阅读说明：本技术 一种纳米导电阻燃功能母粒新材料及其制备方法 (Novel nano conductive flame-retardant master batch material and preparation method thereof ) 是由 李彦波 李宗禹 王兆国 于 2021-07-29 设计创作，主要内容包括：本发明涉及一种纳米阻燃导电功能母粒新材料及其制备方法,包括以下质量份的组份：纳米预分散导电浆组份3-10份、阻燃剂组份65-80份、载体组份10-20份、功能助剂组份5-10份。本发明还涉及一种纳米阻燃导电功能母粒新材料的制备方法,包括纳米预分散导电浆组份制备步骤,熔融改性,磨面切粒成型步骤。本发明制备的纳米导电阻燃功能母粒与聚合物共混使用,可赋予材料导电、阻燃双重功能,本技术产品具备协同效应,功能效率高、添加比例小、材料物性良好、使用方便等优点。(The invention relates to a novel nanometer flame-retardant conductive master batch material and a preparation method thereof, wherein the novel nanometer flame-retardant conductive master batch material comprises the following components in parts by mass: 3-10 parts of nano pre-dispersed conductive paste component, 65-80 parts of flame retardant component, 10-20 parts of carrier component and 5-10 parts of functional auxiliary agent component. The invention also relates to a preparation method of the novel nanometer flame-retardant conductive master batch material, which comprises the steps of preparing nanometer pre-dispersed conductive slurry components, carrying out fusion modification, and carrying out ground surface granulation molding. The nanometer conductive flame-retardant master batch prepared by the invention is used by blending with a polymer, so that the material can have dual functions of conductivity and flame retardance, and the technical product has the advantages of synergistic effect, high functional efficiency, small addition proportion, good material physical property, convenience in use and the like.)

1. A novel nanometer flame-retardant conductive master batch material and a preparation method thereof are characterized by comprising the following components in parts by mass: 3-10 parts of nano pre-dispersed conductive paste component, 65-75 parts of flame retardant component, 10-20 parts of carrier component and 5-10 parts of functional auxiliary agent component;

the nanometer pre-dispersion conductive paste comprises the following components: dispersing solvent, stabilizer and conductive nano material;

the mass ratio of the dispersing solvent to the stabilizer to the conductive nano material is 60-80: 10-20: 2-5.

2. The new nano flame-retardant conductive master batch material as claimed in claim 1, wherein the dispersant solution is a composition of polyethylene glycol and paraffin mineral oil, and the mass ratio of the polyethylene glycol to the paraffin mineral oil is 20-40: 60-80 parts;

the stabilizer is polyamide-amine (PAMAM) with a highly branched structure, wherein-NH is contained in the PAMAM₂、-OH、-COOCH₃At least 2 or more functional groups capable of reacting with a coupling agentAnd (4) graft crosslinking reaction.

3. The new nano flame-retardant conductive masterbatch material according to claim 1, wherein the conductive nano material in the nano pre-dispersed conductive paste component is a single-walled carbon nanotube, wherein the particle size of the nano material is 10-50 nm.

4. The new nano material of the flame-retardant conductive masterbatch according to claim 3,

the conductive nano material component accounts for 2-5% of the total mass component of the nano pre-dispersed conductive paste component.

5. The novel nano flame-retardant conductive master batch material as claimed in claim 1, wherein the flame retardant component includes but is not limited to halogen-antimony composite system, phosphorus-nitrogen composite system or magnesium-aluminum composite system flame retardant or its flame retardant master batch.

6. The new nano-grade flame-retardant conductive master batch material according to claim 1, wherein the carrier component is one or more of polyethylene, polypropylene, ethylene octene, ethylene vinyl acetate.

7. The new nano flame-retardant conductive master batch material according to claim 1, wherein the functional auxiliary agent component comprises an antioxidant, a lubricant and a coupling agent, and the mass ratio of the antioxidant to the lubricant to the coupling agent is 0.3-0.8: 1-3: 1-2.5;

the antioxidant is phosphite antioxidant;

the lubricant is one or a combination of a polymeric wax, ethylene bis stearamide and a fatty acid ester lubricant;

the coupling agent is one or more compositions of silane coupling agents.

