentioned high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material, comprises the steps:
(1) the dry and mixing of raw material: PBT is dried to 5.5 hours at 110 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 7 parts of reactive anti-impact modifiers, 4 parts of nucleators, 0.7 part of processing aid, and in high-speed mixer, mix 4min;
(2) Screw Extrusion: the mixed material of step (1) is joined in the hopper of twin screw extruder, 20 parts, glass fibre is added from glass fiber opening, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, the rotating speed of twin screw extruder is 300r/min, and twin screw extruder Ge district temperature is controlled at 225 ℃.
Embodiment 4
High tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, this matrix material is made by the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is that its compound weight ratio is 2: 1 with the mixture of the toughner EPDM-g-GMA of reactive group and the two oxazoline group benzene of PBT tackifier.Introducing has increased the binding ability of EPDM-g-GMA and matrix on the one hand with the toughner EPDM-g-GMA of reactive group, improved on the other hand the dispersiveness of EPDM-g-GMA in matrix, introducing two oxazoline group benzene is from molecular weight level, to improve the toughness of material, by both combinations, has improved widely the impact property of material.
Nucleator is talcum powder, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, causes material embrittlement, by talcous introducing, can improve the degree of crystallinity of PBT, 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 processed through silane coupling agent.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of above-mentioned high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material, comprises the steps:
(1) the dry and mixing of raw material: PBT is dried to 6 hours at 100 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 6 parts of reactive anti-impact modifiers, 4 parts of nucleators, 0.7 part of processing aid, and in high-speed mixer, mix 5min;
(2) Screw Extrusion: the mixed material of step (1) is joined in the hopper of twin screw extruder, 30 parts, glass fibre is added from glass fiber opening, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, the rotating speed of twin screw extruder is 200r/min, and twin screw extruder Ge district temperature is controlled at 230 ℃.
Embodiment 5
High tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, this matrix material is made by the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is that its compound weight ratio is 2: 1 with the mixture of the toughner POE-g-MAH of reactive group and the two oxazoline group benzene of PBT tackifier.Introducing has increased the binding ability of POE-g-MAH and matrix on the one hand with the toughner POE-g-MAH of reactive group, improved on the other hand the dispersiveness of POE-g-MAH in matrix, introducing the two oxazoline group benzene of tackifier is from molecular weight level, to improve the toughness of material, by both combinations, has improved widely the impact property of material.
Nucleator is nano imvite, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, causes material embrittlement, by the introducing of nano imvite, can improve the degree of crystallinity of PBT, 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 processed through silane coupling agent.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of above-mentioned high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material, comprises the steps:
(1) the dry and mixing of raw material: PBT is dried to 6 hours at 100 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 8 parts of reactive anti-impact modifiers, 4 parts of nucleators, 0.8 part of processing aid, and in high-speed mixer, mix 5min;
(2) Screw Extrusion: the mixed material of step (1) is joined in the hopper of twin screw extruder, 30 parts, glass fibre is added from glass fiber opening, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, the rotating speed of twin screw extruder is 400r/min, and twin screw extruder Ge district temperature is controlled at 230 ℃.
Embodiment 6
High tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, this matrix material is made by the raw material of following component and weight part content:
The limiting viscosity of PBT is 1.0dL/g.
Reactive anti-impact modifier is that its compound weight ratio is 2: 1 with the toughner LLDPE-g-MAH of reactive group and the mixture of PBT tackifier pyromellitic acid anhydride.Introducing has increased the binding ability of LLDPE-g-MAH and matrix on the one hand with the toughner LLDPE-g-MAH of reactive group, improved on the other hand the dispersiveness of LLDPE-g-MAH in matrix, introducing pyromellitic acid anhydride is from molecular weight level, to improve the toughness of material, by both combinations, has improved widely the impact property of material.
Nucleator is calcium carbonate, the Chain Flexibility of PBT is large, therefore the low-temperature epitaxy ability of crystal grain is better, yet its high temperature nucleation ability is not good, and homogeneous nucleation gained spherocrystal is larger, causes material embrittlement, by the introducing of calcium carbonate, can improve the degree of crystallinity of PBT, 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 processed through silane coupling agent.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of above-mentioned high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material, comprises the steps:
(1) the dry and mixing of raw material: PBT is dried to 5 hours at 100 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 9 parts of reactive anti-impact modifiers, 4 parts of nucleators, 0.8 part of processing aid, and in high-speed mixer, mix 4min;
(2) Screw Extrusion: the mixed material of step (1) is joined in the hopper of twin screw extruder, 30 parts, glass fibre is added from glass fiber opening, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, the rotating speed of twin screw extruder is 400r/min, and twin screw extruder Ge district temperature is controlled at 230 ℃.
