CN103881335A - Reactively extruded, branched and toughened PET (polyethylene terephthalate) and preparation method thereof - Google Patents

Abstract

The invention discloses reactively extruded, branched and toughened PET (polyethylene terephthalate) and a preparation method thereof. The preparation method is characterized by comprising the steps of mixing 100 parts of dry PET with 0.1-5 parts of polyisocyanate, 1-20 parts of polyether amine branching agent and 0.1-5 parts of antioxidant uniformly in a high-speed universal pulverizer, and extruding, water-cooling and granulating the mixture in a double-screw extruder, wherein the barrel temperature of the extruder is 250-280 DEG C and the screw speed is 60-80r/min; drying the extruded material at 130 DEG C for 4 hours, thus obtaining the toughened PET product.

Description

A kind of reactivity is extruded branching toughened PET and preparation method thereof

Technical field

The present invention relates to a kind of reactive branching and extrude toughened PET and preparation method thereof, belong to polymkeric substance and synthesize and manufacture field.

Background technology

Polyethylene terephthalate (PET) is nineteen fifty-three to realize the earliest industrialized line style thermoplastic engineering plastic by Dupont company, it is typical semicrystalline polymeric, there is good chemical stability, wear resistance, thermotolerance, electrical insulating property and mechanical property, especially transparent good, be widely used in the fields such as packing bottle, film, synthon.But when PET uses as injection moulding engineering plastics, also exist the shortcomings such as crystallization velocity is slow, dimensional contraction rate is large, goods shock strength is low, its application is produced to detrimentally affect.

Chinese scholars has been carried out extensive work to the toughening modifying of PET.As adopt ethylene-octene copolymer (POE), maleic anhydride graft styrene-butadiene rubber(SBR) (SBR-g-MAH), thermoplastic elastic body styrene-ethene-butylene-styrene segmented copolymer (SEBS) etc. to carry out elastic body toughening modification to PET, though can effectively improve the toughness of blend, but its tensile strength and Young's modulus etc. are significantly declined, and reduced the transparency of PET.Adopt the high tenacity thermoplastic engineering plastics such as polymeric amide, polycarbonate to carry out blending and modifying to PET, in improving its toughness, can keep suitable intensity and Young's modulus, but the raising of the notched Izod impact strength of PET is limited.For improving the each component interface compatibility of blending modification system, chainextender toughening modifying technology obtains broad research in recent years.Guo Weihong, SCI, 2007,28 (11): 2200 – 2204, adopt low temperature solid-state extrusion reaction technology, have studied the impact of chainextender MDI on r-PET/PC/SEBS co-mixing system performance.Research finds, MDI adds the effect that has played increase-volume, obtains a kind of " super toughness " material.This is because MDI can carry out chain extending reaction with PET and PC on the one hand, improves the molecular weight of system; On the other hand, MDI can generate multipolymer with the hydroxyl reaction of the carboxyl of PET, hydroxyl, PC again, thereby improves the consistency of system.

Summary of the invention

The object of the invention is provides a kind of reactivity to extrude toughened PET and preparation method thereof for the deficiencies in the prior art, be characterized in selecting the agent of polyetheramine/polyisocyanates branched modification by reactive extrusion processing toughened PET, obtain the PET of rigidity-toughness balanced, excellent combination property.

Object of the present invention is realized by following technical measures, and wherein said raw material mark, except specified otherwise, is parts by weight.

The starting raw material recipe ingredient that reactivity is extruded branching toughened PET is:

Wherein, the limiting viscosity of PET resin is 0.6-0.8dl/g;

Vulcabond is any in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI);

Polyetheramine branching agent is any in diamino polyoxytrimethylene ether (molecular weight: 2000～5000g/mol), triamino polyoxyethylene ether (molecular weight: 1000～4000g/mol), polyamino polyoxyethylene propylene ether (molecular weight: 500～3000g/mol);

Oxidation inhibitor is four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; N; N'-pair-[3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid stearyl alcohol ester; any in 2,6 di tert butyl 4 methyl phenol.

