WO2018137320A1

WO2018137320A1 - Mt ferrule raw material and preparation method therefor

Info

Publication number: WO2018137320A1
Application number: PCT/CN2017/093166
Authority: WO
Inventors: 黄雪云
Original assignee: 潮州三环（集团）股份有限公司
Priority date: 2017-01-26
Filing date: 2017-07-17
Publication date: 2018-08-02
Also published as: CN106832930A

Abstract

Disclosed are an MT ferrule raw material and a preparation method therefor. Said ferrule raw material comprises the following components in mass percentage: 14.5%-35％ of polyphenylene sulfide, and 55%-85％ of an inorganic filler, wherein the inorganic filler is at least one of zirconium dioxide, silicon dioxide, alumina, iron oxide, zinc oxide and calcium carbonate. Regarding the defects of existing MT ferrule raw materials, the MT ferrule raw material prepared by the method of the present invention has better dimensional stability and a lower thermal expansion coefficient, and at the same time lower costs, and a longer service life.

Description

MT ferrule raw material and preparation method thereof

Technical field

The invention relates to a communication technology, in particular to an MT ferrule raw material and a preparation method thereof.

Background technique

Polyphenylene sulfide is a special engineering plastic with excellent comprehensive performance. It has high temperature resistance, corrosion resistance, radiation resistance, non-combustibility, non-toxicity, excellent mechanical and electrical properties, good dimensional stability of products, and various methods. Forming processing and secondary processing of the product. Polyphenylene sulfide resin has low melt viscosity, can mix a large amount of filler material, and has low molding shrinkage. This material can be used to obtain MT ferrules with high dimensional accuracy, and the obtained MT ferrule has low water absorption rate and small dimensional change after water absorption. , good chemical resistance and good dimensional stability. However, the rigid structure of the polyphenylene sulfide resin determines its superior performance, and also makes its disadvantage, brittleness, extremely obvious.

At present, the raw materials applied to the MT ferrule are mainly PPS (polyphenylene sulfide) and SiO ₂ microspheres. By adding SiO ₂ microspheres, the dimensional stability of the material is ensured and the strength is enhanced. However, the commonly used preparation methods of SiO ₂ microspheres generally require the use of a large amount of organic matter, which is troublesome to recycle, high in cost and environmentally polluted, and requires high equipment, complicated operation, and high energy consumption, and is suitable for existing MT ferrule raw materials. The invention has the advantages that the improved inorganic filler and the optimization of the preparation process enable the prepared MT ferrule raw material to have better dimensional stability, lower thermal expansion coefficient, lower preparation cost and longer service life.

Summary of the invention

Based on this, the object of the present invention is to overcome the above-mentioned deficiencies of the prior art and to provide an MT ferrule raw material which can reduce cost, simplify the process and improve stability, and a preparation method thereof.

In order to achieve the above object, the technical solution adopted by the present invention is: an MT ferrule raw material, the ferrule raw material comprising the following components according to a mass percentage: 14.5-35% polyphenylene sulfide, and 55-85% The inorganic filler is at least one of zirconium dioxide, silicon dioxide, aluminum oxide, iron oxide, zinc oxide, and calcium carbonate.

Preferably, the ferrule raw material further contains 0.1 to 2% of a coupling agent in terms of mass percentage. It should be noted that the coupling agent is used for modifying the inorganic filler, and is modified by the coupling agent to make the PPS and the filler microspheres better connected together, reducing the dropping rate of the filler microspheres and increasing the strength of the material.

Preferably, the coupling agent comprises vinyl silane, stearic acid amide, γ-glyceryloxypropyltrimethoxysilane, γ-methacryloyloxytrimethoxysilane, γ-mercaptopropyltrimethyl At least one of oxysilane and 3-propyl methacrylate trimethoxysilane.

Preferably, the inorganic filler is at least one of zirconium dioxide and aluminum oxide.

The inorganic filler is at least one of calcium carbonate and aluminum oxide. The inventors of the present application have found through repeated tests that when the inorganic filler is selected from calcium carbonate or/and alumina, the impact strength of the obtained MT ferrule raw material is significantly higher than that of other fillers.

Preferably, the polyphenylene sulfide has a mass percentage of 21 to 26%.

Preferably, the inorganic filler has a mass percentage of 57 to 67%.

Preferably, the component of the ferrule raw material further comprises a stabilizer having a mass percentage of 0 to 30%; more preferably, the stabilizer has a mass percentage of 0.17 to 14.4%; most preferably, The mass percentage of the stabilizer is from 1.2 to 3%.

