CN110922747B

CN110922747B - Halogen-free flame-retardant master batch and preparation method thereof, and glass fiber reinforced nylon material and preparation method thereof

Info

Publication number: CN110922747B
Application number: CN201911264879.XA
Authority: CN
Inventors: 许文娟; 许红卫; 窦伟; 栗大利; 刘鹏
Original assignee: Jiangsu Weiguan New Material Technology Co ltd
Current assignee: Jiangsu Weiguan New Material Technology Co ltd
Priority date: 2019-12-11
Filing date: 2019-12-11
Publication date: 2023-03-10
Anticipated expiration: 2039-12-11
Also published as: CN110922747A

Abstract

The invention provides a halogen-free flame-retardant master batch which comprises the following components in percentage by weight: 15-40% of resin, 50-80% of organic phosphinate, 9-30% of organic silicon flame retardant and 1-10% of inorganic silicon synergist; the sum of all the components is 100 percent. The halogen-free flame-retardant master batch has good flame-retardant effect, no precipitation and no corrosion to equipment.

Description

Halogen-free flame-retardant master batch and preparation method thereof, and glass fiber reinforced nylon material and preparation method thereof

Technical Field

The invention relates to the technical field of flame-retardant modification of high polymer materials, in particular to a preparation method and application of a halogen-free flame-retardant master batch for glass fiber reinforced nylon.

Background

Glass fiber reinforced nylon materials are widely used in a plurality of industrial fields due to excellent mechanical properties, chemical stability and thermal stability, but when a heat source exists, the glass fiber reinforced nylon materials are easy to burn, so that a flame retardant is usually added to endow the glass fiber reinforced nylon materials with corresponding flame retardant properties to meet industrial requirements, particularly in the fields of electronics, electrics and new energy automobiles.

The phosphorus flame retardant has high flame retardant efficiency, no halogen and good electrical property and is widely applied to flame retardant modification of glass fiber reinforced nylon. Melamine polyphosphate (MPP) synergistic Aluminum Diethylphosphinate (ADP) is a typical organic phosphine flame retardant system, and due to the high phosphorus content and the synergistic action of phosphorus and nitrogen, the flame retardant can realize high-efficiency flame retardance of glass fiber reinforced nylon, and can not generate extremely toxic gases such as phosphine and the like in the high-temperature processing process. However, this system has the following disadvantages:

1) The flame retardant is in a powder form, has large addition amount and is easy to adsorb on the wall of the feeding hopper, thereby causing the problems of bridging of the blanking, uneven feeding, easy breaking of the granulation and the like;

2) The two components react and decompose at high temperature to generate a small amount of acid gas, and the acid gas can not only cause the color change of materials, but also cause the corrosion of metal parts of processing equipment, thereby bringing the problems of cost increase and production efficiency reduction;

3) The flame retardant is easy to separate out: when ADP and MPP are used in a damp and hot environment, the flame retardant is easy to migrate to the surface of a product, so that the flame retardant is unevenly distributed and lost, and finally, the flame retardance and the electrical property of the material are reduced, which cannot be accepted in the field of electronics and electricity. When the material contains MPP, mold scale is easy to generate in the injection molding process, and the production efficiency is reduced by occasionally stopping and cleaning the mold.

In the prior art, although the problems of blanking and dispersion are solved by adopting the flame-retardant master batch of an ADP/MPP synergistic system, the problems of corrosivity and MPP precipitation still exist; the other special halogen-free flame-retardant master batch for reinforced nylon is a master batch product taking Melamine Cyanurate (MCA) as a flame retardant, and because the decomposition temperature of MCA is low, foaming phenomenon is easy to occur in glass fiber reinforced nylon 66, and meanwhile, the flame-retardant grade of MCA in the glass fiber reinforced nylon can only reach UL94V2, so that the application scene is limited.

In recent years, the search for more efficient ADP flame retardant synergists has been an important research direction.

The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.