8. A preparation method of a novel nano flame-retardant conductive master batch material is characterized by comprising the following steps:

(1) respectively weighing a dispersing solvent and a conductive nano material; sequentially putting into a kettle with a stirrer, mixing for 30-60 minutes, adding a stabilizer, modifying and mixing for 10-30 minutes to obtain nano pre-dispersed conductive paste;

(2) putting the flame retardant components into a high-speed mixer according to the formula proportion for mixing, and then adding the functional assistant coupling agent component to complete coupling, cladding and modification;

(3) melting, plasticizing and granulating through a double-screw extruder, and feeding the flame retardant component treated in the step (2), a carrier and other functional auxiliary agent components in a metering manner through a weightless scale; wherein the nanometer predispersed conductive paste component is fed through a metering pump in a feeding port in the middle of an extruder, and is subjected to melting modification, grinding surface air cooling granulation, so as to obtain the nanometer flame-retardant conductive master batch new material.

9. The method for preparing the new nano material of the masterbatch with the flame-retardant and conductive functions according to claim 8, wherein the step (1) is completed in a reaction kettle with a thermometer, a condenser, a temperature control device and a variable-frequency stirring device, wherein the process pressure and the temperature are set to be 40-120 ℃, and the mixing speed is 50-1200 r/min.

10. The method for preparing a new material of nanometer master batch with flame retardant and conductive functions as claimed in claim 9, wherein the high-speed mixing speed in the step (2) is 1500-3000 r/min;

and (3) granulating the material in the step (3) by parallel double screws, wherein the extrusion temperature is 165-.

Technical Field

The invention belongs to the technical field of nano material technology application and novel polymer materials, and particularly relates to a novel nano conductive flame-retardant master batch material and a preparation method thereof.

Background

The composite material with the functions of electric conduction and flame retardance is widely applied in various industrial fields, and is widely applied in various fields of mine site equipment parts, dangerous gas conveying pipelines, electromagnetic wave shielding films, self-limiting temperature heating and overload protection parts, pressure-sensitive conductive adhesives and the like.

The research and development of new materials with related double functions of electric conduction and flame retardance are obviously lagged. Patent CN202010536985.5 describes a high flame retardant conductive composite material, which uses modified graphene oxide as a conductive material, but has a poor dispersion effect. In the research on the electric conduction and flame retardant properties of polypropylene/graphite composite materials, the composite material which takes expanded graphite as a filler and polypropylene as a matrix and has the electric conduction and flame retardant properties is adopted, but the mechanical properties of the material are seriously deteriorated due to the large total addition amount. The surface pretreatment of flame retardants with pre-dispersants has also been reported in the literature. CN101560313A discloses that the formula contains silane and titanate coupling agent. CN105504519A discloses a halogen-free flame retardant coated with a titanate coupling agent. But does not disclose how the surface treatment is performed.

Most of the existing polymer conductive flame-retardant solutions adopt the method that flame-retardant master batches and conductive master batches are respectively added so as to achieve the purpose of function accumulation, but the two materials have poor synergistic effect in actual production and even have performance opposition; the total addition ratio is too high, which causes deterioration of physical properties of the polymer and increase of cost; the problems of poor plasticizing dispersion, poor process batch stability and the like are easy to produce when the material is processed on conventional equipment.

Disclosure of Invention

In order to solve the problems and realize the flame retardant and conductive dual compound functions of the material, the invention provides a novel efficient nanometer conductive flame retardant master batch material and a preparation method thereof.

The invention relates to a novel nanometer flame-retardant conductive master batch material and a preparation method thereof, wherein the novel nanometer flame-retardant conductive master batch material comprises the following components in parts by mass: 3-10 parts of nano pre-dispersed conductive paste component, 65-80 parts of flame retardant component, 10-20 parts of carrier component and 5-10 parts of functional auxiliary agent component. Simultaneously, the preparation method of the novel nanometer flame-retardant conductive master batch material comprises the steps of preparing nanometer pre-dispersed conductive slurry components, performing fusion modification, and grinding, granulating and molding. The invention aims to provide master batches with functions of endowing a polymer with a conductive function and a flame retardant function and a preparation method thereof.