Preferably, the stabilizer is selected from at least one of a lead salt, a metal soap, an organic rare earth, and an organotin. It should be noted that the lead salt may be a tribasic lead sulfate or a dibasic lead phosphite; the metal soap may be lead stearate, lead 2-ethyl acetate, barium stearate, cadmium stearate or stearic acid. Calcium acid; the organic rare earth may be a carboxylate or a fatty acid salt of a light rare earth element such as lanthanum, cerium, lanthanum or cerium; the organotin may be tin isooctyl dimethyl dimercaptoacetate or isooctyl dimercaptoacetate Octyl tin, di-n-butyltin dilaurate or di-n-octyltin dilaurate.

Preferably, the component of the ferrule raw material further comprises a plasticizer having a mass percentage of 0 to 30%; more preferably, the plasticizer has a mass percentage of 0.1 to 8.3%; Preferably, the plasticizer The mass percentage is from 1 to 3.5%.

Preferably, the plasticizer is at least one of di(2-ethylhexyl) phthalate, DINP, DNOP, DBP, DMP and DEP. Wherein, DINP is diisodecyl phthalate; DNOP is di-n-octyl phthalate; DBP is dibutyl phthalate; DMP is dimethyl phthalate; DEP is N, N- Diethylpropynylamine.

Preferably, the component of the ferrule raw material further comprises an antioxidant having a mass percentage of 0 to 30%; more preferably, the antioxidant has a mass percentage of 0.13 to 13.5%; most preferably, The antioxidant has a mass percentage of 1.9 to 7%.

More preferably, the antioxidant is at least one of 2,6-di-tert-butyl-4-methylphenol, antioxidant 2246, antioxidant 1010, thiodipropionate, and thiophosphite. Kind. It should be noted that the thiodipropionate may be dilauryl thiodipropionate; the thiophosphite may be triphenyl thiophosphite. As another aspect of the present invention, the present invention also provides a method for preparing the above MT ferrule raw material, comprising the following steps:

(1) Preparation of filler microspheres:

a. Dispersing the inorganic filler in an organic solvent, and simultaneously treating the first ultrasonication with the first high-speed stirring to obtain a uniformly dispersed organic filler organic solution;

b, adding a coupling agent to the uniformly dispersed inorganic filler organic solution obtained in the step a, and simultaneously treating with the second ultrasonication by the second high-speed stirring, and drying, the filler microspheres can be obtained;

(2) Mixing of filler microspheres with polyphenylene sulfide:

The filler microspheres obtained in the step (1) are premixed with polyphenylene sulfide, and then melt blended into a twin-screw extruder to obtain a composite material in which the filler microspheres are uniformly dispersed in the polyphenylene sulfide resin matrix, and the composite is obtained. The material is the MT ferrule raw material.

Preferably, the inorganic filler in the step (1) is at least one of zirconium dioxide, silicon dioxide, aluminum oxide, iron oxide, zinc oxide and calcium carbonate. It should be noted that the inventors of the present application have found through experiments that when the inorganic filler in the step (1) is a micron-sized zirconium dioxide particle, the obtained MT material is the most stable, has the lowest thermal expansion coefficient and the highest strength; The spherical particles of zirconium dioxide are easy to control the morphology and have a large specific surface area, which is favorable for subsequent surface modification by a coupling agent.

Preferably, the organic solvent in the step (1) includes at least one of methanol, ethanol, propanol, acetone, toluene, and N-methylpyrrolidone.

Preferably, the coupling agent in the step (1) comprises vinyl silane, stearic acid amide, γ-glyceryloxypropyltrimethoxysilane, γ-methacryloyloxytrimethoxysilane, γ At least one of mercaptopropyltrimethoxysilane and 3-propyl methacrylatetrimethoxysilane.

Preferably, in the step b, at least one of a stabilizer, a plasticizer and an antioxidant is further added to the uniformly dispersed inorganic filler organic solution obtained in the step a.

Preferably, the plasticizer is at least one of di(2-ethylhexyl) phthalate, DINP, DNOP, DBP, DMP and DEP.

Preferably, the antioxidant is at least one of 2,6-di-tert-butyl-4-methylphenol, antioxidant 2246, antioxidant 1010, thiodipropionate and thiophosphite. . It should be noted that the thiodipropionate may be dilauryl thiodipropionate; the thiophosphite may be triphenyl thiophosphite.

Preferably, the stabilizer, the plasticizer, and the antioxidant are each 0 to 30% by mass; more preferably, the stabilizer has a mass percentage of 0.17 to 14.4%; the plasticizing The mass percentage of the agent is 0.1 to 8.3%; the mass percentage of the antioxidant is 0.13 to 13.5%; most preferably, the mass percentage of the stabilizer is 1.2 to 3%; The mass percentage of the agent is from 1 to 3.5%; the mass percentage of the antioxidant is from 1.9 to 7%. The inventors of the present application have found through repeated tests that when the additive includes a coupling agent, a stabilizer, a plasticizer and an antioxidant, the stability of the obtained MT ferrule raw material is significantly stronger than when only some of the additives are used. The obtained MT ferrule raw material.