Disclosure of Invention

Aiming at one or more problems in the prior art, the invention provides the halogen-free flame-retardant master batch, which solves the problems of migration, equipment corrosion and the like of the halogen-free flame-retardant master batch for the glass fiber reinforced nylon material.

The invention provides a halogen-free flame-retardant master batch which comprises the following components in percentage by weight:

15 to 40 percent of resin,

50 to 80 percent of organic phosphinate,

9 to 30% of a silicone-based flame retardant, and

1-10% of inorganic silicon synergist;

the sum of all the components is 100 percent.

As a preferable scheme of the halogen-free flame-retardant master batch, the halogen-free flame-retardant master batch further comprises a lubricant, wherein the mass fraction of the lubricant is 2-4%.

Preferably, the lubricant comprises an external lubricant and/or an internal lubricant.

Preferably, the external lubricant comprises aluminum stearate, lithium stearate, calcium stearate or silicone powder.

Preferably, the internal lubricant comprises one or a combination of two or more of a polyamide wax, montan wax, EBS, TAF, or pentaerythritol stearate. Further preferred is a combination of a polyamide wax with montan wax 1.

EBS is ethylene bis stearamide, is a novel plastic lubricant developed in recent years, and compared with the traditional lubricants such as paraffin wax, polyethylene wax, stearate and the like, the novel plastic lubricant has good external lubrication effect and good internal lubrication effect, so that the fluidity and the mold release property of melt-isolation plastic are improved in plastic molding processing, the yield of plastic processing is improved, the energy consumption is reduced, and the product has extremely high surface smoothness and smoothness.

The lubricant TAF takes EBS as a base material, and under the action of a catalyst, a reactive monomer containing a polar group reacts with the EBS to form a BAB type copolymer. The copolymer not only maintains the lubricating property of EBS, but also has a polar group structure which can be combined with partial polar groups on the surfaces of glass fibers and inorganic fillers.

As a further preferable scheme of the halogen-free flame-retardant master batch, the halogen-free flame-retardant master batch further comprises an antioxidant, wherein the mass fraction of the antioxidant is 0.5-1%.

Preferably, the antioxidant comprises one or more of a combination of a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant or a metal salt antioxidant. Wherein, the phenolic antioxidant preferably adopts antioxidant 1098, antioxidant 1010 or antioxidant 10761076; the phosphorus antioxidant preferably adopts antioxidant 168, antioxidant 626 or antioxidant 627; the thioether antioxidant is preferably antioxidant DLTP or antioxidant DSTP.

In the prior art, an antioxidant is not generally added into the flame-retardant master batch, but is added into the preparation of downstream products. The antioxidant is added in the master batch preparation stage, so that the polymer and the halogen-free flame retardant can be prevented from generating thermal oxidation degradation in the processing process, and the forming processing can be smoothly carried out.

According to one aspect of the invention, the halogen-free flame-retardant master batch comprises the following components:

30-40% of resin,

50-60% of organic phosphinate,

10 to 15 percent of organic silicon flame retardant,

5-8% of inorganic silicon synergist;

2-4% of a lubricant;

0.5 to 1 percent of antioxidant;

the sum of all the components is 100 percent.

According to one aspect of the invention, the resin is selected from one or a combination of two or more of PA6, PA66, PA12, PA1315 or PAMXD 6.

According to one aspect of the invention, the resin has a relative viscosity of 2.0 to 2.8. The physical properties of the modified polymer are reduced due to the fact that the master batches with too high viscosity are not extruded smoothly and the master batches with too low viscosity are applied in downstream. The relative viscosity, also known as the viscosity ratio, is the ratio of the absolute viscosity of a liquid to the absolute viscosity of another liquid at a certain temperature, and the liquid used for comparison is usually water or a suitable liquid.

According to one aspect of the invention, the organic phosphinate salt comprises one or a combination of two or more of aluminum dialkylphosphinate, zinc dialkylphosphinate, iron dialkylphosphinate, or aluminum phenylphosphinate. Further preferred is aluminum diethylphosphinate.

