CN102532864B - Continuous long fiber reinforced thermoplastic polyurethane material and preparation method thereof - Google Patents
Continuous long fiber reinforced thermoplastic polyurethane material and preparation method thereof Download PDFInfo
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- CN102532864B CN102532864B CN201010576695.XA CN201010576695A CN102532864B CN 102532864 B CN102532864 B CN 102532864B CN 201010576695 A CN201010576695 A CN 201010576695A CN 102532864 B CN102532864 B CN 102532864B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7461—Combinations of dissimilar mixers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
- B29B7/46—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with more than one shaft
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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Abstract
The invention belongs to the technical field of high polymer materials and discloses a continuous long fiber reinforced thermoplastic polyurethane material and a preparation method thereof. The continuous long fiber reinforced thermoplastic polyurethane material disclosed by the invention comprises the following components in parts by weight: 200-800 parts of thermoplastic polyurethane, 800-200 parts of continuous long fiber reinforcing agent, 10-30 parts of compatilizer, 10-20 parts of antioxidant, 2-6 parts of lubricating agent and 5-10 parts of crosslinking agent. Compared with the prior art, the continuous long fiber reinforced thermoplastic polyurethane material disclosed by the invention is simple in structure, reasonable in design and strong in practicability; and a long glass fiber reinforced thermoplastic polyurethane material is adopted, thereby greatly improving the rigidity and strength of the material and obviously improving the anti-impact property and heat-resistant property of the material.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of continuous fiber reinforced thermoplastic polyurethane material and preparation method thereof.
Background technology
TPU (Polyurethane Thermoplastic Elastomer) is emerging plastics variety, because TPU has good processibility, weathering resistance, the feature of environmental protection, is widely used in the relevant industries such as footwear material, tubing, film, roller, cable and wire.The feature that Polyurethane Thermoplastic Elastomer is outstanding is that excellent in abrasion resistance, ozone resistance are fabulous, low temperature resistant, has good oil resistant, chemical-resistant resistance and environmental resistance, and in wet environment, polyether-type ester stability to hydrolysis far exceedes polyester type.But the shortcomings such as the intensity of Polyurethane Thermoplastic Elastomer material own is not high, poor heat resistance, thereby greatly limit its application at other field as engineering plastics.Owing to adding intensity and the rigidity that can increase substantially Polyurethane Thermoplastic Elastomer after fiber enhancer, so day by day come into one's own.But the glass fibre using at present strengthens Polyurethane Thermoplastic Elastomer material is generally short glass fiber enhancing, prepare through twin-screw extrusion machining melt kneading by glass fibre and thermoplastic elastomer, in this kind of material, glass fibre is destroyed by the strong shearing of screw rod, length is shorter, only have 0.2～0.4mm left and right, improve limited to the mechanical property of material.
The publication that has had pair polyurethane material to strengthen both at home and abroad, as related to a kind of glass fiber reinforced polyurethane skeleton for inside gadgets such as fascia, door-plate, air conditioner covers in CN 1432593A (publication date: 2003.07.30) patent.This invention is by entering long glass fibres at mould middle berth in advance, mix on the glass fibre that injects above-mentioned mould with polyethers and isocyanic ester again, after matched moulds, in polyethers and isocyanate reaction foaming process, make glass fibre be evenly distributed in the urethane of its generation, be so just molded to the glass fiber reinforced polyurethane skeleton of the inside gadgets such as required fascia, door-plate, air conditioner cover.This skeleton can meet the property indices of automotive upholstery, and there is good looking appearance, lightweight, good springiness, physical strength is high, heat-resisting, moisture resistance, geometrical dimension stable, low cost and other advantages.The defect of this method is that Length of Glass Fiber used is 3～5mm., reinforced effects to polyurethane material is limited, the method utilizes polyethers and isocyanic ester foamable reaction in mould to form in addition, and production process is inevitably used a large amount of organic solvents, and operator's health is had a certain impact.
