CN103881335B - A kind of Reaction extrusion branching toughened PET and preparation method thereof - Google Patents

Abstract

The present invention discloses a kind of Reaction extrusion branching toughened PET and preparation method thereof, be characterized in: PET100 part of drying and polyisocyanates 0.1 ~ 5 part, polyetheramine branching agent 1 ~ 20 part, 0.1 ~ 5 part, oxidation inhibitor are mixed in high speed Universalpulverizer, extrude in twin screw extruder, 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.

Description

A kind of Reaction extrusion 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 Macroscopic single crystal and manufacture field.

Background technology

Polyethylene terephthalate (PET) realizes industrialized linear thermoplastic's engineering plastics the earliest by Dupont company at nineteen fifty-three, it is typical semicrystalline polymeric, there is excellent 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 there is the shortcomings such as crystallization velocity is slow, dimensional contraction rate is large, goods shock strength is low, detrimentally affect is produced to its application.

The toughening modifying of Chinese scholars to PET has carried out extensive work.As adopted ethylene-octene copolymer (POE), maleic anhydride graft styrene-butadiene rubber(SBR) (SBR-g-MAH), thermoplastic elastic body styrene-ethylene-butylene, Styrene segmented copolymer (SEBS) etc., elastic body toughening modification is carried out to PET, though the toughness of blend effectively can be improved, but its tensile strength and Young's modulus etc. are significantly declined, and reduces the transparency of PET.Adopt the high-toughness thermoplastic such as polymeric amide, polycarbonate engineering plastics to carry out blending and modifying to PET, suitable intensity and Young's modulus can be kept while its toughness of raising, but the notched Izod impact strength of PET improves limited.For improving each component interface compatibility of blending modification system, chainextender toughening modifying technology is extensively studied 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 serving increase-volume, obtains a kind of " ultra-tough " material.This is because MDI can carry out chain extending reaction with PET and PC on the one hand, improve 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, thus improves the consistency of system.

Summary of the invention

The object of the invention is to provide a kind of Reaction extrusion toughened PET and preparation method thereof for the deficiencies in the prior art, be characterized in selecting polyetheramine/polyisocyanates branched modification agent 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 of Reaction extrusion branching toughened PET is:

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

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

Polyetheramine branching agent is any one in the polyamino polyoxyethylene propylene ether of the diamino polyoxytrimethylene ether of molecular weight 2000 ~ 5000g/mol, the triamino polyoxyethylene ether of molecular weight 1000 ~ 4000g/mol, 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 octadecyl; any one in 2,6 di tert butyl 4 methyl phenol.

The preparation of Reaction extrusion branching toughened PET

PET100 part of drying and polyisocyanates 0.1 ~ 5 part, polyetheramine branching agent 1 ~ 20 part, 0.1 ~ 5 part, oxidation inhibitor are mixed in high speed Universalpulverizer, extrude in twin screw extruder, 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 at a kind of Reaction extrusion branching toughened PET material of preparation; there is following features: because the end group (-NCO) of vulcabond is very active; reacted by the terminal hydroxy group of itself and PET, end carboxyl and polyetheramine Amino End Group; PET molecule is introduced polyether soft molecular chain; reactive processing is adopted to prepare structure multi-arm long chain branch PET controlled to a certain extent; give the higher toughness of PET by the physical entanglement effect of its molecule, thus realize the in-situ flexible to PET.

Embodiment

Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that the 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 according to the content of the invention described above to the present invention.

Embodiment 1

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

Embodiment 2

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

Embodiment 3

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

Claims (2)

1. a Reaction extrusion branching toughened PET, 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 one in tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI);

Polyetheramine branching agent is any one in the polyamino polyoxyethylene propylene ether of the diamino polyoxytrimethylene ether of molecular weight 2000 ~ 5000g/mol, the triamino polyoxyethylene ether of molecular weight 1000 ~ 4000g/mol, 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 octadecyl; any one in 2,6 di tert butyl 4 methyl phenol.

2. the preparation method of Reaction extrusion branching toughened PET as claimed in claim 1, is characterized in that the method comprises the following steps:

PET100 part of drying and polyisocyanates 0.1 ~ 5 part, polyetheramine branching agent 1 ~ 20 part, 0.1 ~ 5 part, oxidation inhibitor are mixed in high speed Universalpulverizer, extrude in twin screw extruder, 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.