Substitute antimony trioxide composite flame-retardant master batch

Abstract

The application relates to the technical field of flame-retardant materials, and particularly discloses a composite flame-retardant master batch for replacing antimony trioxide. The raw materials of the composite flame-retardant master batch for replacing antimony trioxide include antimony powder, nano stannate, silicate, organic silicone oil modified by special functional groups and linear low-density polyethylene. The composite flame-retardant master batch for replacing antimony trioxide provided by the application can be applied to PBT and nylon materials, can realize efficient flame retardation of the materials, and can reach V-0 level in terms of flame retardation; the master batch has excellent carbonization, can greatly improve the glowing wire ignition temperature and CTI index of the materials, and has high mechanical properties. The master batch does not need to add antimony trioxide, and the production cost is greatly reduced.

Description

Technical Field

[0001] This invention relates to the field of flame retardant materials technology, specifically to a composite flame retardant masterbatch that can replace antimony trioxide. Background Technology

[0002] In recent years, antimony trioxide (Sb2O3), as a key synergist in halogenated flame retardant systems, has seen its price continuously break historical highs since 2024, remaining stable at over 120 yuan / kg, leading to a surge in the production cost of flame retardant materials. Although the industry has attempted to use alternatives such as zinc borate and metal hydroxides to reduce antimony usage, these solutions generally have significant drawbacks: the amount of the alternative component needs to be significantly increased (up to 25-40 parts) to match the synergistic effect of traditional antimony, and it is prone to causing deterioration in the adaptability of processing technology (such as requiring modifications to screw assembly and temperature control system). More seriously, it leads to a significant decline in the flame retardant performance of materials, such as a 15-30% decrease in limiting oxygen index (LOI) and a degradation of the UL-94 rating from V0 to V2. At the same time, although existing flame retardant masterbatch technology can improve dispersibility, it has not been able to get rid of its high dependence on antimony trioxide (the amount of antimony trioxide in commercially available products is still 40-60 wt%), forcing downstream customers to continue to bear the pressure of raw material costs; moreover, the application of such masterbatch requires precise and synchronous adjustment of the bromine-antimony ratio, resulting in low operational error tolerance, and it lacks composite functions such as smoke suppression and anti-dripping.

[0003] Therefore, it is necessary to provide an alternative antimony trioxide composite flame retardant masterbatch that does not require the addition of antimony trioxide, thereby achieving highly efficient flame retardancy of the material and greatly reducing production costs. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art. To this end, the present invention proposes an alternative to antimony trioxide composite flame retardant masterbatch, which eliminates the need to add antimony trioxide, thereby achieving high-efficiency flame retardancy of the material and greatly reducing production costs.

[0005] The first aspect of the present invention provides an alternative to antimony trioxide composite flame retardant masterbatch.

[0006] Specifically, the raw materials for replacing the antimony trioxide composite flame retardant masterbatch include antimony powder, nano-stannate, silicate, organosilicon oil modified with special functional groups, and linear low-density polyethylene.

[0007] Preferably, the raw materials for replacing antimony trioxide composite flame retardant masterbatch include, by weight parts:

[0008] 2-15 parts antimony powder;

[0009] 5-28 parts of nano-stannate;

[0010] 15-42 parts of silicate;

[0011] 1-12 parts of organosilicon oil modified with special functional groups;

[0012] 40-70 parts of linear low-density polyethylene.

[0013] More preferably, the raw materials for replacing antimony trioxide composite flame retardant masterbatch include, by weight parts:

[0014] 2-10 parts antimony powder;

[0015] 5-25 parts of nano-stannate;

[0016] 15-40 parts silicate;

[0017] 1-10 parts of organosilicon oil modified with special functional groups;

[0018] 40-70 parts of linear low-density polyethylene.

[0019] More preferably, the raw materials used to replace the antimony trioxide composite flame retardant masterbatch include, by weight parts:

[0020] 3-8 parts antimony powder;

[0021] 10-20 parts of nano-stannate;

[0022] 15-30 parts of silicate;

[0023] 1-5 parts of organosilicon oil modified with special functional groups;

[0024] 45-65 parts of linear low-density polyethylene.

[0025] Preferably, the antimony powder is high-purity antimony powder; the high-purity antimony powder is selected from elemental antimony powder with a purity of 99.8% or higher.