Preferably, the first high-speed stirring rate in the step (1) is 2000-5000r/min, the first time The ultrasonic power is 2000-8000W, and the first ultrasonic treatment time is 1~3h;

The second high-speed stirring rate in the step (1) is 3000-6000r/min, the second ultrasonic power is 2000-8000W, and the second ultrasonic processing time is 4-48h;

The drying temperature is 60 to 100 ° C, and the drying time is 1 to 10 days.

Preferably, the filler microspheres prepared in the step (1) have a particle size of 0.5 to 70 um, wherein the filler microspheres have an average particle size of 6 to 15 um.

Compared with the prior art, the beneficial effects of the present invention are:

1, MT ferrule material of the present invention as compared to SiO ₂ composite materials, better dimensional stability, a lower coefficient of thermal expansion;

2. Compared with the existing preparation process of SiO ₂ microspheres, the modification process of the invention is more simplified, the cost is lower and the service life is longer.

detailed description

The present invention will be further described with reference to specific embodiments in order to better illustrate the objects, aspects and advantages of the invention. It should be noted that the strengths in Examples 1 to 5 of the present invention were flexural strength, and the flexural strength was tested by a universal testing machine.

Example 1

A method for preparing a MT ferrule raw material, comprising the following steps:

1. Preparation of filler microspheres (surface modification of inorganic fillers)

(1) Dispersing the micron-sized particulate alumina in an organic solvent methanol, and subjecting it to high-speed stirring and ultrasonic treatment for a period of time to obtain a uniformly dispersed alumina organic solution, wherein 55 parts by mass of alumina is used. , methanol is 27.5 parts, high-speed stirring rate is 2000r/min, ultrasonic power is 2000W, processing time is 1h;

(2) uniformly adding the coupling agent vinyl silane to the zirconia organic solution uniformly dispersed in the above step (1), subjecting it to high-speed stirring and ultrasonic treatment for a period of time, and then drying at a certain temperature for a certain period of time to obtain an even The alumina microspheres after the treatment, wherein the amount of vinyl silane is 1 part by mass, the high-speed stirring rate is 3000r/min, the ultrasonic power is 2000W, the treatment time is 4h, and the drying temperature is 60 ° C, drying time is 1 day; the obtained alumina microspheres have a particle size of 0.5 to 90 um, and the alumina microspheres have an average particle size of 6 to 15 um.

2. Mixing of alumina microspheres with PPS (polyphenylene sulfide)

The alumina microspheres treated with the coupling agent are premixed with PPS, and then melt blended by using a twin-screw extruder to prepare a composite material in which alumina microspheres are uniformly dispersed in a PPS resin matrix. MT ferrule raw materials. Among them, the polyphenylene sulfide is 35 parts by mass, the premixing stirring rate is 1000 r/min, and the stirring temperature is ≤80 °C.

Extrusion temperature of twin-screw extruder: temperature in one zone: 260-280 °C; temperature in two zones: 290-310 °C; temperature in three zones: 300-320 °C; temperature in four zones: 300-320 °C; temperature in five zones: 300 ~ 320 ° C, screw speed 50r / min.

The MT ferrule raw material prepared in this embodiment has better dimensional stability than the SiO ₂ composite material; the dimensional stability can be expressed by the thermal expansion coefficient, and the commercially available silica composite material has a thermal expansion coefficient of generally 13 ～17PPm/K, the strength is 80-120MPa, and the MT ferrule raw material obtained by the present embodiment has a thermal expansion coefficient of 12PPm/K and a strength of 144 MPa.

Example 2

(1) Dispersing micron-sized iron oxide and zinc oxide particles (mass ratio of iron oxide and zinc oxide to 3:1) in an organic solvent ethanol, and subjecting to high-speed stirring and ultrasonic treatment for a period of time to obtain uniformly dispersed iron oxide. And an organic solution of zinc oxide, wherein, according to the parts by mass, iron oxide and zinc oxide are 63 parts, ethanol is 120 parts, high-speed stirring rate is 2800 r/min, ultrasonic power is 3500 W, and processing time is 1.5 h;

(2) uniformly adding the coupling agent stearic acid amide to the organic solution of iron oxide and zinc oxide uniformly dispersed in the above step (1), subjected to high-speed stirring and ultrasonic treatment for a certain period of time, and then dried at a certain temperature for a certain period of time. The iron oxide and zinc oxide microspheres prepared by the coupling agent are prepared, wherein the stearic acid amide is 1.5 parts by mass, the high-speed stirring rate is 3800r/min, the ultrasonic power is 3500W, the processing time is 15h, and the drying is performed. The temperature is 70 ° C and the drying time is 3 days; the prepared zirconium dioxide microspheres have a particle size of 0.5 to 90 μm, and the zirconium dioxide microspheres have an average particle size of 6 to 15 μm.