According to one aspect of the invention, the average particle size D50 of the organic phosphinic acid salt is from 20 to 50 μm. Too large or too small particle size can lead to poor dispersibility of the flame retardant and influence on flame retardant effect and physical and mechanical properties.

According to one aspect of the present invention, the silicone-based flame retardant includes one or a combination of two or more of polysiloxane, cage-type silsesquioxane, hydroxy silicone oil, or silicone rubber. Silicone rubber is preferred.

The organic silicon flame retardant is a novel halogen-free flame retardant which is efficient, low in toxicity, anti-dripping and environment-friendly, is combined with a polymer through a mechanism similar to partial crosslinking of an Interpenetrating Polymer Network (IPN), and limits the flow of the flame retardant in the polymer to a great extent, so that the organic silicon flame retardant has no migration phenomenon. When the organic silicon flame retardant is burnt, the flame retardant which starts to melt passes through the gaps of the base material and migrates to the surface of the base material to form a compact and stable silicon-containing coked carbon protective layer.

Meanwhile, the organic silicon can increase the dispersibility of the leached flame retardant in the base material, so that the using amount of the organic phosphinate is reduced, the processing performance of the base material is improved, the influence of physical and mechanical properties is small, the corrosion and precipitation are relieved, and the modified organic silicon modified flame retardant is an ideal substitute for MPP.

According to one aspect of the invention, the inorganic silicon-based synergist comprises one or a combination of more than two of phyllosilicate, nano-silica or low-melting glass powder, preferably nano-silica.

The flame retardant effect of the organic silicon synergistic organic phosphinate is not good when the organic silicon synergistic organic phosphinate is used alone, and the inorganic silicon is compounded, so that high flame retardant property can be met. The inorganic silicon synergist can be used as a synergistic flame retardant, and when the flame retardant material is burnt, the generated silicon dioxide forms an amorphous silicon protective layer on the surface of the system. Inorganic silicon-based flame retardants have been developed: silica, microporous and low melting point glasses, silica gel/potassium carbonate, talc, aluminum silicate, and the like.

The invention also provides a preparation method of the halogen-free flame-retardant master batch, which comprises the following steps:

step 1): evenly mixing organic phosphinate, organic silicon flame retardant and inorganic silicon synergist and adding into resin;

step 2): and (2) carrying out melt blending on the uniformly mixed mixture obtained in the step 1), and extruding to obtain the halogen-free flame-retardant master batch.

According to one aspect of the invention, in the step 1), before the organic phosphinate, the organic silicon flame retardant and the inorganic silicon synergist are added into the resin, the resin is pretreated, and the pretreatment method comprises the step of uniformly mixing the resin and the antioxidant.

According to one aspect of the present invention, in the step 1), when the organic phosphinate, the organic silicon-based flame retardant and the inorganic silicon-based synergist are mixed, a lubricant is further added for mixing. The lubricant has the lubricating effect and also has the dispersing effect, so that the organic phosphinate, the organic silicon flame retardant and the inorganic silicon synergist are mixed more uniformly, and the three components are better dispersed in the resin.

According to one aspect of the invention, in the step 2), an extruder is adopted for the extrusion, and the temperature of each zone of the extruder is controlled to be 180-200 ℃. Preferably, the extruder temperature zone is 12 sections, the temperature in the region 1-11 is 180 deg.C, 200 deg.C, 190 deg.C, 180 deg.C, the head temperature was 200 ℃. If the temperature is too low, the nylon resin cannot be melted. If the temperature is more than 200 ℃, the flame retardant is subjected to a certain decomposition reaction, which causes a series of problems such as degradation of the polymer, discoloration, and reduction in physical properties (e.g., tensile resistance). Through long-term intensive research and practice, the effect is best by adopting the zone temperature.

Preferably, in the step 2), a screw extruder, preferably a single screw extruder or a double screw extruder, is used for the extrusion; preferably, the screw of the screw extruder has a rotational speed of 100rpm to 250rpm.