[0026] More preferably, the antimony powder does not contain antimony trioxide. Antimony powder mainly acts as a flame retardant synergist, especially in synergy with halogenated flame retardants. Too little antimony powder results in a weak effect, while too much increases cost and may affect mechanical properties.

[0027] Preferably, the nano-stannate includes at least one of zinc stannate, sodium stannate, potassium stannate, and hydrated zinc stannate.

[0028] More preferably, the nano-stannate is zinc stannate. Zinc stannate is an important environmentally friendly flame retardant / smoke suppressant that promotes char formation and inhibits smoke. It provides effective flame retardancy and smoke suppression while avoiding excessive impact on the processability and physical properties of the base resin.

[0029] Preferably, the particle size of the nano-stannate is 20–100 nm.

[0030] More preferably, the particle size of the nano-stannate is 20-50 nm.

[0031] More preferably, the particle size of the nano-stannate is 25 nm.

[0032] Preferably, the silicate includes at least one of talc, mica, wollastonite, kaolin, and montmorillonite.

[0033] More preferably, the silicate is talc or mica powder. Silicates primarily function as inorganic fillers and flame retardant additives, improving char formation, enhancing dimensional stability, reducing costs, and exhibiting a certain barrier effect. This invention uses silicates to balance the effects of filling, flame retardancy contribution, cost, and flowability / toughness.

[0034] Preferably, the organosilicon oil modified with special functional groups is a polydimethylsiloxane or a polyether-modified siloxane with at least one functional group selected from amino, epoxy, hydroxyl, mercapto, carboxyl, or alkoxy on its side chain or end group.

[0035] More preferably, the organosilicon oil modified with special functional groups is an amino-modified silicone oil or an epoxy-modified silicone oil.

[0036] Pre-treatment with silicone oil coating for all powders (antimony powder, nano-stannates, silicates) can improve their dispersibility and compatibility in the resin matrix, enhance processing fluidity, and potentially aid in flame retardancy by promoting char formation or migration to the surface to form a protective layer. Too low a dosage will have little effect, while too high a dosage may lead to precipitation or excessive cost. The choice of functional groups directly affects their interaction with the powder filler and resin.

[0037] Preferably, the melt index (190℃ / 2.16kg) of the linear low-density polyethylene is 30~100g / 10min.

[0038] More preferably, the melt index (190℃ / 2.16kg) of the linear low-density polyethylene is 40-90g / 10min.

[0039] More preferably, the melt index (190℃ / 2.16kg) of the linear low-density polyethylene is 50-80g / 10min.

[0040] Linear low-density polyethylene (LLDPE) is used as the carrier resin for the masterbatch. A high melt index (MI) ensures good flowability and dispersibility of the masterbatch during subsequent processing (such as blown film, injection molding, and spinning), guaranteeing that the flame retardant can be uniformly dispersed into the final product substrate.

[0041] Preferably, the raw materials used to replace the antimony trioxide composite flame retardant masterbatch also include other additives.

[0042] Preferably, the other additives include antioxidants and lubricants.

[0043] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0044] The antimony trioxide-alternative composite flame-retardant masterbatch provided by this invention, when applied to PBT and nylon materials, achieves highly efficient flame retardancy, reaching a V-0 level. Furthermore, the masterbatch exhibits excellent char-forming properties, significantly increasing the glow wire ignition temperature and CTI index of the material, while also possessing high mechanical properties. This invention eliminates the need for antimony trioxide, greatly reducing production costs. Detailed Implementation

[0045] To enable those skilled in the art to more clearly understand the technical solutions described in this invention, the following embodiments are provided for illustration. It should be noted that the following embodiments do not constitute a limitation on the scope of protection claimed by this invention.

[0046] Unless otherwise specified, the raw materials, reagents or devices used in the following examples are available from conventional commercial sources or can be obtained by existing known methods.

[0047] Example 1

[0048] A composite flame retardant masterbatch that can replace antimony trioxide.

[0049] The raw materials that replace antimony trioxide composite flame retardant masterbatch include, by weight parts:

[0050] Three parts of antimony powder with a purity of 99.8%;

[0051] 10 parts of 25nm zinc stannate;

[0052] 30 parts talcum powder;

[0053] One part of amino-modified silicone oil;

[0054] 56 parts of linear low-density polyethylene, with a melt index (190℃ / 2.16kg) of 50g / 10min.

[0055] Example 2

[0056] A composite flame retardant masterbatch that can replace antimony trioxide.