2. Mixture of iron oxide and zinc oxide microspheres with PPS (polyphenylene sulfide)

The iron oxide and zinc oxide microspheres treated by the coupling agent are premixed with PPS, and then melt blended by using a twin-screw extruder to prepare iron oxide and zinc oxide microspheres uniformly dispersed in the PPS resin matrix. The composite material, that is, the MT ferrule raw material. Among them, 33 parts by mass of polyphenylene sulfide, the mixing rate of premixing: 1250r/min, stirring temperature ≤ 80 °C.

Extrusion temperature of twin-screw extruder: temperature in one zone: 260-280 °C; temperature in two zones: 290-310 °C; temperature in three zones: 300-320 °C; temperature in four zones: 300-320 °C; temperature in five zones: 300 ~ 320 ° C, screw speed 90r / min.

The MT ferrule raw material prepared in this embodiment has better dimensional stability than the SiO ₂ composite material; the dimensional stability can be expressed by the thermal expansion coefficient, and the commercially available silica composite material has a thermal expansion coefficient of generally 13 ～17PPm/K, the strength is 80-120MPa, and the MT ferrule raw material obtained by the present embodiment has a thermal expansion coefficient of 13PPm/K and a strength of 130MPa.

Example 3

(1) dispersing the micron-sized zirconia in a particulate state in an organic solvent mixed with propanol and acetone, and subjecting it to high-speed stirring and ultrasonic treatment for a period of time to obtain a uniformly dispersed organic solution of zirconium dioxide, wherein, according to the mass part The number of zirconium dioxide is 71 parts, the amount of ethanol is 390 parts, the high-speed stirring rate is 3600r/min, the ultrasonic power is 500W, and the treatment time is 2 hours;

(2) uniformly adding a coupling agent (a mixture of γ-glyceryloxypropyltrimethoxysilane and γ-methacryloyloxytrimethoxysilane in a mass ratio of 3:1) to the above step (1) The uniformly dispersed zirconia organic solution is subjected to high-speed stirring and ultrasonic treatment for a certain period of time, and then dried at a certain temperature for a certain period of time to obtain a zirconia microsphere after the coupling agent treatment, wherein γ by mass - 2 parts mixture of glyceryloxypropyltrimethoxysilane and γ-methacryloyloxytrimethoxysilane, high-speed stirring rate of 4400r/min, ultrasonic power of 5000W, treatment time of 26h, drying temperature The drying time is 5 days at 80 ° C; the prepared zirconium dioxide microspheres have a particle size of 0.5-90 um, and the zirconium dioxide microspheres have an average particle size of 6-15 um.

2. Mixing of ZrO ₂ microspheres with PPS (polyphenylene sulfide)

The ZrO ₂ microspheres treated with the coupling agent are premixed with PPS, and then melt blended by a twin-screw extruder to prepare a composite material in which ZrO ₂ microspheres are uniformly dispersed in the PPS resin matrix, thereby preparing the composite material. MT ferrule raw materials. Among them, the polyphenylene sulfide is 27 parts by mass, the premixing stirring rate is 1500 r/min, and the stirring temperature is ≤80 °C.

Extrusion temperature of twin-screw extruder: temperature in one zone: 260-280 °C; temperature in two zones: 290-310 °C; temperature in three zones: 300-320 °C; temperature in four zones: 300-320 °C; temperature in five zones: 300 ~ 320 ° C, screw speed 130r / min.

The MT ferrule raw material prepared in this embodiment has better dimensional stability than the SiO ₂ composite material; the dimensional stability can be expressed by the thermal expansion coefficient, and the commercially available silica composite material has a thermal expansion coefficient of generally 13 -17PPm/K, the strength is 80-120MPa, and the MT ferrule raw material obtained by the present embodiment has a thermal expansion coefficient of 10PPm/K and a strength of 160MPa.

Example 4

(1) dispersing the micron-sized granular calcium carbonate in the organic solvent toluene, and performing high-speed stirring and ultrasonic treatment for a period of time to obtain a uniformly dispersed calcium carbonate organic solution, wherein 78 parts by mass of calcium carbonate are used. , ethanol is 840 parts, high-speed stirring rate is 4300r/min, ultrasonic power is 6500W, processing time is 2.5h;

(2) uniformly adding the coupling agent γ-mercaptopropyltrimethoxysilane to the organic solution of calcium carbonate uniformly dispersed in the above step (1), subject to high-speed stirring and ultrasonic treatment for a period of time, and then drying at a certain temperature for a period of time. After the time, the calcium carbonate microspheres after the coupling agent treatment were prepared, wherein 0.5 parts by mass of γ-mercaptopropyltrimethoxysilane, a high-speed stirring rate of 5200 r/min, and an ultrasonic power of 6500 W, treatment time It is 37h, the drying temperature is 90 ° C, and the drying time is 7 days; the obtained calcium carbonate microspheres have a particle size of 0.5 to 90 um, and the calcium carbonate microspheres have an average particle size of 6 to 15 um.