The technical scheme of the invention is as follows:

a novel nanometer flame-retardant conductive master batch material and a preparation method thereof comprise the following components in parts by mass: 3-10 parts of nano pre-dispersed conductive paste component, 65-75 parts of flame retardant component, 10-20 parts of carrier component and 5-10 parts of functional auxiliary agent component;

the nanometer pre-dispersion conductive paste comprises the following components: dispersing solvent, stabilizer and conductive nano material;

the mass ratio of the dispersing solvent to the stabilizer to the conductive nano material is 60-80: 10-20: 2-5.

Preferably, the dispersant solution is a composition of polyethylene glycol and paraffin mineral oil, and the mass ratio of the polyethylene glycol to the paraffin mineral oil is 20-40: 60-80 parts;

the stabilizer is polyamide-amine (PAMAM) with a highly branched structure, wherein-NH is contained in the PAMAM₂、-OH、-COOCH₃At least 2 or more functional groups capable of reacting with a coupling agentGraft-crosslinking reaction takes place.

Preferably, the conductive nano material in the nano pre-dispersion conductive paste component is a single-walled carbon nanotube, wherein the particle size of the nano material is 10-50 nm.

Preferably, the conductive nano material component accounts for 2-5% of the total mass component of the nano pre-dispersed conductive paste component.

Preferably, the flame retardant component includes, but is not limited to, halogen-antimony composite system, phosphorus-nitrogen composite system or magnesium-aluminum composite system flame retardant or its flame retardant master batch.

Preferably, the carrier component is one or more of polyethylene, polypropylene, ethylene octene and ethylene vinyl acetate.

Preferably, the functional auxiliary agent component comprises an antioxidant, a lubricant and a coupling agent, and the mass ratio of the antioxidant to the lubricant to the coupling agent is 0.3-0.8: 1-3: 1-2.5;

the antioxidant is phosphite antioxidant;

the lubricant is one or a combination of a polymeric wax, ethylene bis stearamide and a fatty acid ester lubricant;

the coupling agent is one or more compositions of silane coupling agents.

A preparation method of a novel nano flame-retardant conductive master batch material comprises the following steps:

(1) respectively weighing a dispersing solvent and a conductive nano material; sequentially putting into a kettle with a stirrer, mixing for 30-60 minutes, adding a stabilizer, modifying and mixing for 10-30 minutes to obtain nano pre-dispersed conductive paste;

(2) putting the flame retardant components into a high-speed mixer according to the formula proportion for mixing, and then adding the functional assistant coupling agent component to complete coupling, cladding and modification;

(3) melting, plasticizing and granulating through a double-screw extruder, and feeding the flame retardant component treated in the step (2), a carrier and other functional auxiliary agent components in a metering manner through a weightless scale; wherein the nanometer predispersed conductive paste component is fed through a metering pump in a feeding port in the middle of an extruder, and is subjected to melting modification, grinding surface air cooling granulation, so as to obtain the nanometer flame-retardant conductive master batch new material.

Preferably, the step (1) is completed in a reaction kettle with a thermometer, a condenser, a temperature control device and a variable-frequency stirring device, wherein the process pressure and temperature are set to be 40-120 ℃, and the mixing speed is 50-1200 r/min.

Preferably, the high-speed mixing rotation speed in the step (2) is 1500-3000 r/min; the rotating speed of the low-speed mixer is 60-200 revolutions per minute;

and (3) granulating the material in the step (3) by parallel double screws, wherein the extrusion temperature is 165-.

The invention has the beneficial effects that:

1. according to the invention, the nano conductive material is used as a conductive agent, and the pre-dispersed conductive slurry is prepared, so that the problems of use of nano powder and difficulty in dispersion are solved, the dispersibility of the nano conductive material in a polymer is effectively improved, and the structural advantages of the nano material can be maintained when the nano conductive material is processed by conventional equipment;

2. the predispersed nano conductive paste material prepared by the technology has good stability and compatibility, wherein the stabilizer component with a branched structure can improve the dissolution stability and the dissolution saturation of the nano conductive material component in a solvent, and the branched structure material contains NH₂、-OH、-COOCH₃The functional group of-COONa can generate graft crosslinking reaction with the coupling agent of the coated flame retardant, so that the compatibility of the integral material is improved;

