CN104861453A - Core-shell particle filling PTT composite material and preparation method therefor - Google Patents

Abstract

The invention discloses a core-shell particle filling PTT composite material and a preparation method therefor. The composite material comprises the following ingredients, by weight, 65%-85% of PTT, 8%-12% of glass fibers, 5%-15% of calcium carbonate particles, 0.5%-2% of diisocyanate, 1%-4% of glycol, 0.1%-0.5% of anti-oxidants and 0.1%-1% of lubricants. The beneficial effects are that polyurethane elastomers are generated through in situ polymerization and cover surfaces of the calcium carbonate particles, core-shell particles with calcium carbonate particles as cores and with the elastomers as shells are formed to fill PTT; glass is employed for enhancement modification, and thus the prepared PTT composite material has advantages of high impact resistance, high intensity, high heat resistant stability and the like.

Description

PTT matrix material that a kind of core-shell particle is filled and preparation method thereof

Technical field

The present invention relates to technical field of polymer materials, PTT matrix material of specifically a kind of core-shell particle filling and preparation method thereof.

Background technology

Poly(Trimethylene Terephthalate) (PTT) is as a kind of new polyester macromolecular material of excellent combination property, the fields such as fiber, film, engineering plastics are widely used at present, but notched Izod impact strength is low, notch sensitivity is large defect that unmodified PTT exists, this greatly limits PTT and applies widely in every field.Elastomerics is dispersed in PTT matrix in the mode of dispersed particle, good toughening effect can be had, but the shortcoming of this method for toughening is after the rubber particles adding low modulus in a large number, reduces the performances such as its intensity, rigidity and thermotolerance while the toughness of PTT can be made to be improved, when adopting rigid particles to carry out toughness reinforcing to PTT, rigid particles is while raising PTT toughness, also can improve the intensity of PTT, rigidity and thermotolerance, and contribute to improving rheological performance, it is lower that Rigid Particles Toughened can obtain cost from the starting material of cheapness, the high-performance PTT that moulding processability is good, but Rigid Particles Toughened must carry out necessary modification to rigid particles surface, as passed through coupling agent, compatilizer improves the compatibility problem of rigid particles and PTT matrix, but use coupling agent merely, compatilizer also far can not solve rigid particles completely and be difficult to toughness reinforcing problem.So, propose to use the multiple elements design system of PTT/ elastomerics/stiff differential equations to fill activeness and quietness, namely rubber particles-rigid particles " coated " structure or so-called " shell-core " structure is formed, play rubber particles (improve toughness but sacrifice modulus) and (improve rigidity easy with rigid particles, but it is difficult to improve toughness) respective advantage, to play effective collaborative activeness and quietness effect.Because for elastomerics/inorganic rigid particle composite toughening PTT system, add the toughness that improve matrix on the one hand due to elastomeric, when adding inorganic rigid particle, its toughening effect is just particularly evident, thus demonstrates coordination plasticizing effect; On the one hand, when elastomerics and inorganic rigid particle form " soft core-duricrust " structure, flexible interface layer is there is between rigid particles and matrix, enhance the interfacial adhesion of matrix and filler, be beneficial to the transmission of stress from matrix to mineral filler, the dispersiveness of filler can be improved in addition, reduce its aggregation tendency, improve the comprehensive mechanical property of compound system.

Summary of the invention

PTT matrix material that the object of the present invention is to provide a kind of core-shell particle to fill and preparation method thereof.

The technical solution adopted for the present invention to solve the technical problems is: the PTT matrix material that a kind of core-shell particle is filled, and its component by mass percent proportioning is: PTT 65% ~ 85%, glass fibre 8% ~ 12%, calcium carbonate particles 5% ~ 15%, vulcabond 0.5% ~ 2%, ethylene glycol 1% ~ 4%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.

Described PTT is the Poly(Trimethylene Terephthalate) of limiting viscosity 0.7 ~ 1.2dL/g.

Described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process.

Described calcium carbonate particles is the water-ground limestone particulate that particle diameter is less than 5 μm.

Described oxidation inhibitor is the one in the compound of antioxidant 1010, antioxidant 1076, antioxidant 1010 or antioxidant 1076 and irgasfos 168.

Described lubricant is the one in calcium stearate, pentaerythritol stearate, modification ethylene bis-fatty acid amides.

The preparation method of the PTT matrix material that above-mentioned a kind of core-shell particle is filled, comprises the following steps:

(1) forced air circulation baking oven, by PTT is placed at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles at 60 DEG C ~ 100 DEG C temperature dry 1 ~ 2 hour, stand-by;

(2), take dry calcium carbonate particles by weight ratio and add barrel temperature in 40 DEG C ~ 70 DEG C mixing machines, add the ethylene glycol taken by weight ratio simultaneously, make stirring at low speed 5 ~ 30 minutes together, add the vulcabond taken by weight ratio again, and high-speed stirring 5 ~ 60 minutes, make abundant addition polymerization and coated caco3 particle, then dry PTT is added by important proportioning, and add the oxidation inhibitor and lubricant that take by weight ratio, make to stir 3 ~ 15 minutes together, discharging after fully mixing;

(3), the compound of step (2) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 120 ~ 400r/min, processing temperature is 200 DEG C ~ 280 DEG C scopes, then extrude, cooling granulation, drying, obtain the present invention.