The invention also provides a glass fiber reinforced nylon 66 material, which comprises: the halogen-free flame-retardant master batch, the nylon 66, the glass fiber and the auxiliary agent. Preferably, the auxiliary agent is a 1098 and calcium stearate 1. Further preferably, the halogen-free flame-retardant master batch: nylon-66: glass fiber: the mass ratio of the auxiliary agent is 3:4:3:0.5.

the invention also provides a preparation method of the glass fiber reinforced nylon material, which comprises the following steps:

step 1): uniformly mixing the halogen-free flame-retardant master batch, the nylon 66 and the auxiliary agent;

step 2): melting and extruding the mixture obtained in the step 1), and feeding glass fibers from a glass fiber port; and granulating and drying to obtain the glass fiber reinforced nylon material.

The invention has the beneficial effects that:

the halogen-free flame-retardant master batch provided by the invention has the characteristics of stable color, no migration, no corrosion to equipment and the like, and can be well adapted to a glass fiber reinforced nylon material system; meanwhile, the master batch product solves the problem of blanking of the powder flame retardant, and improves the dispersibility of the flame retardant in a system in the modification process of the master batch product. The silicon-based flame retardant can improve the dispersion effect of the halogen-free phosphine-based flame retardant in the system, so that the color is stable.

The glass fiber reinforced nylon material provided by the invention has no precipitation and no corrosion to equipment, and the UL94 flame retardant rating reaches 0.8mm-V0.

The component materials involved in the present invention are commercially available.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a schematic view of a corrosion test method;

FIG. 2 is a photograph of the halogen-free flame retardant masterbatch of the present invention;

wherein, 1 is a copper pipe, and 2 is a sample.

Detailed Description

In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the drawings and description are to be regarded as illustrative in nature, and not as restrictive.

The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.

Example 1A:

the embodiment shows a halogen-free flame-retardant master batch and a preparation process thereof, and the components of the halogen-free flame-retardant master batch are shown in table 1.

The preparation process comprises the following steps:

step 1): the resin (PA 6) and the antioxidant (phenolic antioxidant 1098) are mixed evenly and then added into an extruder by an active feeding device.

Step 2): and then evenly mixing organic phosphinate (aluminum diethylphosphinate, the average particle size D50 is 30 μm), organic silicon flame retardant (silicone rubber), inorganic silicon synergist (nano-silica) and lubricant (a combination of silicone powder and lithium stearate 1), and adding the mixture into the extruder through a side feeding device of the extruder.

Step 3): melt blending and extruding the mixture of the step 1). The temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃, specifically, the temperature zone of the extruder is 12 sections, and the temperature of the zones 1 to 11 is 180 ℃, 200 ℃, 190 ℃, 180 ℃, and 200 ℃ of the head. And adopting a double-screw extruder to melt and extrude at the screw rotating speed of 150rpm-250 rpm. And then cooling, granulating, sieving and drying to obtain the halogen-free flame-retardant master batch, which is shown in the attached figure 2.

Example 1B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 1A, including the steps of:

step 1): uniformly mixing 2.5kg of the halogen-free flame-retardant master batch prepared by the method in the embodiment 1A, 664.5kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

step 2): and (3) finishing extrusion granulation by using a double-screw extruder with phi 36 and the length-diameter ratio of 40, sieving and drying the granulated material to obtain the glass fiber reinforced nylon material, wherein the properties of the glass fiber reinforced nylon material are shown in table 2.

Example 2A:

The preparation process comprises the following steps:

step 1): the resin (PA 12) and the antioxidant (thioether antioxidant DLTP) are uniformly mixed and then are added into an extruder through an active feeding device.

Step 2): and then uniformly mixing organic phosphinate (aluminum phenylphosphinate with the average particle size D50 of 20 microns), organic silicon flame retardant (polyhedral oligomeric silsesquioxane), inorganic silicon synergist (low-melting glass powder) and lubricant (aluminum stearate), and adding the mixture into the extruder through a side feeding device of the extruder.

