CN1927933A

CN1927933A - Method of improving PP-R resin capability

Info

Publication number: CN1927933A
Application number: CN 200510098310
Authority: CN
Inventors: 邹敏; 刘国钦; 王军; 王琪琳; 李玉峰
Original assignee: Panzhihua University
Current assignee: Panzhihua University
Priority date: 2005-09-07
Filing date: 2005-09-07
Publication date: 2007-03-14

Abstract

The present invention relates to modified PP-R resin. The modified PP-R resin is prepared through mixing PP-R resin in 96 wt% and modifying zinc oxide whisker in 0-4 wt%, kneading in high speed kneading machine, discharging at about 130 deg.c, mixing with treated nanometer TiO2 in 0-4 wt% in a double roller machine at about 210 deg.c and palletizing in a double screw extruder, with the total amount of the zinc oxide whisker and the nanometer TiO2 being 4 wt%. The modified PP-R resin has high thermal deformation temperature, high elongation at break and excellent antibiotic performance.

Description

A kind of method of improving the PP-R resin property

Technical field

The present invention relates to the study on the modification of PP-R resin, mainly is to adopt inorganic nano-particle to improve the PP-R resin property.

Background technology

The PP-R material has the better heat-resisting performance, and its vicat softening temperature is 131.5 ℃, and maximum operating temperature can reach 95 ℃, and the life-time service temperature generally can reach 70 ℃, can satisfy the water delivery requirement under the general condition fully.But in some in particular cases (as the conveying of winter hot water, heating installation etc.), when the temperature of delivery medium surpasses 100 ℃, then must carry out modification, could satisfy service requirements the PP-R material.In addition, the anti-microbial property that is related to the PP-R material of human health and environment protection also more and more causes people's attention.

Chinese patent CN03118438.3 system adopts metallocene polymers modifying PP-R coil pipe and preparation method thereof, and this patent is to add the Freon-free flame-retardant agent to improve its fire resistance at the PP-R material.The PP-R tubing of Chinese patent CN03225671.X, CN03267082.6, CN02113511.8 report all has the antimicrobial advantage; Its antimicrobial efficiency is all about 90%, and not seeing up to now has that heat-drawn wire surpasses 100 ℃, anti-microbial property surpasses the achievement in research report of 90% PP-R material simultaneously.On some other non-patent literature, also have use temperature to surpass the report of 100 ℃ modifying PP-R resin, but do not report its concrete technology in the document, and the indication of heat resisting temperature is indeterminate.

The invention provides a kind of heat resisting temperature height, a kind of method of improving the PP-R resin property that antibacterial ability is higher.

Technology contents

The present invention is to be that the KH560 coupling agent of whisker quality 0.5% dissolves in the alcohol solvent with quality, carries out the ultrasonic dispersing of 20min after the longer whisker of zinc oxide being put into, and filtering also becomes the modified zinc oxide whisker after the oven dry down at 100 ℃, at TiO ₂In the oar material, add water miscible Na ₂SiO ₃, be neutralized to pH=8-9 with acid, make silicon with Si (OH) ₄Form be deposited in TiO ₂Back oven dry becoming modified Nano TiO is filtered on the particulate surface ₂, then, stir after modified zinc oxide whisker with 0～4% and 96% the PP-R resin batching, mediate 130 ℃ of left and right sides dischargings in high speed kneader high speed; With 0～4% the nano-TiO of handling well ₂Blend on twin-roll machine, temperature are about 210 ℃, wherein long whisker of zinc oxide and nano-TiO ₂Total amount and be 4%; Through double-screw extruding pelletizing.

The present invention has the following advantages:

1, the PP-R resin heat-drawn wire after modification can reach 102 ℃, can satisfy fully in some in particular cases (as the conveying of the hot water of northern area in winter, heating installation etc.), service requirements when the temperature of delivery medium surpasses 100 ℃ has huge economic benefit and use prospect.

2, the antibiotic rate of the PP-R resin after modification can reach 99%, can satisfy the needs of protection environment and human health fully, is a kind of novel environment-friendly materials.

3, the kind of properties-correcting agent and quantity can change according to the concrete needs that use, and is alternative strong.