3. completing chemical grafting modification and melting plasticizing granulation in a screw by using double-screw extruder equipment;

4. melting and plasticizing by using a double-screw extruder, feeding the flame retardant, the carrier and the auxiliary agent components through weightless weighing and metering, and feeding the nano pre-dispersed conductive paste components through a metering pump in a feeding port in the middle of the extruder to complete the preparation of the dynamic formula combination;

5. the screw barrel chemical grafting modification is completed in physical mixing dispersion and melting plasticization through double-screw equipment; the grinding surface air cooling granulation molding is adopted, so that the hydrolysis can be effectively avoided, and the preparation of the master batch with high concentration content is completed;

6. the functional master batch material prepared by the technology can be processed by direct injection molding, extrusion, tape casting, film blowing and the like after being mixed with the polymer, and has the advantages of uniform dispersion, stable process, excellent material performance, high cost performance and the like.

Detailed Description

Examples

Example 1

(1) Weighing 40kg of dispersing solvent polyethylene glycol and 40kg of paraffin oil, putting into a reaction kettle, starting high-speed stirring at the temperature of 80 ℃, the speed of 500r/min and the time of 5 minutes; then 15kg of polyamide-amine (PBMAMA) branched stabilizer is added, the temperature is 80 ℃, the mixing speed is 1800r/min, and the time is 20 minutes; then 5kg of single-walled carbon nanotubes (with the particle size of 20 nm) are added, and the high-speed stirring is continuously kept for 30 minutes; then reducing the stirring speed to 60r/min for 30 minutes, and cooling to room temperature to prepare a nano conductive pre-dispersed slurry material test example A;

(2) weighing 60kg of decabromodiphenylethane and 20kg of antimony trioxide, putting into a high-speed mixer, starting stirring, setting the temperature at 120 ℃, and keeping the time for 25 minutes; 960g of silane coupling agent (KH 560) was then added, and stirring was continued for 5 minutes to obtain flame retardant test example # 1;

(3) the nano pre-dispersed conductive paste test example a was weighed: 10kg, flame retardant test example # 1: 65kg, 19.5kg of a carrier component of ethylene vinyl acetate (EVA, VA content 28), 0.5kg of an antioxidant (type B215) of a functional additive component and 5kg of a lubricant (polyethylene wax, molecular weight 3000), and plasticizing and granulating by a double-screw extruder; wherein the predispersed nano conductive paste material is metered from a middle feeding port, and the rest components are metered by a weightless scale and injected into the double screws from the roots of the screws; the new nano conductive flame-retardant functional master batch material of the EVA carrier is prepared by grinding, air cooling and grain cutting, and the product number is test example No. 1.

Example 2

(1) Weighing 30kg of dispersing solvent polyethylene glycol and 30kg of paraffin oil, putting into a reaction kettle, starting high-speed stirring at the temperature of 80 ℃, the speed of 500r/min and the time of 5 minutes; then 10kg of polyamide-amine (PBMAMA) branched stabilizer is added, the temperature is 80 ℃, the mixing speed is 1800r/min, and the time is 20 minutes; then 3kg of single-walled carbon nanotubes (with the particle size of 20 nm) are added, and the high-speed stirring is continuously kept for 20 minutes; then, the stirring speed is reduced to 60r/min for 25 minutes, and the mixture is cooled to room temperature to prepare a nano conductive pre-dispersed slurry material test example B;

(2) weighing 88.5kg of polymeric magnesium hydroxide (with the particle size of 3 um) and 5kg of montmorillonite (with the particle size of 1.5 um) and putting into a high-speed mixer, starting stirring, setting the temperature at 120 ℃ and keeping the time for 30 minutes; then, 1.5kg of a silane coupling agent (KH 560) was added thereto, and the mixture was continuously stirred for 15 minutes to prepare flame retardant test example # 2;

(3) the nano pre-dispersed conductive paste test example B was weighed: 10kg, flame retardant test example # 2: 65kg, 19.5kg of a carrier component of ethylene vinyl acetate (EVA, VA content 28), 0.5kg of an antioxidant (type B215) of a functional additive component and 5kg of a lubricant (polyethylene wax, molecular weight 3000), and plasticizing and granulating by a double-screw extruder; wherein the predispersed nano conductive paste material is metered from a middle feeding port, and the rest components are metered by a weightless scale and injected into the double screws from the roots of the screws; the new nano conductive flame-retardant functional master batch material of the EVA carrier is prepared by grinding, air cooling and grain cutting, and the product number is test example No. 2.