Patent CN 1208055A (publication date: 1999.02.17) adopts the glass fibre and the polyurethane combined material that contain finished product gross weight 25～30%, in polyurethane combined material, contain the polyethers of finished product gross weight 25～35% and 35～45% isocyanic ester, its production technique comprises the mould-injection molding-foaming of heat-glass fibre of mould paving, solidifies-processing steps such as the demoulding, and its finished product are mainly used as the substitute of some metal insert in automobile manufacture industry.The defect of this method is that Length of Glass Fiber is only 0.3～0.6mm, and more weak with the interaction of urethane resin matrix, and solidify after product can not recycle.
Summary of the invention
The defect existing in order to overcome above-mentioned prior art, the object of this invention is to provide a kind of continuous fiber reinforced thermoplastic polyurethane elastomer material, this material has higher rigidity and intensity, and excellent shock resistance and resistance toheat, and this material can be by injection moulding straight forming, production efficiency is high, and the product after use can be recycled after crushed.
Another object of the present invention is to provide a kind of preparation method of above-mentioned continuous fiber reinforced thermoplastic polyurethane material.
Technical scheme of the present invention is as follows:
The invention provides a kind of continuous fiber reinforced thermoplastic polyurethane material, this material comprises following component and weight part:
Thermoplastic polyurethane 200～800
Continuous fiber toughener 800～200
Compatilizer 10～30
Oxidation inhibitor 10～20
Lubricant 2～6
Linking agent 5～10
Described thermoplastic polyurethane is PAUR, and its Rockwell hardness is 90～120R, the urethane raw that preferably Rockwell hardness is 100～110R.
Described continuous fiber toughener is selected from the one in continuous glass fibre (alkali free glass fibre), carbon fiber, steel fiber or synthetic resin fiber.If need high preferably carbon fiber of intensity, as do not have particular requirement can select the alkali free glass fibre that sexual valence is higher.The average fiber length of this fortifying fibre in material is 3～60mm, and mean diameter is 3～30 μ m, and its length is identical with final material bodies length, and is arranged in parallel along central principal axis.
Described compatilizer is selected from the one in SMA resin (phenylethylene-maleic anhydride resin), chromium of organic acid complex compound, organic coupling agent, titanate coupling agent or aluminate coupling agent.
Described oxidation inhibitor is selected from one or more the mixture in Hinered phenols, hindered amines or phosphite ester kind antioxidant, preferably antioxidant 1010 (four (β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester), oxidation inhibitor 1098 (3,5-di-t-butyl-4 hydroxybenzene propionyl-hexanediamine), irgasfos 168 (tricresyl phosphite-(2,4-di-tert-butyl phenolic ester) or oxidation inhibitor PEPQ (four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites) etc. in one or more mixture.
Described lubricant is stearate, preferably the mixture of one or several in calcium stearate (CaSt), Zinic stearas (ZnSt) or tetramethylolmethane stearate (PETS).
Described linking agent is epoxy compounds, preferably the mixture of one or both in isocyanuric acid three-glycidyl ester (TGIC) or TriMethylolPropane(TMP) (TMP) etc.
The present invention also provides a kind of preparation method of above-mentioned continuous fiber reinforced thermoplastic polyurethane material, and the method comprises the following steps:
By 200～800 parts of dry thermoplastic polyurethanes, 10～30 parts of compatilizers, 10～20 parts of oxidation inhibitor, 2～6 parts of lubricants, 5～10 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
Adopt impregnating equipment (the Chinese patent CN1488674 of continuous fiber reinforced thermoplastic material, publication date: 2004.04.14), by the shape size (2.0～4.0mm) of mouthful mould of selection, adjust forcing machine rotating speed and main frame feeding simultaneously, adjust the content of continuous fiber toughener in continuous fiber reinforced thermoplastic polyurethane material, continuous fiber toughener content can be controlled at 30～50%; The cutting knife rotating speed of adjusting dicing machine, makes the pelletizing length of the continuous fiber reinforced thermoplastic polyurethane material preparing be controlled at 11-13mm, particle diameter 2.0～4.0mm.
Described dry thermoplastic polyurethane is thermoplastic polyurethane to be placed in to moisture eliminator be dried, drying temperature: 90～100 ℃; Time of drying: 6～8h.