Step 3): melt blending and extruding the mixture of the step 1). The temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃, specifically, the temperature zone of the extruder is 12 sections, and the temperature of the zones 1 to 11 is 180 ℃, 200 ℃, 190 ℃, 180 ℃, and 200 ℃ of the head. And (3) performing melt extrusion by adopting a double-screw extruder at the screw rotating speed of 150-250 rpm, and then cooling, granulating, sieving and drying to obtain the halogen-free flame-retardant master batch.

Example 2B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 2A, comprising the steps of:

step 1): uniformly mixing 3.0kg of the halogen-free flame-retardant master batch prepared by the method in the embodiment 2A, 664.0kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

step 2): and (3) finishing extrusion granulation by using a double-screw extruder with phi 36 and a length-diameter ratio of 40, sieving the granulated material, and drying to obtain the glass fiber reinforced nylon material, wherein the performance of the glass fiber reinforced nylon material refers to table 2.

Example 3A:

The preparation process comprises the following steps:

step 1): the resin (PA 66) and the antioxidant (phosphorus antioxidant 168) are uniformly mixed and then added into an extruder through an active feeding device.

Step 2): the organic phosphinate (zinc dialkylphosphinate, with an average particle size D50 of 50 μm), the silicone flame retardant (polysiloxane), the inorganic silicone synergist (layered silicate), and the lubricant (combination of polyamide wax and montan wax 1) were mixed uniformly and added to the extruder through a side-feeding device of the extruder.

Step 3): melt blending and extruding the mixture of the step 1). The temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃, specifically, the temperature zone of the extruder is 12 sections, the temperature of the 1-11 region is 180 ℃, 200 ℃, 190 ℃, 180 ℃, the head temperature was 200 ℃. And (3) melting and extruding by adopting a double-screw extruder at the screw rotating speed of 150-250 rpm, cooling, granulating, sieving and drying to obtain the halogen-free flame-retardant master batch.

Example 3B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 3A, comprising the steps of:

step 1): uniformly mixing 3.0kg of the halogen-free flame-retardant master batch prepared by the method in the embodiment 3A, 664.0kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

Example 4A:

The preparation process comprises the following steps:

step 1): the resin (PA 1315) and the antioxidant (phenolic antioxidant 1010) are uniformly mixed and then added into an extruder through an active feeding device.

Step 2): and then uniformly mixing organic phosphinate (iron dialkyl phosphinate with the average particle size D50 of 40 mu m), organic silicon flame retardant (hydroxyl silicone oil), inorganic silicon synergist (nano silicon dioxide) and lubricant (calcium stearate), and adding the mixture into the extruder through a side feeding device of the extruder.

And step 3): melt blending and extruding the mixture of the step 1). The temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃, specifically, the temperature zone of the extruder is 12 sections, and the temperature of the zones 1 to 11 is 180 ℃, 200 ℃, 190 ℃, 180 ℃, and 200 ℃ of the head. And (3) performing melt extrusion by adopting a double-screw extruder at the screw rotating speed of 150-250 rpm, and then cooling, granulating, sieving and drying to obtain the halogen-free flame-retardant master batch.

Example 4B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 4A, comprising the steps of:

step 1): uniformly mixing 3.0kg of the halogen-free flame-retardant master batch prepared by the method in the embodiment 4A, 664.0kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

Example 5A:

The preparation process comprises the following steps:

step 1): the resin (PAMXD 6) and the antioxidant (thioether antioxidant DSTP) are uniformly mixed and then are added into an extruder through an active feeding device.

Step 2): and uniformly mixing organic phosphinate (aluminum phenylphosphinate, the average particle size D50 of 35 microns), an organic silicon flame retardant (mixture of polysiloxane and hydroxyl silicone oil according to the mass ratio of 10.

And step 3): melt blending and extruding the mixture of the step 1). The temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃, specifically, the temperature zone of the extruder is 12 sections, and the temperature of the zones 1 to 11 is 180 ℃, 200 ℃, 190 ℃, 180 ℃, and 200 ℃ of the head. And (3) melting and extruding by adopting a double-screw extruder at the screw rotating speed of 150-250 rpm, cooling, granulating, sieving and drying to obtain the halogen-free flame-retardant master batch.