[0057] The raw materials that replace antimony trioxide composite flame retardant masterbatch include, by weight parts:

[0058] 8 parts of antimony powder with a purity of 99.8%;

[0059] 20 parts of 25nm zinc stannate;

[0060] 15 parts talcum powder;

[0061] 5 parts of amino-modified silicone oil;

[0062] 52 parts of linear low-density polyethylene, with a melt index (190℃ / 2.16kg) of 50g / 10min.

[0063] Example 3

[0064] A composite flame retardant masterbatch that can replace antimony trioxide.

[0065] The raw materials that replace antimony trioxide composite flame retardant masterbatch include, by weight parts:

[0066] Three parts of antimony powder with a purity of 99.8%;

[0067] 10 parts of 25nm nano zinc stannate;

[0068] 30 parts talcum powder;

[0069] 1 part epoxy-modified silicone oil;

[0070] 56 parts of linear low-density polyethylene, with a melt index (190℃ / 2.16kg) of 50g / 10min.

[0071] Example 4

[0072] A composite flame retardant masterbatch that can replace antimony trioxide.

[0073] The raw materials that replace antimony trioxide composite flame retardant masterbatch include, by weight parts:

[0074] Three parts of antimony powder with a purity of 99.8%;

[0075] 10 parts of 25nm nano zinc stannate;

[0076] 30 parts talcum powder;

[0077] One part of amino-modified silicone oil;

[0078] 56 parts of linear low-density polyethylene, with a melt index (190℃ / 2.16kg) of 80g / 10min.

[0079] Comparative Example 1

[0080] A composite flame retardant masterbatch.

[0081] The raw materials for composite flame retardant masterbatch, by weight, include:

[0082] Three parts of antimony powder with a purity of 99.8%;

[0083] 45 parts of 25nm zinc stannate;

[0084] 30 parts talcum powder;

[0085] One part of amino-modified silicone oil;

[0086] 56 parts of linear low-density polyethylene, with a melt index (190℃ / 2.16kg) of 50g / 10min.

[0087] Comparative Example 2

[0088] A composite flame retardant masterbatch.

[0089] The raw materials for composite flame retardant masterbatch, by weight, include:

[0090] Three parts of antimony powder with a purity of 99.8%;

[0091] 10 parts of 25nm zinc stannate;

[0092] 30 parts talcum powder;

[0093] 1 part unmodified ordinary silicone oil;

[0094] 56 parts of linear low-density polyethylene, with a melt index (190℃ / 2.16kg) of 50g / 10min.

[0095] Comparative Example 3

[0096] A composite flame retardant masterbatch.

[0097] The raw materials for composite flame retardant masterbatch, by weight, include:

[0098] Three parts of antimony powder with a purity of 99.8%;

[0099] 10 parts of 25nm zinc stannate;

[0100] 30 parts talcum powder;

[0101] One part of amino-modified silicone oil;

[0102] 56 parts of ordinary MI linear low-density polyethylene have a melt index (190℃ / 2.16kg) of 5g / 10min.

[0103] Comparative Example 4

[0104] A traditional composite flame retardant masterbatch.

[0105] The raw materials for traditional composite flame retardant masterbatches, by weight, include:

[0106] 3 parts antimony trioxide powder;

[0107] 10 parts of 25nm zinc stannate;

[0108] 30 parts talcum powder;

[0109] One part of amino-modified silicone oil;

[0110] 56 parts of linear low-density polyethylene, with a melt index (190℃ / 2.16kg) of 50g / 10min.

[0111] Application Example 1

[0112] A bromine-antimony PBT material, by mass percentage, is prepared from the following raw materials: 3.5% of the antimony trioxide composite flame retardant masterbatch (as described in Example 1), 50% PBT, 12.5% ​​brominated epoxy, 3% toughening agent, 30% glass fiber, and 1% other additives.

[0113] Application Examples 2-4

[0114] The difference from Application Example 1 is that in Application Examples 2 to 4, the alternative antimony trioxide composite flame retardant masterbatch provided in Example 1 is replaced with the alternative antimony trioxide composite flame retardant masterbatch provided in Examples 2 to 4, respectively.

[0115] Application Example 5

[0116] A nylon material, by mass percentage, is prepared from the following raw materials: 5% of the antimony trioxide composite flame retardant masterbatch (as described in Example 1), 47.5% of polyamide 66, 13.5% of decabromodiphenyl ethane, 3% of grafted POE, 30% of glass fiber, and 1% of other additives.