Described forcing machine is twin screw extruder, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40: 1, mixed melting Temperature Setting is: 160～180 ℃ of first paragraphs, 180～190 ℃ of second segments, the 3rd section 190～200 ℃, the 4th section 200～210 ℃, the 5th section 210～220 ℃, 205～215 ℃ of melt temperatures, 195～205 ℃ of head temperatures.
The present invention is owing to having adopted above technical scheme, adopt long glass fibres to strengthen thermoplastic polyurethane material, in this material, glass fibre is orientated by same direction, and the length of fiber is greater than 4mm, thereby increased substantially rigidity and the intensity of material, and shock resistance and resistance toheat.
Compared with the existing technology, tool has the following advantages and beneficial effect in the present invention:
1, with prior art first than, the present invention adopts long glass fibres to strengthen thermoplastic polyurethane, carry out dispersed by impregnating equipment to continuous glass-fiber, thorough impregnation, improve the interface interaction of glass and urethane resin, guarantee the useful length of glass, thereby greatly improved rigidity and the intensity of this material, obviously improved shock resistance and the resistance toheat of material simultaneously.
2, the present invention is reasonable in design, simple in structure, practical, product is the pellet (grain length: 11～13mm with certain length, diameter: 2.0～4.0mm), directly injection moulding after drying treatment, production efficiency is high, and product can also be recycled through pulverization process after using, free from environmental pollution.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The invention provides a kind of continuous fiber reinforced thermoplastic polyurethane material, this polyurethane material pelletizing length 11-13mm, particle diameter 2.0～4.0mm, comprises following component and weight part:
Thermoplastic polyurethane 600
Continuous glass fibre 400
Compatilizer 10
Oxidation inhibitor 12
Lubricant 5
Linking agent 5
Described thermoplastic polyurethane is PAUR, and its Rockwell hardness is 110R;
Described continuous fiber toughener is continuous alkali free glass fibre, and Fibre diameter is 27 μ m;
Described compatilizer is SMA resin (phenylethylene-maleic anhydride resin), and wherein maleic anhydride content is 0.5～1.5%;
Described oxidation inhibitor is antioxidant 1010 (four (β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester), with oxidation inhibitor PEPQ (four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites) mixture, the two weight ratio is 1: 2;
Described lubricant is tetramethylolmethane stearate (PETS);
Linking agent used is isocyanuric acid three-glycidyl ester (TGIC);
Continuous fiber reinforced thermoplastic polyurethane material is prepared by following methods, and the method comprises the following steps:
(1) dry preparation: the PAUR raw material that is 110R by Rockwell hardness is placed in moisture eliminator, drying temperature: 90～100 ℃; Time of drying: 6～8h;
(2) batch mixing is prepared; By 600 parts of urethane raws, 10 parts of compatilizers, 12 parts of oxidation inhibitor, 5 parts of lubricants, 5 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
(3) preparation of continuous fibre enhancement polyurethane material; Adopt the impregnating equipment (CN1488674 of continuous fiber reinforced thermoplastic material, publication date: 2004.04.14), continuous fiber toughener is added into impregnating equipment by glass fiber opening, by the shape size (3.0mm) of mouthful mould of selection, adjust the engine speed of forcing machine at 11～13Hz simultaneously, rate of feeding is at 7.0～8.0Hz, continuous fiber toughener content is controlled at 40 ± 2%, adjust the cutting knife rotating speed of dicing machine, make the continuous fiber enhancing polyurethane material pelletizing length preparing be controlled at 11-13mm, particle diameter 2.0～4.0mm; Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40: 1, mixed melting Temperature Setting is: 160～180 ℃ of first paragraphs, 180～190 ℃ of second segments, the 3rd section 190～200 ℃, the 4th section 200～210 ℃, the 5th section 210～220 ℃, 205～215 ℃ of melt temperatures, 195～205 ℃ of head temperatures.