4, technology is simple, and is practical.

Description of drawings

Fig. 1 is a process flow sheet of the present invention.

Some explanation to process chart:

1, the modification of the long whisker of zinc oxide: the KH560 coupling agent of 0.5% (in the whisker quality) is dissolved in the alcohol solvent, and the ultrasonic wave that carries out 20min after the longer whisker of zinc oxide being put into disperses, and filters and dry under 100 ℃ rear for subsequent use.

2, nano-TiO₂Modification: at TiO₂In the oar material, add water miscible Na₂SiO ₃, be neutralized to pH=8-9 with acid, make silicon with Si (OH)₄Form be deposited in TiO₂The surface of particle is filtered rear 60 ℃ of lower dry for standby.

3, stir after the PP-R resin batching with the modified zinc oxide whisker of 0-4% and 96%, mediate 130 ℃ of dischargings in high-speed kneading machine high speed; The nano-TiO of handling well with 0-4%₂Particle is blend on twin-roll machine, and temperature is about 210 ℃, wherein the long whisker of zinc oxide and nano-TiO₂Total amount and be 4%; Through double-screw extruding pelletizing, obtain the modifying PP-R resin.

Process conditions of the present invention are:

The long whisker of zinc oxide: long 10-30 μ m, four angular pin shapes

KH560: reagent, analyze pure

Nano-TiO ₂: granularity 20～50nm, crystal formation are anatase titanium dioxide

NaSiO3 solid: analytical pure

Sulfuric acid: 98%

Ethanol: analytical pure

PP-R resin: the trade mark 401, melting index 3g/10min

KH560: the long whisker of zinc oxide=0.5: 100

The long whisker of zinc oxide: nano-TiO ₂: PP-R resin=3.5: 0.5: 96

The ultrasonic dispersing time: 20min

The long whisker bake out temperature of modified zinc oxide: 100 ℃

Nano-TiO ₂PH value during modification: 8-9

TiO ₂Bake out temperature: 60 ℃

Mediate temperature: 130 ℃

Blending temperature: 210 ℃

Adopt the modifying PP-R resin of above-mentioned processing condition availability excellence, its technical indicator and unmodified PP-R resin are relatively as table 1:

Properties-correcting agent kind and consumption/%	Tensile strength MPa	Maximum elongation rate %	Heat-drawn wire ℃	Softening temperature ℃	Antibiotic rate %
Properties-correcting agent kind and consumption/%	Tensile strength MPa	Maximum elongation rate %	Heat-drawn wire ℃	Softening temperature ℃	Antibiotic rate %	Do not use properties-correcting agent	24	45	72	132	17
The long whisker of 3.5%ZnO+0.5% nano-TiO ₂	27	112	101	145	99	Do not use properties-correcting agent	24	45	72	132	17

Table 1: through the long whisker of 3.5%ZnO+0.5% nano-TiO ₂The PP-R resin of modification and unmodified PP-R tree

The fat performance relatively

As seen from the above table, through the long whisker of 3.5%ZnO+0.5% nano-TiO ₂The PP-R resin of modification is compared with unmodified PP-R resin, and every performance index of resin have all had significant raising after the modification, and wherein the raising of elongation at break, heat-drawn wire, antibiotic rate is especially obvious.

In above-mentioned steps 3, the kind of properties-correcting agent and quantity all can change according to concrete needs, and the performance of resulting modifying PP-R material also respective change will take place, and see Table 2:

Properties-correcting agent kind and consumption/%	Tensile strength MPa	Maximum elongation rate %	Heat-drawn wire ℃	Softening temperature ℃	Antibiotic rate
Properties-correcting agent kind and consumption/%	Tensile strength MPa	Maximum elongation rate %	Heat-drawn wire ℃	Softening temperature ℃	Antibiotic rate	The long whisker of 4%ZnO	27	112	102	143	20％
The long whisker of 3.5%ZnO+0.5% nano-TiO ₂	27	112	101	145	99％	The long whisker of 4%ZnO	27	112	102	143	20％
The long whisker of 3.5%ZnO+0.5% nano-TiO ₂	27	112	101	145	99％	4% nano-TiO ₂	26	90	90	143	98％