The invention has the beneficial effects as follows, the present invention generates polyurethane elastomer by in-situ polymerization and is coated on calcium carbonate particles surface, the core-shell particle that formation is core with calcium carbonate particles, elastomerics is shell is filled PTT, adopt glass strengthening modification simultaneously, make the PTT matrix material obtained have the advantages such as high impact properties, high strength, high heat-resistant stability.

Embodiment

Technical scheme of the present invention is further illustrated below in conjunction with concrete preferred embodiment.

Embodiment 1:

The PTT matrix material that a kind of core-shell particle is filled, its component by mass percent proportioning is: PTT 66%, glass fibre 12%, calcium carbonate particles 15%, vulcabond 2%, ethylene glycol 4%, antioxidant 1010 0.2%, calcium stearate 0.8%, described PTT is the Poly(Trimethylene Terephthalate) of limiting viscosity 0.7 ~ 1.2dL/g, described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process, and described calcium carbonate particles is the water-ground limestone particulate that particle diameter is less than 5 μm.

Preparation method: (1), PTT is placed in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles at 60 DEG C ~ 100 DEG C temperature dry 1 ~ 2 hour, stand-by; (2), take dry calcium carbonate particles by weight ratio and add barrel temperature in 40 DEG C ~ 70 DEG C mixing machines, add the ethylene glycol taken by weight ratio simultaneously, make stirring at low speed 5 ~ 30 minutes together, add the vulcabond taken by weight ratio again, and high-speed stirring 5 ~ 60 minutes, make abundant addition polymerization and coated caco3 particle, then dry PTT is added by important proportioning, and add the antioxidant 1010 and calcium stearate that take by weight ratio, make to stir 3 ~ 15 minutes together, discharging after fully mixing; (3), the compound of step (2) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 120 ~ 400r/min, processing temperature is 200 DEG C ~ 280 DEG C scopes, then extrude, cooling granulation, drying, obtain the present invention.

Embodiment 2:

The PTT matrix material that a kind of core-shell particle is filled, its component by mass percent proportioning is: the compound 0.2% of PTT 77%, glass fibre 8%, calcium carbonate particles 10%, vulcabond 1.5%, ethylene glycol 3%, antioxidant 1076 and irgasfos 168, modification ethylene bis-fatty acid amides 0.3%, described PTT is the Poly(Trimethylene Terephthalate) of limiting viscosity 0.7 ~ 1.2dL/g, described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process, and described calcium carbonate particles is the water-ground limestone particulate that particle diameter is less than 5 μm.

Preparation method: (1), PTT is placed in forced air circulation baking oven at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles at 60 DEG C ~ 100 DEG C temperature dry 1 ~ 2 hour, stand-by, (2), take dry calcium carbonate particles by weight ratio and add barrel temperature in 40 DEG C ~ 70 DEG C mixing machines, add the ethylene glycol taken by weight ratio simultaneously, make stirring at low speed 5 ~ 30 minutes together, add the vulcabond taken by weight ratio again, and high-speed stirring 5 ~ 60 minutes, make abundant addition polymerization and coated caco3 particle, then dry PTT is added by important proportioning, and add the compound of antioxidant 1076 and the irgasfos 168 taken by weight ratio, modification ethylene bis-fatty acid amides, make to stir 3 ~ 15 minutes together, discharging after fully mixing, (3), the compound of step (2) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 120 ~ 400r/min, processing temperature is 200 DEG C ~ 280 DEG C scopes, then extrude, cooling granulation, drying, obtain the present invention.

Claims (4)

1. the PTT matrix material of a core-shell particle filling, it is characterized in that, its component by mass percent proportioning is: PTT 65% ~ 85%, glass fibre 8% ~ 12%, calcium carbonate particles 5% ~ 15%, vulcabond 0.5% ~ 2%, ethylene glycol 1% ~ 4%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.

2. the PTT matrix material of a kind of core-shell particle filling according to claim 1, is characterized in that, described glass fibre is the alkali-free short glass fiber of surface through silane coupling agent process.

3. the PTT matrix material of a kind of core-shell particle filling according to claim 1, it is characterized in that, described calcium carbonate particles is the water-ground limestone particulate that particle diameter is less than 5 μm.

4. the preparation method of the PTT matrix material of a kind of core-shell particle filling according to claim 1, is characterized in that, comprise the following steps:

(1) forced air circulation baking oven, by PTT is placed at 110 DEG C ~ 120 DEG C temperature dry 6 ~ 8 hours, by calcium carbonate particles at 60 DEG C ~ 100 DEG C temperature dry 1 ~ 2 hour, stand-by;

(2), take dry calcium carbonate particles by weight ratio and add barrel temperature in 40 DEG C ~ 70 DEG C mixing machines, add the ethylene glycol taken by weight ratio simultaneously, make stirring at low speed 5 ~ 30 minutes together, add the vulcabond taken by weight ratio again, and high-speed stirring 5 ~ 60 minutes, make abundant addition polymerization and coated caco3 particle, then dry PTT is added by important proportioning, and add the oxidation inhibitor and lubricant that take by weight ratio, make to stir 3 ~ 15 minutes together, discharging after fully mixing;

(3), the compound of step (2) is added the main spout of twin screw extruder, add from the side spout of twin screw extruder the glass fibre taken by weight ratio simultaneously, by twin screw extruder melting mixing 1 ~ 2 minute, screw speed controls at 120 ~ 400r/min, processing temperature is 200 DEG C ~ 280 DEG C scopes, then extrude, cooling granulation, drying, obtain the present invention.