(4) injection moulding and batten test: continuous glass-fiber obtained above is strengthened to thermoplastic polyurethane material carry out injection moulding after 90～100 ℃ of dry 6～8h in baking oven, injection moulding batten is ASTM batten, and injection temperature is as follows:
Blanking section: 200～210 ℃; Second segment: 210～220 ℃; The 3rd section: 220～230 ℃; Nozzle: 210～220 ℃
Injection moulding batten is put in and in baking oven, carries out aftertreatment: treatment temp: 90 ℃; Treatment time: 16h; The performance test results is in table 1.
Embodiment 2
Thermoplastic polyurethane 600
Continuous glass fibre 400
Compatilizer 15
Oxidation inhibitor 12
Lubricant 5
Linking agent 10
Described thermoplastic polyurethane is PAUR, and its Rockwell hardness is 110R;
Described continuous fiber toughener is continuous alkali free glass fibre, and Fibre diameter is 27 μ m;
Described compatilizer is SMA resin (phenylethylene-maleic anhydride resin), and wherein maleic anhydride content is 0.5～1.5%;
Described oxidation inhibitor is antioxidant 1010 (four (β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester), with oxidation inhibitor PEPQ (four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites) mixture, the two weight ratio is 1: 2;
Described lubricant is tetramethylolmethane stearate (PETS);
Linking agent used is isocyanuric acid three-glycidyl ester (TGIC);
Described continuous fiber strengthens polyurethane material and is prepared by following methods, and the method comprises the following steps:
(1) dry preparation: urethane raw is placed in to moisture eliminator, drying temperature: 90～100 ℃; Time of drying: 6～8h;
(2) batch mixing is prepared; By 600 parts of urethane, 15 parts of compatilizers, 12 parts of oxidation inhibitor, 5 parts of lubricants, 10 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
(3) preparation of continuous fibre enhancement polyurethane material; Adopt the impregnating equipment (CN1488674 of continuous fiber reinforced thermoplastic material, publication date: 2004.04.14), continuous fiber toughener is added into impregnating equipment by glass entrance, by the shape size (3.0mm) of mouthful mould of selection, adjust the engine speed of forcing machine at 11～13Hz simultaneously, rate of feeding is at 7.0～8.0Hz, continuous fiber toughener content is controlled at 40 ± 2%, the cutting knife rotating speed of adjusting dicing machine, makes the continuous fibre enhancement polyurethane material pelletizing length preparing be controlled at 11-13mm;
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40: 1, mixed melting Temperature Setting is: 160～180 ℃ of first paragraphs, 180～190 ℃ of second segments, the 3rd section 190～200 ℃, the 4th section 200～210 ℃, the 5th section 210～220 ℃, 205～215 ℃ of melt temperatures, 195～205 ℃ of head temperatures.
(4) injection moulding and batten test: continuous glass-fiber obtained above is strengthened to thermoplastic polyurethane material carry out injection moulding after 90～100 ℃ of dry 6～8h in baking oven, injection moulding batten is ASTM batten, and injection temperature is as follows:
Blanking section: 200～210 ℃; Second segment: 210～220 ℃; The 3rd section: 220～230 ℃; Nozzle: 210～220 ℃
Injection moulding batten is put in and in baking oven, carries out aftertreatment: treatment temp: 90 ℃; Treatment time: 16h; The performance test results is in table 1.