2. Mixing of calcium carbonate microspheres with PPS (polyphenylene sulfide)

The calcium carbonate microspheres treated by the coupling agent are premixed with PPS, and then melt blended by using a twin-screw extruder to prepare a composite material in which calcium carbonate microspheres are uniformly dispersed in a PPS resin matrix. MT ferrule raw materials. Among them, 21 parts by mass of polyphenylene sulfide, premixed stirring speed Rate: 1750r/min, stirring temperature ≤ 80 °C.

Extrusion temperature of twin-screw extruder: temperature in one zone: 260-280 °C; temperature in two zones: 290-310 °C; temperature in three zones: 300-320 °C; temperature in four zones: 300-320 °C; temperature in five zones: 300 ~ 320 ° C, screw speed 170r / min.

The MT ferrule raw material prepared in this embodiment has better dimensional stability than the SiO ₂ composite material; the dimensional stability can be expressed by the thermal expansion coefficient, and the commercially available silica composite material has a thermal expansion coefficient of generally 13 ～17PPm/K, the strength is 80-120MPa, and the MT ferrule raw material obtained by the present embodiment has a thermal expansion coefficient of 12PPm/K and a strength of 139 MPa.

Example 5

(1) Dispersing micron-sized zirconia and alumina particles (mass ratio of zirconia and alumina to 1:1) in an organic solvent NMP (N-methylpyrrolidone), and subjecting to high-speed stirring and ultrasonic treatment For a period of time, a uniformly dispersed organic solution of zirconium dioxide and aluminum oxide is obtained, wherein 85 parts by mass of zirconium dioxide and aluminum oxide, 1500 parts of ethanol, a high-speed stirring rate of 5000 r/min, and an ultrasonic power of 8000 W are obtained. , processing time 3h;

(2) uniformly adding the coupling agent 3-methacrylic acid trimethoxysilane to the organic solution of the zirconium dioxide and aluminum oxide uniformly dispersed in the above step (1), and subject to high-speed stirring and ultrasonic treatment for a period of time, then After drying at a certain temperature for a certain period of time, the coupling agent-treated zirconium dioxide and alumina microspheres were prepared, wherein the mass fraction of 3-methacrylic acid trimethoxysilane was 0.1 parts, and the high-speed stirring rate was obtained. It is 6000r/min, ultrasonic power is 8000W, processing time is 48h, drying temperature is 100°C, drying time is 10 days; prepared zirconium dioxide and alumina microspheres have particle size of 0.5-90um, zirconium dioxide and oxidation The average particle size of the aluminum microspheres is 6 to 15 um.

2. Mixing of zirconia and alumina microspheres with PPS (polyphenylene sulfide)

The zirconia and alumina microspheres treated with the coupling agent are premixed with PPS, and then melt blended using a twin-screw extruder to prepare a zirconium dioxide and alumina microspheres uniformly dispersed in the PPS resin matrix. In the composite material, the MT ferrule raw material is produced. Among them, the polyphenylene sulfide is 14.5 parts by mass, the premixing stirring rate is 2000 r/min, and the stirring temperature is ≤80 °C.

Extrusion temperature of twin-screw extruder: temperature in one zone: 260-280 °C; temperature in two zones: 290-310 °C; temperature in three zones: 300-320 °C; temperature in four zones: 300-320 °C; temperature in five zones: 300 ~ 320 ° C, screw speed 200r / min.

The MT ferrule raw material prepared in this embodiment has better dimensional stability than the SiO ₂ composite material; the dimensional stability can be expressed by the thermal expansion coefficient, and the commercially available silica composite material has a thermal expansion coefficient of generally 13 ～17PPm/K, the strength is 80-120MPa, and the MT ferrule raw material obtained by the present embodiment has a thermal expansion coefficient of 11PPm/K and a strength of 152 MPa.

When the MT ferrule is prepared by using the existing raw material SiO ₂ , if the fluidity during molding is improved, the mechanical properties are lowered, and the size of the filler microspheres in the present invention is easy to control, the thermal stability is better, and the surface can be better. Modification, so that the filler particles are better combined with PPS, and the obtained ferrule material has better mechanical properties.

Example 6

An embodiment of the MT ferrule raw material of the present invention, the ferrule raw material comprises the following components in terms of mass percentage: 14.5 polyphenylene sulfide, 14.4% tribasic lead sulfate, 0.1% 3-methyl acrylate Lipoxytrimethoxysilane and 71% iron oxide.