Reactivity is extruded the preparation of branching toughened PET

0.1～5 part of 0.1～5 part of dry PET100 part and polyisocyanates, 1～20 part of polyetheramine branching agent, oxidation inhibitor is mixed in high speed Universalpulverizer, in twin screw extruder, extrude, water-cooled, granulation, extruder barrel temperature is 250-280 DEG C, and screw speed is 60～80r/min; Extruded stock, in 130 DEG C of dry 4h, obtains toughened PET product.

Tool of the present invention has the following advantages

The present invention calls in a kind of reactivity of preparation and extrudes branching toughened PET material; there is following features: because the end group (-NCO) of vulcabond is very active; terminal hydroxy group, end carboxyl and polyetheramine end amino by itself and PET react; on PET molecule, introduce polyethers flexible molecule chain; adopt reactive processing to prepare structure controlled multi-arm long chain branch PET to a certain extent; give the higher toughness of PET by the physical entanglement effect of its molecule, thereby realize the in-situ flexible to PET.

Embodiment

Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the content of the invention described above.

Embodiment 1

The PET10Kg that is 0.68dl/g by dry limiting viscosity and polyisocyanates 0.05Kg, diamino polyoxytrimethylene ether (molecular weight: 2000g/mol) 0.5Kg, four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 0.03Kg mixes in high speed Universalpulverizer, in twin screw extruder, extrude, water-cooled, granulation, extruder barrel temperature is 260-270 DEG C, and screw speed is 80r/min; Extruded stock, in 130 DEG C of dry 4h, obtains toughened PET product, and its tensile strength is 59.9MPa, and notched Izod impact strength is 3.5KJ/m ².

Embodiment 2

The PET10Kg that is 0.72dl/g by dry limiting viscosity and polyisocyanates 0.1Kg, triamino polyoxyethylene ether (molecular weight: 4000g/mol) 1.5Kg, N, N'-pair-[3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine 0.1Kg mixes in high speed Universalpulverizer, in twin screw extruder, extrude, water-cooled, granulation, extruder barrel temperature is 260-280 DEG C, and screw speed is 70r/min; Extruded stock, in 130 DEG C of dry 4h, obtains toughened PET product, and its tensile strength is 58.3MPa, and notched Izod impact strength is 5KJ/m ².

Embodiment 3

The PET10Kg that is 0.80dl/g by dry limiting viscosity and polyisocyanates 0.2Kg, polyamino polyoxyethylene propylene ether (molecular weight: 3000g/mol) 2Kg, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid stearyl alcohol ester 0.2Kg mixes in high speed Universalpulverizer, in twin screw extruder, extrude, water-cooled, granulation, extruder barrel temperature is 270-280 DEG C, and screw speed is 60r/min; Extruded stock, in 130 DEG C of dry 4h, obtains toughened PET product, and its tensile strength is 57.0MPa, and notched Izod impact strength is 7KJ/m ².

Claims (2)

1. reactivity is extruded a branching toughened PET, it is characterized in that the starting raw material recipe ingredient of this material is by weight:

Wherein, the limiting viscosity of PET resin is 0.6-0.8dl/g;

Vulcabond is any in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI);

Polyetheramine branching agent is any in diamino polyoxytrimethylene ether (molecular weight: 2000～5000g/mol), triamino polyoxyethylene ether (molecular weight: 1000～4000g/mol), polyamino polyoxyethylene propylene ether (molecular weight: 500～3000g/mol);

Oxidation inhibitor is four [β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; N; N'-pair-[3-(3; 5-di-tert-butyl-hydroxy phenyl) propionyl] hexanediamine, β-(4-hydroxyl-3,5-di-tert-butyl-phenyl) propionic acid stearyl alcohol ester; any in 2,6 di tert butyl 4 methyl phenol.

2. the reactive preparation method who extrudes branching toughened PET as claimed in claim 1, is characterized in that the method comprises the following steps:

0.1～5 part of 0.1～5 part of dry PET100 part and polyisocyanates, 1～20 part of polyetheramine branching agent, oxidation inhibitor is mixed in high speed Universalpulverizer, in twin screw extruder, extrude, water-cooled, granulation, extruder barrel temperature is 250-280 DEG C, and screw speed is 60～80r/min; Extruded stock, in 130 DEG C of dry 4h, obtains toughened PET product.