Embodiment 3
Thermoplastic polyurethane 600
Continuous glass fibre 400
Compatilizer 15
Oxidation inhibitor 12
Lubricant 5
Linking agent 15
Described thermoplastic polyurethane is PAUR, and its Rockwell hardness is 110R;
Described continuous fiber toughener is continuous alkali free glass fibre, and Fibre diameter is 27 μ m;
Described compatilizer is SMA resin (phenylethylene-maleic anhydride resin), and wherein maleic anhydride content is 0.5～1.5%;
Described oxidation inhibitor is antioxidant 1010 (four (β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester), with oxidation inhibitor PEPQ (four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites) mixture, the two weight ratio is 1: 2;
Described lubricant is tetramethylolmethane stearate (PETS);
Linking agent used is isocyanuric acid three-glycidyl ester (TGIC);
Described continuous fiber strengthens polyurethane material and is prepared by following methods, and the method comprises the following steps:
(1) dry preparation: urethane raw is placed in to moisture eliminator, drying temperature: 90～100 ℃; Time of drying: 6～8h;
(2) batch mixing is prepared; By 600 parts of urethane, 15 parts of compatilizers, 12 parts of oxidation inhibitor, 5 parts of lubricants, 10 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
(3) preparation of continuous fibre enhancement polyurethane material; Adopt the impregnating equipment (CN1488674 of continuous fiber reinforced thermoplastic material, publication date: 2004.04.14), continuous fiber toughener is added into impregnating equipment by glass entrance, by the shape size (3.0mm) of mouthful mould of selection, adjust the engine speed of forcing machine at 11～13Hz simultaneously, rate of feeding is at 7.0～8.0Hz, continuous fiber toughener content is controlled at 40 ± 2%, the cutting knife rotating speed of adjusting dicing machine, makes the continuous fibre enhancement polyurethane material pelletizing length preparing be controlled at 11-13mm;
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40: 1, mixed melting Temperature Setting is: 160～180 ℃ of first paragraphs, 180～190 ℃ of second segments, the 3rd section 190～200 ℃, the 4th section 200～210 ℃, the 5th section 210～220 ℃, 205～215 ℃ of melt temperatures, 195～205 ℃ of head temperatures.
(4) injection moulding and batten test: continuous glass-fiber obtained above is strengthened to thermoplastic polyurethane material carry out injection moulding after 90～100 ℃ of dry 6～8h in baking oven, injection moulding batten is ASTM batten, and injection temperature is as follows:
Blanking section: 200～210 ℃; Second segment: 210～220 ℃; The 3rd section: 220～230 ℃; Nozzle: 210～220 ℃
Injection moulding batten is put in and in baking oven, carries out aftertreatment: treatment temp: 90 ℃; Treatment time: 16h; The performance test results is in table 1.
Comparing embodiment 1
Thermoplastic polyurethane 600
Continuous glass fibre 400
Compatilizer 10
Oxidation inhibitor 12
Lubricant 5
Linking agent 5
Described thermoplastic polyurethane is PAUR, and its Rockwell hardness is 110R;
Described continuous fiber toughener is continuous alkali free glass fibre, and Fibre diameter is 27 μ m;
Described compatilizer is SMA resin (phenylethylene-maleic anhydride resin), and wherein maleic anhydride content is 0.5～1.5%;
Described oxidation inhibitor is antioxidant 1010 (four (β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester), with oxidation inhibitor PEPQ (four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites) mixture, the two weight ratio is 1: 2;
Described lubricant is tetramethylolmethane stearate (PETS);
Linking agent used is isocyanuric acid three-glycidyl ester (TGIC);
Described continuous fiber strengthens polyurethane material and is prepared by following methods, and the method comprises the following steps:
(1) dry preparation: urethane raw is placed in to moisture eliminator, drying temperature: 90～100 ℃; Time of drying: 6～8h;
(2) batch mixing is prepared; By 600 parts of urethane, 10 parts of compatilizers, 12 parts of oxidation inhibitor, 5 parts of lubricants, 5 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
(3) preparation of fiber reinforcement polyurethane material; In order to compare, adopt the preparation method of conventional fibre reinforced thermoplasticity plastics, continuous glass fibre is directly entered into twin screw extruder from the glass entrance of forcing machine, under the shearing action of screw rod, glass and urethane resin carry out dispersing and mixing, and glass fiber content is controlled at 40 ± 2%.
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40: 1, mixed melting Temperature Setting is: 160～180 ℃ of first paragraphs, 180～190 ℃ of second segments, the 3rd section 190～200 ℃, the 4th section 200～210 ℃, the 5th section 210～220 ℃, 205～215 ℃ of melt temperatures, 195～205 ℃ of head temperatures.
(4) injection moulding and batten test: continuous glass-fiber obtained above is strengthened to thermoplastic polyurethane material carry out injection moulding after 90～100 ℃ of dry 6～8h in baking oven, injection moulding batten is ASTM batten, and injection temperature is as follows:
Blanking section: 200～210 ℃; Second segment: 210～220 ℃; The 3rd section: 220～230 ℃; Nozzle: 210～220 ℃
Injection moulding batten is put in and in baking oven, carries out aftertreatment: treatment temp: 90 ℃; Treatment time: 16h; The performance test results is in table 1.