Example 3

(1) Weighing 30kg of dispersing solvent polyethylene glycol and 40kg of paraffin oil, putting into a reaction kettle, starting high-speed stirring at the temperature of 60 ℃, the speed of 800r/min and the time of 3 minutes; then 20kg of polyamide-amine (PBMAMA) branched stabilizer is added, the temperature is 80 ℃, the mixing speed is 3000r/min, and the time is 10 minutes; then 2.5kg of single-walled carbon nanotubes (with the particle size of 20 nm) are added, and the high-speed stirring is continuously kept for 10 minutes; then, the stirring speed is reduced to 100r/min for 25 minutes, and the mixture is cooled to room temperature to prepare a nano conductive pre-dispersed slurry material test example C;

(2) weighing 60kg of piperazine pyrophosphate and 20kg of melamine polyphosphate, putting the weighed materials into a high-speed mixer, starting stirring, setting the temperature to be 80 ℃, and keeping the time for 10 minutes; then, 1.2kg of a silane coupling agent (KH 560) was added thereto, and the mixture was continuously stirred for 15 minutes to prepare flame retardant test example # 3;

(3) the nano pre-dispersed conductive paste test example C was weighed: 10kg, flame retardant test example # 3: 70kg of carrier component ethylene octylene (POE, MI is 20) 15kg, functional additive component antioxidant (type B215) 0.5kg and lubricant (EBS) 4.5kg, and plasticizing and granulating by a double-screw extruder; wherein the predispersed nano conductive paste material is metered from a middle feeding port, and the rest components are metered by a weightless scale and injected into the double screws from the roots of the screws; the POE carrier nano-conductive flame-retardant master batch new material is prepared by grinding, air cooling and granulating, and the product number is test example No. 3.

Example 4

(1) Weighing 20kg of dispersing solvent polyethylene glycol and 60kg of paraffin oil, putting into a reaction kettle, starting high-speed stirring at the temperature of 80 ℃, the speed of 500r/min and the time of 5 minutes; then 10kg of polyamide-amine (PBMAMA) branched stabilizer is added, the temperature is 80 ℃, the mixing speed is 2000r/min, and the time is 10 minutes; then 2kg of single-walled carbon nanotubes (with the particle size of 20 nm) are added, and the high-speed stirring is continuously kept for 10 minutes; then, the stirring speed is reduced to 600r/min for 30 minutes, and the mixture is cooled to room temperature to prepare a nano conductive pre-dispersed slurry material test example D;

(2) weighing 20kg of coated red phosphorus and 45kg of aluminum hydroxide, putting into a high-speed mixer, starting stirring, setting the temperature to 80 ℃, and keeping the time for 15 minutes; then, 1.5kg of a silane coupling agent (KH 560) was added thereto, and the mixture was kept stirred for 15 minutes to prepare flame retardant test example # 4;

(3) the nano pre-dispersed conductive paste test example D was weighed: 10kg, flame retardant test example # 4: 70kg of carrier component polyethylene (LDPE, MI is 40) 15kg, functional additive component antioxidant (type B215) 0.5kg, lubricant (polyethylene wax) 2.5kg and EBS2kg, and plasticizing and granulating by a double-screw extruder; wherein the predispersed nano conductive paste material is metered from a middle feeding port, and the rest components are metered by a weightless scale and injected into the double screws from the roots of the screws; the new nano conductive flame-retardant functional master batch material of the EVA carrier is prepared by grinding, air cooling and grain cutting, and the product number is test example No. 4.

Table 1

Comparative data obtained by mixing the samples of the examples with HDPE (type HDPE 6100M) in different mass ratios and injection moulding are shown in Table 2

Table 2

The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.