Comparative example
A fiber glass reinforced PBT matrix material, this matrix material is made by the raw material of following component and weight part content: PBT100 part, 10 parts of composite toughing agents, 5 parts, calcium carbonate, 30 parts, glass fibre, 1 part of processing aid.
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 processed through silane coupling agent.
Processing aid is terephthalic acid cyclobutanediol ester.
The preparation method of fiber glass reinforced PBT matrix material comprises the steps:
(1) the dry and mixing of raw material: PBT is dried to 6 hours at 120 ℃, gets the raw materials ready according to following component and weight part content: PBT100 part, 10 parts of composite toughing agents, 5 parts, calcium carbonate, 1 part of processing aid, and in high-speed mixer, mix 5min;
(2) Screw Extrusion: the mixed material of step (1) is joined in the hopper of twin screw extruder, 30 parts, glass fibre is added from glass fiber opening, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, the rotating speed of twin screw extruder is 400r/min, and twin screw extruder Ge district temperature is controlled at 230 ℃.
Above-described embodiment 1～embodiment 6 is as shown in table 1 with the performance of the PBT matrix material that comparative example makes.
The performance synopsis of table 1, PBT matrix material
In embodiment 2 and comparative example, be 30 weight part fiber glass reinforced PBT matrix materials, from above-mentioned data, compare with conventional modification technology resulting materials, the toughness of the PBT matrix material that the inventive method makes and thermal characteristics are all improved greatly.
Claims (10)
1. high tenacity, a high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, this matrix material is made by the raw material of following component and weight part content:
2. a kind of high tenacity according to claim 1, high-heat-resisting glass fiber enhanced PBT matrix material, 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 enhanced PBT matrix material, it is characterized in that, described reactive anti-impact modifier is with the toughner of reactive group and the mixture of PBT tackifier, and is 3: 2～4: 1 with the toughner of reactive group and the mass ratio of PBT tackifier.
4. a kind of high tenacity according to claim 3, high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, the described toughner with reactive group is selected from a kind of in EPDM-g-GMA, POE-g-MAH or LLDPE-g-MAH.
5. a kind of high tenacity according to claim 3, high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, described PBT tackifier are selected from a kind of in pyromellitic acid anhydride or two oxazoline group benzene.
6. a kind of high tenacity according to claim 1, high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, described nucleator is selected from a kind of in talcum powder, nano imvite or calcium carbonate.
7. a kind of high tenacity according to claim 1, high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, described glass fibre is that alkali-free is long fine, and described fiberglass surfacing is processed through silane coupling agent.
8. a kind of high tenacity according to claim 1, high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, described processing aid is terephthalic acid cyclobutanediol ester.
9. the high tenacity as described in as arbitrary in claim 1～8, a preparation method for high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, the method comprises the following steps:
(1) the dry and mixing of raw material: PBT is dried to 5～6 hours at 100～120 ℃, according to following component and weight part content, get the raw materials ready: PBT100 part, 5～10 parts of reactive anti-impact modifiers, 3～5 parts of nucleators, 0.5～1 part of processing aid, and in high-speed mixer, mix 3～5min;
(2) Screw Extrusion: the mixed material of step (1) is joined in twin screw extruder, 15～30 parts, glass fibre is added, through melt blending extrude, tie rod, through water-cooled, dry, pelletizing, make high tenacity, high-heat-resisting glass fiber enhanced PBT matrix material.
10. the preparation method of a kind of high tenacity according to claim 9, high-heat-resisting glass fiber enhanced PBT matrix material, is characterized in that, the rotating speed of twin screw extruder is 200～400r/min, and twin screw extruder Ge district temperature is controlled at 210～230 ℃.
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| CN112778708A (en) * | 2019-11-04 | 2021-05-11 | 现代自动车株式会社 | Composition of radar transmission cover of vehicle |
| CN112778715A (en) * | 2020-12-30 | 2021-05-11 | 广东顺德顺炎新材料股份有限公司 | Modified PBT (polybutylene terephthalate) material suitable for thermal sublimation transfer printing and preparation method thereof |
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