Comparing embodiment 2
Thermoplastic polyurethane 600
Continuous glass fibre 400
Compatilizer 15
Oxidation inhibitor 12
Lubricant 5
Linking agent 10
Described thermoplastic polyurethane is PAUR, and its Rockwell hardness is 110R;
Described continuous fiber toughener is continuous alkali free glass fibre, and Fibre diameter is 27 μ m;
Described compatilizer is SMA resin (phenylethylene-maleic anhydride resin), and wherein maleic anhydride content is 0.5～1.5%;
Described oxidation inhibitor is antioxidant 1010 (four (β-(3,5-di-t-butyl-4 hydroxy phenyl) propionic acid) pentaerythritol ester), with oxidation inhibitor PEPQ (four (2,4-di-tert-butylphenol)-4,4 '-xenyl diphosphites) mixture, the two weight ratio is 1: 2;
Described lubricant is tetramethylolmethane stearate (PETS);
Linking agent used is isocyanuric acid three-glycidyl ester (TGIC);
Described continuous fiber strengthens polyurethane material and is prepared by following methods, and the method comprises the following steps:
(1) dry preparation: urethane raw is placed in to moisture eliminator, drying temperature: 90～100 ℃; Time of drying: 6～8h;
(2) batch mixing is prepared; By 600 parts of urethane, 10 parts of compatilizers, 12 parts of oxidation inhibitor, 5 parts of lubricants, 5 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
(3) preparation of fiber reinforcement polyurethane material; In order to compare, adopt the preparation method of conventional fibre reinforced thermoplasticity plastics, continuous glass fibre is directly entered into twin screw extruder from the glass entrance of forcing machine, under the shearing action of screw rod, glass and urethane resin carry out dispersing and mixing, and glass fiber content is controlled at 40 ± 2%.
Twin screw extruder used, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40: 1, mixed melting Temperature Setting is: 160～180 ℃ of first paragraphs, 180～190 ℃ of second segments, the 3rd section 190～200 ℃, the 4th section 200～210 ℃, the 5th section 210～220 ℃, 205～215 ℃ of melt temperatures, 195～205 ℃ of head temperatures.
(4) injection moulding and batten test: continuous glass-fiber obtained above is strengthened to thermoplastic polyurethane material carry out injection moulding after 90～100 ℃ of dry 6～8h in baking oven, injection moulding batten is ASTM batten, and injection temperature is as follows:
Blanking section: 200～210 ℃; Second segment: 210～220 ℃; The 3rd section: 220～230 ℃; Nozzle: 210～220 ℃
Injection moulding batten is put in and in baking oven, carries out aftertreatment: treatment temp: 90 ℃; Treatment time: 16h; The performance test results is in table 1.
Table 1
Be not difficult to find out according to the data in table 1, continuous fiber reinforced thermoplastic polyurethane material has the tensile strength, resistance to impact shock and the resistance toheat that are obviously better than chopped strand enhancing thermoplastic polyurethane material, especially aspect shock strength, continuous fiber reinforced thermoplastic urethane advantage is more outstanding.
In addition, along with the increase of compatilizer and linking agent add-on, the intensity of continuous fiber reinforced thermoplastic polyurethane material and rigidity all increase thereupon, but linking agent add-on reaches after 15 parts, the mechanical property of material declines to some extent, and the optimal addn that can obtain thus linking agent is 10 parts.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiment, and General Principle described herein is applied in other embodiment and needn't passes through performing creative labour.Therefore, the invention is not restricted to the embodiment here, those skilled in the art are according to announcement of the present invention, and not departing from the improvement that category of the present invention makes and revise all should be within protection scope of the present invention.