The MT ferrule raw material preparation method of the present embodiment is the same as that of the embodiment 2 except that the coupling agent and the stabilizer (tribasic lead sulfate) are added to the organic solution of the dispersed inorganic filler.

Example 7

An embodiment of the MT ferrule raw material of the present invention, the ferrule raw material comprises the following components in terms of mass percentage: 17% polyphenylene sulfide, 0.1% di(2-ethylhexyl) phthalate, 13.5% 2,6-di-tert-butyl-4-methylphenol, 0.4% gamma-mercaptopropyltrimethoxysilane and 69% zinc oxide.

The preparation method of the MT ferrule raw material of the present embodiment is the same as that of the third embodiment except that the coupling agent is added to the organic solution of the dispersed inorganic filler, and the plasticizer (bis(2-ethyl) phthalate Ethyl ester) and antioxidant (2,6-di-tert-butyl-4-methylphenol).

Example 8

An embodiment of the MT ferrule raw material of the present invention, the ferrule raw material comprises the following components in mass percentage: 21% polyphenylene sulfide, 0.17% bismuth laurate, 1% DINP and DNOP (wherein DINP and The mass ratio of DNOP is 1:4), 10.13% of antioxidant 1010, 0.7% of vinyl silane and stearic acid amide (wherein the mass ratio of vinyl silane to stearic acid amide is 1:1) and 67% Zirconium dioxide.

The preparation method of the MT ferrule raw material of the present embodiment is the same as that of the third embodiment except that the coupling agent is added to the organic solution of the dispersed inorganic filler, and the stabilizer (yttrium laurate) and the plasticizer (DINP and DNOP) and antioxidants (antioxidant 1010).

Example 9

An embodiment of the MT ferrule raw material of the present invention, the ferrule raw material comprises the following components in mass percentage: 23.5% polyphenylene sulfide, 3% isooctyl dimethyl dimercaptoacetate, 4% Dilauryl thiodipropionate and triphenyl thiophosphite (mass ratio of dilauryl thiodipropionate and triphenyl thiophosphite 2:1), 3.5% DBP, 1% Γ-methacryloyloxytrimethoxysilane and 65% of zirconium dioxide and aluminum oxide (wherein the mass ratio of zirconium dioxide to aluminum oxide is 2:1).

The preparation method of the MT ferrule raw material of the present embodiment is the same as that of the embodiment 4 except that the coupling agent is added to the organic solution of the dispersed inorganic filler, and the stabilizer (isooctyl dimethyl dimercaptoacetate) is also added. , plasticizer (DBP) and antioxidants (dilauryl thiodipropionate and triphenyl thiophosphite).

Example 10

An embodiment of the MT ferrule raw material of the present invention, the ferrule raw material comprises the following components in terms of mass percentage: 26% polyphenylene sulfide, 1.2% dibasic lead phosphite and lead stearate (dibasic The mass ratio of lead phosphite to lead stearate is 1:1), 3.5% DBP, DMP and DEP (mass ratio of DBP, DMP and DEP is 1:2:1), 7% of 2,6- Di-tert-butyl-4-methylphenol, 1.3% vinyl silane and 61% calcium carbonate.

The preparation method of the MT ferrule raw material of the present embodiment is the same as that of the embodiment 2 except that the coupling agent is added to the organic solution of the dispersed inorganic filler, and the stabilizer (dibasic lead phosphite and lead stearate) ), plasticizers (DBP, DMP and DEP) and antioxidants (2,6-di-tert-butyl-4-methylphenol).

Example 11

An embodiment of the MT ferrule raw material of the present invention, the ferrule raw material comprises the following components in mass percentage: 29.5% polyphenylene sulfide, 1.7% lead 2-ethyl acetate, 8.3% DMP, 1.9% Dilauryl thiodipropionate, 1.6% stearic acid amide and 57% zirconium dioxide.

The preparation method of the MT ferrule raw material of the present embodiment is the same as that of the third embodiment, except that the coupling agent is added to the organic solution of the dispersed inorganic filler, and the stabilizer (2-ethyl acetate lead) and the plasticizer are added. (DMP) and an antioxidant (dilauryl thiodipropionate).

Example 12

An embodiment of the MT ferrule raw material of the present invention, the ferrule raw material comprises the following components in terms of mass percentage: 35% polyphenylene sulfide, 7.87% cadmium stearate, 0.13% antioxidant 1010, 2 % γ-glyceryloxypropyltrimethoxysilane and 55% alumina.

The MT ferrule raw material preparation method of the present embodiment is the same as that of the embodiment 4 except that the coupling agent, the stabilizer (cadmium stearate) and the antioxidant (antioxidation) are added to the organic solution of the dispersed inorganic filler. Agent 1010).