Example 5B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 5A, comprising the steps of:

step 1): uniformly mixing 3.0kg of the halogen-free flame-retardant master batch prepared by the method in the embodiment 5A, 664.0kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

Example 6A:

The preparation process comprises the following steps:

step 1): the resin (PA 6) and the antioxidant (the phosphorus antioxidant is the antioxidant 626) are mixed uniformly and then added into an extruder through an active feeding device.

Step 2): and uniformly mixing organic phosphinate (dialkyl aluminum phosphinate, the average particle size D50 is 45 microns), organic silicon flame retardant (hydroxyl silicone oil), inorganic silicon synergist (nano silicon dioxide) and lubricant (pentaerythritol stearate), and adding the mixture into the extruder through a side feeding device of the extruder.

Step 3): melt blending and extruding the mixture of the step 1). The temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃, specifically, the temperature zone of the extruder is 12 sections, and the temperature of the zones 1 to 11 is 180 ℃, 200 ℃, 190 ℃, 180 ℃, and 200 ℃ of the head. And (3) melting and extruding by adopting a double-screw extruder at the screw rotating speed of 150-250 rpm, cooling, granulating, sieving and drying to obtain the halogen-free flame-retardant master batch.

Example 6B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 6A, including the steps of:

step 1): uniformly mixing 3.0kg of the halogen-free flame-retardant master batch prepared by the method in the embodiment 6A, 664.0kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

Example 7A:

The preparation process comprises the following steps:

step 1): the resin (PA 6) and the antioxidant (phenolic antioxidant adopts antioxidant 10761076) are mixed evenly and then added into the extruder by an active feeding device.

Step 2): and then evenly mixing organic phosphinate (aluminum dialkyl phosphinate, the average particle size D50 is 25 microns), organic silicon flame retardant (polysiloxane), inorganic silicon synergist (nano silicon dioxide) and lubricant (EBS), and adding the mixture into the extruder through a side feeding device of the extruder.

Step 3): melt blending and extruding the mixture of the step 1). The temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃, specifically, the temperature zone of the extruder is 12 sections, the temperature of the zones 1 to 11 is 180 ℃, 200 ℃, 190 ℃, 180 ℃ and the temperature of the machine head is 200 ℃. And (3) melting and extruding by adopting a double-screw extruder at the screw rotating speed of 150-250 rpm, cooling, granulating, sieving and drying to obtain the halogen-free flame-retardant master batch.

Example 7B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 7A, comprising the steps of:

step 1): uniformly mixing 3.0kg of the halogen-free flame-retardant master batch prepared by the method of the embodiment 7A, 664.0kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

Example 8A:

The preparation process comprises the following steps:

step 1): the resin (PA 6) and the antioxidant (the phosphorus antioxidant is the antioxidant 627) are mixed uniformly and then are added into an extruder through an active feeding device.

Step 2): and uniformly mixing organic phosphinate (aluminum phenylphosphinate, the average particle size D50 is 32 mu m), organic silicon flame retardant (polysiloxane), inorganic silicon synergist nano silicon dioxide) and lubricant (TAF), and adding the mixture into the extruder through a side feeding device of the extruder.

Example 8B:

this example illustrates a process for preparing a glass fiber reinforced nylon material using the method of example 8A, comprising the steps of:

step 1): uniformly mixing 3.0kg of the halogen-free flame-retardant master batch prepared by the method in the embodiment 8A, 664.0kg of nylon, 3.0kg of glass fiber and 0.5kg of auxiliary agent;

Table 1:

comparative example 3:

comparative example 3 shows a process for the preparation of glass fibre reinforced PA66 flame retarded with ADP, comprising the steps of:

18 parts by mass of ADP, 0.3 part by mass of an antioxidant 1098, 0.3 part by mass of silicone powder, and 51.4 parts by mass of PA66 were mixed, and 30 parts by mass of glass fiber was added to prepare glass fiber-reinforced PA66, and the properties of this glass fiber-reinforced PA66 were as shown in Table 2.