[0117] Application Examples 6-8

[0118] The difference from Application Example 5 is that in Application Examples 6 to 8, the alternative antimony trioxide composite flame retardant masterbatch provided in Example 1 is replaced with the alternative antimony trioxide composite flame retardant masterbatch provided in Examples 2 to 4, respectively.

[0119] Application Comparative Examples 1-4

[0120] The difference from Application Example 1 is that in Application Comparative Examples 1 to 4, the alternative antimony trioxide composite flame retardant masterbatch provided in Example 1 is replaced with the composite flame retardant masterbatch provided in Comparative Examples 1 to 4 respectively.

[0121] The performance of the bromo-antimony materials in Application Examples 1-4 and Comparative Examples 1-4 was tested, and the results are shown in Table 1.

[0122] Relevant performance testing methods:

[0123] (1) Flame retardant performance test: The flame retardant performance of the sample was tested according to the UL-94 standard.

[0124] (2) Glow wire (GWIT) test: The sample is subjected to a glow wire test according to IEC 60695-2-13 standard.

[0125] (3) Tensile strength test: The tensile strength of the specimen is tested according to ISO 527-2 standard.

[0126] (4) Cantilever beam notch impact strength test: Tested according to ISO180 standard.

[0127] (5) Solid insulation tracking index (CTI index) test: Tested according to GB / T4207-2022 standard.

[0128] Table 1 Results of each performance test

[0129]

[0130] As shown in Table 1, the PBT materials in Application Examples 1-4, using the alternative antimony trioxide composite flame-retardant masterbatch provided by this invention, achieve a flame retardancy rating of V-0, the same as that of Application Comparative Example 4 using traditional antimony trioxide. Furthermore, the alternative antimony trioxide composite flame-retardant masterbatch provided by this invention, due to its excellent char-forming properties, significantly improves the glow wire ignition temperature and CTI index in PBT or nylon materials, surpassing those of Application Comparative Example 4. In addition, this invention also exhibits higher mechanical properties, all superior to those using traditional antimony trioxide. This invention eliminates the need for antimony trioxide in its raw materials, resulting in lower overall costs. Based on current market prices for antimony trioxide, it can reduce the cost of PBT or nylon materials by 500-1500 yuan per ton. Moreover, the masterbatch is made from environmentally friendly and sustainable materials, complying with regulatory requirements.

[0131] The preferred embodiments of the present invention have been described in detail above. It should be understood that those skilled in the art can make numerous modifications and variations based on the concept of the present invention without creative effort. Therefore, any technical solutions obtained by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concept of the present invention and on the existing technology should be within the scope of protection defined by the claims.

Claims

1. A substitute for antimony trioxide composite flame retardant masterbatch, characterized in that, The raw materials of the antimony trioxide composite flame-retardant master batch include, by weight fraction: Antimony powder 3-8 parts; Nano stannate 10-20 parts; Silicate 15-30 parts; Organic silicone oil modified by special functional groups 1-5 parts; Linear low-density polyethylene 45-65 parts; The organic silicone oil modified by special functional groups is polydimethylsiloxane or polyether-modified siloxane with at least one functional group of amino, epoxy, hydroxyl, mercapto, carboxyl or alkoxy in side chains or end groups.

2. The substitute antimony trioxide composite flame retardant masterbatch as claimed in claim 1, wherein, The antimony powder is high-purity antimony powder; the high-purity antimony powder is selected from antimony powder with a purity of 99.8% or above.

3. The substitute for antimony trioxide composite flame retardant master batch according to claim 1, characterized in that, The nano stannate includes at least one of zinc stannate, sodium stannate, potassium stannate and hydrated zinc stannate.

4. The substitute antimony trioxide composite flame retardant masterbatch as claimed in claim 3, wherein, The particle size of the nano stannate is 20-100 nm.

5. The substitute for antimony trioxide composite flame retardant master batch as claimed in claim 1, wherein, The silicate includes at least one of talc powder, mica powder, wollastonite, kaolin and montmorillonite.

6. The substitute for antimony trioxide composite flame retardant master batch as claimed in claim 1, wherein, The linear low-density polyethylene has a melt index of 30-100 g / 10 min.

7. The substitute for antimony trioxide composite flame retardant master batch as claimed in claim 1, wherein, The raw materials of the antimony trioxide composite flame-retardant master batch further include an antioxidant and a lubricant.

Images