Table 2: the performance of PP-R material under different properties-correcting agent kinds and the consumption condition

As can be seen from Table 2, the present invention can adjust the kind and the consumption of properties-correcting agent according to the needs that use.When service requirements is that properties-correcting agent can be selected 4% the long whisker of ZnO when improving the resistance toheat of PP-R resin; When service requirements is that properties-correcting agent can be selected 4% nano-TiO when improving the antibiotic rate of PP-R resin ₂, when service requirements be should improve the resistance toheat of resin, when improving the antibiotic rate of resin again, properties-correcting agent can be selected the long whisker of 3.5%ZnO+0.5% nano-TiO ₂

Embodiment

Example 1:

Taking by weighing the long whisker of the zinc oxide after modification of 4% (mass ratio), is to stir after 96% the P-R resin batching with mass ratio, mediate in high speed kneader high speed, and 130 ℃ of dischargings, blend on twin-roll machine, temperature is about 210 ℃; Through double-screw extruding pelletizing, the technical indicator that obtains the modifying PP-R resin is: tensile elongation 27Mpa, maximum elongation rate 112%, 102 ℃ of heat-drawn wires, 143 ℃ of softening temperatures, antibiotic rate 20%.

Example 2:

Take by weighing 4% (mass ratio) through modified TiO ₂, be to stir after 96% the P-R resin batching with mass ratio, mediate in high speed kneader high speed, 130 ℃ of dischargings, blend on twin-roll machine, temperature is about 210 ℃; Through double-screw extruding pelletizing, the technical indicator that obtains the modifying PP-R resin is: tensile elongation 26Mpa, maximum elongation rate 90%, 90 ℃ of heat-drawn wires, 143 ℃ of softening temperatures, antibiotic rate 98%.

Example 3:

Take by weighing mass ratio and be 3.5% long whisker of modified zinc oxide and mass ratio and be and stir after 96% PP-R resin is prepared burden by a certain percentage, mediate 130 ℃ of dischargings in high speed kneader high speed; With the nano TiO 2 of handling well (mass ratio is 0.5%) blend on twin-roll machine, temperature is about 210 ℃; Through double-screw extruding pelletizing, the technical indicator that obtains the modifying PP-R resin is: tensile elongation 27Mpa, maximum elongation rate 112%, 101 ℃ of heat-drawn wires, 143 ℃ of softening temperatures, antibiotic rate 99%.

Claims

1, a kind of method of improving the PP-R resin property, it is characterized in that: with quality is that the KH560 coupling agent of whisker quality 0.5% dissolves in the alcohol solvent, carry out the ultrasonic dispersing of 20min after the longer whisker of zinc oxide being put into, filtration also becomes the modified zinc oxide whisker after drying under 100 ℃, at TiO ₂In the oar material, add water miscible Na ₂SiO ₃, be neutralized to pH=8-9 with acid, make silicon with Si (OH) ₄Form be deposited in TiO ₂Back oven dry becoming modified Nano TiO is filtered on the particulate surface ₂, then, stir after the modified zinc oxide whisker with 0～4% and 96% the PP-R resin batching, to mediate in high speed kneader high speed, 130 ℃ of left and right sides dischargings are with 0～4% the nano-TiO of handling well ₂Blend on twin-roll machine, temperature are about 210 ℃, wherein long whisker of modified zinc oxide and modified Nano TiO ₂Total amount and be 4% is through double-screw extruding pelletizing.

2, a kind of method of improving the PP-R resin property as claimed in claim 1 is characterized in that stirring after the PP-R resin batching with 3.5% modified zinc oxide whisker and 96%, mediates 130 ℃ of left and right sides dischargings in high speed kneader high speed; With 0.5% the nano-TiO of handling well ₂Blend on twin-roll machine, temperature are about 210 ℃, through double-screw extruding pelletizing.

3, a kind of method of improving the PP-R resin property as claimed in claim 1 is characterized in that not using the long whisker of modified zinc oxide, nano-TiO ₂Usage quantity be 4%.

4, a kind of method of improving the PP-R resin property as claimed in claim 1, its feature is characterized in that not using modified Nano TiO ₂, the usage quantity of the long whisker of zinc oxide is 4%.