Claims (9)
1. a continuous fiber reinforced thermoplastic polyurethane material, is characterized in that: this material comprises following component and weight part,
Described linking agent is one or both the mixture in isocyanuric acid three-glycidyl ester or TriMethylolPropane(TMP);
Described compatilizer is selected from SMA resin;
The preparation method of described continuous fiber reinforced thermoplastic polyurethane material, comprises step:
By 200～800 parts of dry thermoplastic polyurethanes, 10～30 parts of compatilizers, 10～20 parts of oxidation inhibitor, 2～6 parts of lubricants, 5～10 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
Adopt the impregnating equipment of continuous fiber reinforced thermoplastic material, by the shape size of mouthful mould of selection, adjust forcing machine rotating speed and main frame feeding simultaneously, adjust the content of continuous fiber toughener in continuous fiber reinforced thermoplastic polyurethane material, continuous fiber toughener content can be controlled at 30～50%; The cutting knife rotating speed of adjusting dicing machine, makes the pelletizing length of the continuous fiber reinforced thermoplastic polyurethane material preparing be controlled at 11-13mm, particle diameter 2.0～4.0mm.
2. a kind of continuous fiber reinforced thermoplastic polyurethane material according to claim 1, is characterized in that: described thermoplastic polyurethane is PAUR, its Rockwell hardness is 90～120R.
3. a kind of continuous fiber reinforced thermoplastic polyurethane material according to claim 1, is characterized in that: described continuous fiber toughener is selected from the one in continuous glass fibre, carbon fiber, steel fiber or synthetic resin fiber.
4. a kind of continuous fiber reinforced thermoplastic polyurethane material according to claim 1, is characterized in that: described oxidation inhibitor is selected from one or several the mixture in Hinered phenols, hindered amines or phosphite ester kind antioxidant.
5. a kind of continuous fiber reinforced thermoplastic polyurethane material according to claim 1, is characterized in that: described lubricant is stearate.
6. a kind of continuous fiber reinforced thermoplastic polyurethane material according to claim 5, is characterized in that: described stearate is one or several the mixture in calcium stearate, Zinic stearas or tetramethylolmethane stearate.
7. the preparation method of the arbitrary described a kind of continuous fiber reinforced thermoplastic polyurethane material of claim 1 to 6, is characterized in that: the method comprises the following steps:
By 200～800 parts of dry thermoplastic polyurethanes, 10～30 parts of compatilizers, 10～20 parts of oxidation inhibitor, 2～6 parts of lubricants, 5～10 parts of linking agents, join successively in high mixer, mixture temperature is controlled at 40～60 ℃, after mixing time 3-5 minute, stop, then mixed material is added in the hopper of forcing machine for subsequent usely, the drying temperature of forcing machine hopper is set as 80～90 ℃;
Adopt the impregnating equipment of continuous fiber reinforced thermoplastic material, by the shape size of mouthful mould of selection, adjust forcing machine rotating speed and main frame feeding simultaneously, adjust the content of continuous fiber toughener in continuous fiber reinforced thermoplastic polyurethane material, continuous fiber toughener content can be controlled at 30～50%; The cutting knife rotating speed of adjusting dicing machine, makes the pelletizing length of the continuous fiber reinforced thermoplastic polyurethane material preparing be controlled at 11-13mm, particle diameter 2.0～4.0mm;
Described linking agent is one or both the mixture in isocyanuric acid three-glycidyl ester or TriMethylolPropane(TMP).
8. the preparation method of a kind of continuous fiber reinforced thermoplastic polyurethane material according to claim 7, is characterized in that: described dry thermoplastic polyurethane is thermoplastic polyurethane to be placed in to moisture eliminator be dried, drying temperature: 90～100 ℃; Time of drying: 6～8h.
9. the preparation method of a kind of continuous fiber reinforced thermoplastic polyurethane material according to claim 7, it is characterized in that: described forcing machine is twin screw extruder, screw diameter 65mm, the length-to-diameter ratio of screw rod is 40:1, mixed melting Temperature Setting is: 160～180 ℃ of first paragraphs, 180～190 ℃ of second segments, the 3rd section 190～200 ℃, the 4th section 200～210 ℃, the 5th section 210～220 ℃, 205～215 ℃ of melt temperatures, 195～205 ℃ of head temperatures.
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