Example 13 MT ferrule raw material stability test of the present invention

Test object: MT ferrule raw materials prepared in Examples 2, 3, 4, 6, 7, 8, 9, 10, 11, and 12;

Test method: detection by thermal expansion coefficient meter;

Sample preparation: diameter 3-5mm height 4-6mm; test temperature range: 0-150 ° C;

Heating rate: 5 ° C / min;

Test results: as shown in Table 1 below.

Table 1 Results of the stability test of the MT ferrule raw material of the present invention

MT插芯原材料MT ferrule raw material	热膨胀系数(PPm/K)Thermal expansion coefficient (PPm/K)
实施例2Example 2	13.413.4
实施例3Example 3	11.811.8
实施例4Example 4	12.412.4
实施例6Example 6	10.510.5
实施例7Example 7	11.211.2
实施例8Example 8	10.710.7
实施例9Example 9	10.110.1
实施例10Example 10	11.111.1
实施例11Example 11	10.810.8
实施例12Example 12	10.310.3

It can be seen from the above Table 1 that the thermal expansion coefficients of the MT ferrule raw materials obtained in Examples 6 to 8 are lower than those in Examples 2 to 4, indicating that the thermal stability of the MT ferrule raw materials obtained in Examples 6 to 8 is better than that of the implementation. The MT ferrule raw materials of Examples 2 to 4; wherein the MT ferrule raw material obtained in Example 9 had the best thermal stability.

Example 14 Effect of inorganic fillers on mechanical properties of MT ferrule raw materials

Test object: MT ferrule raw material, including the control group and the MT ferrule raw materials of Examples 4, 9 and 12, wherein the raw material ratio and preparation method of the control group were the same as those of Example 4 except that the inorganic filler was only used.

Test method: test the impact strength by pendulum test;

Test results: as shown in Table 2 below.

Table 2 Test results of mechanical properties of MT ferrule raw materials of the present invention

MT插芯原材料MT ferrule raw material	无机填料Inorganic filler	抗冲击强度Impact strength
对照组1Control group 1	二氧化硅Silica	810KJ/m² 810KJ / m ²
对照组2Control group 2	二氧化锆zirconium dioxide	814KJ/m² 814KJ/m ²
对照组3Control group 3	氧化铝Alumina	820KJ/m² 820KJ/m ²
对照组4Control group 4	氧化铁Iron oxide	816KJ/m² 816KJ/m ²
对照组5Control group 5	氧化锌Zinc oxide	814KJ/m² 814KJ / m ²
实施例4Example 4	碳酸钙Calcium carbonate	822KJ/m² 822KJ/m ²
实施例9Example 9	碳酸钙Calcium carbonate	835KJ/m² 835KJ/m ²
实施例12Example 12	碳酸钙Calcium carbonate	827KJ/m² 827KJ/m ²

It can be seen from the above Table 2 that when the inorganic filler is alumina or calcium carbonate, the impact strength of the MT ferrule raw material is significantly higher than that of other groups of MT ferrule raw materials, wherein the MT ferrule raw material when the inorganic filler is calcium carbonate The best impact strength.

It should be noted that the above embodiments are only intended to illustrate the technical solutions of the present invention and are not intended to limit the scope of the present invention, although the present invention will be described in detail with reference to the preferred embodiments, The technical solutions of the present invention may be modified or equivalently substituted without departing from the spirit and scope of the technical solutions of the present invention.