Comparative example 4:

comparative example 4 shows a process for the preparation of glass fiber reinforced PA66 flame retarded with MPP in combination with ADP, comprising the steps of:

15 parts by mass of ADP, 3 parts by mass of MPP, 0.3 part by mass of antioxidant 1098, 0.3 part by mass of silicone powder and 51.4 parts by mass of PA66 were mixed, and 30 parts by mass of glass fiber was added to prepare glass fiber-reinforced PA66, the properties of which are shown in Table 2.

Comparative example 5:

comparative example 5 shows a process for the preparation of glass fibre reinforced PA66 flame retarded with MPP in combination with ADP, comprising the steps of:

15 parts by mass of ADP, 2 parts by mass of MPP, 1 part by mass of anhydrous zinc borate, 0.3 part by mass of antioxidant 1098, 0.3 part by mass of silicone powder and 51.4 parts by mass of PA66 were mixed, and 30 parts by mass of glass fiber was added to prepare glass fiber-reinforced PA66, the properties of which are shown in Table 2.

Comparative example 6:

comparative example 6 shows a process for preparing glass fiber reinforced PA66 flame retardant with an organophosphine based flame retardant using OP1400 (clariant), comprising the steps of:

OP1400 in an amount of 18 parts by mass, an antioxidant 1098 in an amount of 0.3 parts by mass, a silicone powder in an amount of 0.3 parts by mass, and PA66 in an amount of 51.4 parts by mass, and 30 parts by mass of glass fiber were added to prepare glass fiber reinforced PA66, and the properties of the glass fiber reinforced PA66 are shown in table 2.

Table 2:

as can be seen from Table 2, the halogen-free flame-retardant master batch of the invention has smooth processing and blanking, high tensile strength and impact strength, halogen-free flame-retardant grade reaching V0, no migration and no corrosion.

The following are the methods tested in table 2:

and (3) mechanical test: tensile strength and notched impact strength were tested according to ISO527, ISO179 test standard.

And (3) flame retardant test: the test was performed according to the UL94V0 test standard.

And (3) migration resistance test: the prepared glass fiber reinforced nylon material and glass fiber reinforced PA66 sample are placed in a constant temperature and humidity box, the temperature is set to be 85 ℃, the relative humidity is 85%, and the state of the surface of the sample after 168 hours is observed visually.

And (3) corrosion test: as shown in fig. 1, the prepared glass fiber reinforced nylon material and glass fiber reinforced PA66 sample 2 are respectively placed in a glass cup, a copper tube 1 is inserted in the middle of the sample, the sample is placed in a constant temperature and humidity chamber, the temperature is 85 ℃, the relative humidity is 85%, the corrosion state of the surface of the copper tube 1 after 168 hours is observed visually, and the corrosion degree is: no corrosion, normal and serious.

Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A glass fiber reinforced nylon material, comprising: the halogen-free flame-retardant master batch comprises the following components in percentage by weight:

30-40% of resin,

50-60% of organic phosphinate,

10 to 15 percent of organic silicon flame retardant,

5-8% of inorganic silicon synergist;

2-4% of a lubricant;

0.5 to 1 percent of antioxidant;

the sum of all components in the halogen-free flame-retardant master batch is 100%;

the organic silicon flame retardant is hydroxyl silicone oil;

the inorganic silicon synergist is nano silicon dioxide;

the resin is PA1315 or PA6;

the relative viscosity of the resin is 2.0-2.8;

halogen-free flame-retardant master batch: nylon-66: glass fiber: the mass ratio of the auxiliary agent is 3:4:3:0.5.

2. the glass fiber reinforced nylon material of claim 1, wherein the auxiliary agent is a 1098 and calcium stearate 1.

3. The glass fiber reinforced nylon material of claim 1, wherein the lubricant comprises an external lubricant and/or an internal lubricant.

4. The glass-fiber reinforced nylon material of claim 3, wherein the external lubricant comprises one or a combination of two or more of aluminum stearate, lithium stearate, calcium stearate, or silicone powder.

5. The glass fiber reinforced nylon material according to claim 4, wherein the external lubricant is a combination of silicone powder and lithium stearate 1.

6. The glass-reinforced nylon material of claim 3, wherein the internal lubricant comprises one or a combination of two or more of a polyamide wax, montan wax, EBS, TAF, or pentaerythritol stearate.

7. The glass fiber reinforced nylon material of claim 6, wherein the internal lubricant is a combination of a polyamide wax and a montan wax of 1.

8. The glass fiber reinforced nylon material of claim 1, wherein the antioxidant comprises one or a combination of more than two of phenolic antioxidants, phosphorus antioxidants, thioether antioxidants or metal salt antioxidants.

9. The glass fiber reinforced nylon material of claim 8, wherein the phenolic antioxidant is antioxidant 1098, antioxidant 1010 or antioxidant 1076.

10. The glass fiber reinforced nylon material of claim 8, wherein the phosphorus antioxidant is selected from the group consisting of antioxidant 168, antioxidant 626 and antioxidant 627.

11. The glass fiber reinforced nylon material of claim 8, wherein the thioether antioxidant is DLTP or DSTP.

12. The glass fiber reinforced nylon material of claim 1, wherein the organic phosphinate comprises one or a combination of two or more of aluminum dialkylphosphinate, zinc dialkylphosphinate, iron dialkylphosphinate, or aluminum phenylphosphinate.

13. The glass fiber reinforced nylon material of claim 1, wherein the organic phosphinate is aluminum diethylphosphinate.

14. The glass fiber reinforced nylon material according to claim 1, characterized in that the organic phosphinate has an average particle size D50 of 20-50 μ ι η.

15. A method of making a glass fiber reinforced nylon material according to any of claims 1-14, comprising the steps of:

step 1): uniformly mixing the halogen-free flame-retardant master batch, the nylon 66 and the auxiliary agent, and adding the glass fiber from a glass fiber opening in the middle of an extrusion machine;

step 2): extruding, granulating and drying the mixture obtained in the step 1) to obtain the glass fiber reinforced nylon material.

16. The preparation method of the glass fiber reinforced nylon material according to claim 15, wherein the preparation method of the halogen-free flame retardant master batch comprises the following steps:

step 1): uniformly mixing organic phosphinate, organic silicon flame retardant and inorganic silicon synergist and adding the mixture into resin;

step 2): carrying out melt blending and extrusion on the uniformly mixed mixture obtained in the step 1) to obtain halogen-free flame retardant master batch;

before adding the organic phosphinate, the organic silicon flame retardant and the inorganic silicon synergist into resin, pretreating the resin, wherein the pretreatment method is to uniformly mix the resin and the antioxidant;

in the step 1), when the organic phosphinate, the organic silicon flame retardant and the inorganic silicon synergist are mixed, a lubricant is also added for mixing.

17. The method for preparing glass fiber reinforced nylon material according to claim 16, wherein in step 2) of the method for preparing halogen-free flame retardant master batch, an extruder is used for the extrusion, and the temperature of each zone of the extruder is controlled between 180 ℃ and 200 ℃.

18. The method for preparing glass fiber reinforced nylon material according to claim 16, wherein in the method for preparing the halogen-free flame-retardant masterbatch, the temperature zone of the extruder is 12 sections, the temperature in the region 1-11 is 180 deg.C, 200 deg.C, 190 deg.C, 180 deg.C, the head temperature was 200 ℃.

19. The method for preparing glass fiber reinforced nylon material according to claim 16, wherein in step 2) of the method for preparing halogen-free flame retardant master batch, a screw extruder is used for the extrusion.

20. The method of claim 19, wherein the extruding is performed by a single screw extruder or a twin screw extruder.

21. The method of claim 20, wherein the screw of the screw extruder is rotated at 100rpm to 250rpm.