Claims

An MT ferrule raw material, characterized in that the ferrule raw material comprises the following components in terms of mass percentage: 14.5-35% polyphenylene sulfide, and 55-85% inorganic filler, the inorganic filler is dioxide At least one of zirconium, silica, alumina, iron oxide, zinc oxide, and calcium carbonate.
The MT ferrule raw material according to claim 1, wherein the ferrule raw material further contains 0.1 to 2% of a coupling agent in terms of a mass percentage.
The MT ferrule raw material according to claim 2, wherein the coupling agent comprises vinyl silane, stearic acid amide, γ-glyceryloxypropyltrimethoxysilane, γ-methacryloyl group. At least one of oxytrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and 3-propyl methacrylatetrimethoxysilane.
The MT ferrule raw material according to claim 1, wherein the inorganic filler is at least one of zirconium dioxide and aluminum oxide.
The MT ferrule raw material according to claim 1, wherein the inorganic filler is at least one of calcium carbonate, silica, and alumina.
The MT ferrule raw material according to claim 1, wherein the polyphenylene sulfide has a mass percentage of 21 to 26%.
The MT ferrule raw material according to claim 1, wherein the inorganic filler has a mass percentage of 57 to 67%.
The MT ferrule raw material according to claim 1, wherein the composition of the ferrule raw material further comprises a stabilizer having a mass percentage of 0 to 30%.
The MT ferrule raw material according to claim 8, wherein the stabilizer has a mass percentage of from 0.17 to 14.4%.
The MT ferrule raw material according to claim 9, wherein the stabilizer has a mass percentage of 1.2 to 3%.
The MT ferrule according to any one of claims 8 to 10, wherein the stabilizer is at least one selected from the group consisting of a lead salt, a metal soap, an organic rare earth, and an organotin.
The MT ferrule raw material according to claim 1, wherein the composition of the ferrule raw material further comprises a plasticizer having a mass percentage of 0 to 30%.
The MT ferrule according to claim 12, wherein the plasticizer has a mass percentage of 0.1 to 8.3%.
The MT ferrule according to claim 13, wherein the plasticizer has a mass percentage of from 1 to 3.5%.
The MT ferrule according to any one of claims 12 to 14, wherein the plasticizer is di(2-ethylhexyl) phthalate or diisononyl phthalate. At least one of di-n-octyl phthalate, dibutyl phthalate, dimethyl phthalate, and N,N-diethylpropynylamine.
The MT ferrule raw material according to claim 1, wherein the composition of the ferrule raw material further comprises an antioxidant having a mass percentage of 0 to 30%.
The MT ferrule raw material according to claim 16, wherein the antioxidant has a mass percentage of 0.13 to 13.5%.
The MT ferrule raw material according to claim 17, wherein the antioxidant has a mass percentage of 1.9 to 7%.
The MT ferrule according to any one of claims 16 to 18, wherein the antioxidant is 2,6-di-tert-butyl-4-methylphenol, antioxidant 2246, and antioxidant 1010. At least one of thiodipropionate and thiophosphite.
The method for preparing a MT ferrule raw material according to claim 3, comprising the steps of:

(1) Preparation of filler microspheres:

a. Dispersing the inorganic filler in an organic solvent, the first high-speed stirring and the first ultrasonic effect Time treatment to obtain a uniformly dispersed organic filler organic solution;

b, adding a coupling agent to the uniformly dispersed inorganic filler organic solution obtained in the step a, and simultaneously treating with the second ultrasonication by the second high-speed stirring, and drying, the filler microspheres can be obtained;

(2) Mixing of filler microspheres with polyphenylene sulfide:

The filler microspheres obtained in the step (1) are premixed with polyphenylene sulfide, and then melt blended into a twin-screw extruder to obtain a composite material in which the filler microspheres are uniformly dispersed in the polyphenylene sulfide resin matrix, and the composite is obtained. The material is the MT ferrule raw material.
The method according to claim 20, wherein the inorganic filler in the step (1) is at least one of zirconium dioxide, silicon dioxide, aluminum oxide, iron oxide, zinc oxide, and calcium carbonate.
The preparation method according to claim 20, wherein the organic solvent in the step (1) comprises at least one of methanol, ethanol, propanol, acetone, toluene, and N-methylpyrrolidone.
The preparation method according to claim 20, wherein the coupling agent in the step (1) comprises vinyl silane, stearic acid amide, γ-glyceryloxypropyltrimethoxysilane, γ-甲At least one of acryloxytrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and 3-propyl methacrylatetrimethoxysilane.
The preparation method according to claim 20, wherein in the step b, at least one of a stabilizer, a plasticizer, and an antioxidant is further added to the uniformly dispersed inorganic filler organic solution obtained in the step a.
The method according to claim 24, wherein the stabilizer is at least one selected from the group consisting of a lead salt, a metal soap, an organic rare earth, and an organotin.
The preparation method according to claim 24, wherein the plasticizer is di(2-ethylhexyl) phthalate, diisononyl phthalate, di-n-octyl phthalate. At least one of an ester, dibutyl phthalate, dimethyl phthalate, and N,N-diethylpropynylamine.
The preparation method according to claim 24, wherein the antioxidant is 2,6-di-tert-butyl-4-methylphenol, antioxidant 2246, antioxidant 1010, thiodipropionate. And at least one of thiophosphites.
The preparation method according to claim 24, wherein the mass percentage of the stabilizer is 0.17 to 14.4%; the mass percentage of the plasticizer is 0.1 to 8.3%; and the mass percentage of the antioxidant is 0.13. ~ 13.5%.
The preparation method according to claim 20, wherein the first high-speed stirring rate in the step (1) is 2000 to 5000 r/min, and the first ultrasonic power is 2000 to 8000 W, and the first ultrasonic processing time is 1~3h;

The second high-speed stirring rate in the step (1) is 3000-6000r/min, the second ultrasonic power is 2000-8000W, and the second ultrasonic processing time is 4-48h;

The drying temperature is 60 to 100 ° C, and the drying time is 1 to 10 days.
The preparation method according to claim 20, wherein the filler microspheres obtained in the step (1) have a particle size distribution ranging from 0.5 to 90 um, wherein the filler microspheres have an average particle size of 6 to 15 um.