CN115772285A - Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate - Google Patents
Preparation method of modified piperazine pyrophosphate and modified piperazine pyrophosphate Download PDFInfo
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- CN115772285A CN115772285A CN202211596218.9A CN202211596218A CN115772285A CN 115772285 A CN115772285 A CN 115772285A CN 202211596218 A CN202211596218 A CN 202211596218A CN 115772285 A CN115772285 A CN 115772285A
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- piperazine pyrophosphate
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Abstract
The invention relates to the technical field of modified flame retardants, and particularly relates to a preparation method of modified piperazine pyrophosphate. The method comprises the steps of providing a first mixture of a surface treatment agent and water, uniformly mixing piperazine pyrophosphate and the first mixture, and filtering to obtain a first modified intermediate; and treating the first modified intermediate by a water-resistant agent to obtain modified piperazine pyrophosphate. By carrying out surface treatment on the piperazine pyrophosphate flame retardant, the surface performance of piperazine pyrophosphate is improved, the problem that piperazine pyrophosphate is easy to agglomerate is reduced, the performance stability of the flame retardant material is improved, and the problems of low yield, high cost and high defective rate of the flame retardant material are solved.
Description
Technical Field
The invention belongs to the technical field of modified flame retardants, and particularly relates to a preparation method of modified piperazine pyrophosphate and the modified piperazine pyrophosphate.
Background
Piperazine Pyrophosphate (PAPP) is an intumescent flame retardant with an acid source, a carbon source and a gas source integrated, has the characteristics of high char formation efficiency, good thermal stability, low smoke, no toxicity, light aging resistance, low hygroscopicity and the like, is increasingly strict along with environmental protection supervision, has outstanding advantages in environmental protection, cost, performance and the like, and can be used in the fields of polypropylene (PP), polyethylene (PE), polyurethane (PU), acrylonitrile-butadiene-styrene (ABS), epoxy resin (EP) and the like.
Compared with other intumescent flame retardants, the PAPP is easy to agglomerate, and the agglomeration is serious, so that the dispersion is uneven in the compounding process of downstream manufacturers. In the actual production process, a weightlessness scale metering system is generally adopted to meter and discharge resin particles and the compound intumescent flame retardant in proportion, and easy caking can cause unsmooth discharge of the compound flame retardant and even cause bridge frame to interrupt the discharge, so that the discharge of the flame retardant is unstable, the performance stability of the flame retardant material is influenced, and the problems of yield reduction, cost improvement, defective rate improvement and the like of the flame retardant material are caused.
The prior art schemes involving piperazine pyrophosphate modification include: CN114539618A discloses improvement of piperazine pyrophosphate by hydrogen-containing silicone oil and silicone oil dispersant; WO2022110392A1 discloses that piperazine pyrophosphate can be modified by piperazine phosphate after surface coating with epoxy resin, UV curable polyacrylate, melamine, silane, titanate, or aluminate; CN111592711A discloses that piperazine pyrophosphate is modified by using methyl silicone oil, a silane coupling agent and hydrogen-containing silicone oil; CN110746706B discloses that piperazine pyrophosphate polymer is modified by one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, hydrogen-containing silicone oil, methyl silicone oil and hydroxyl silicone oil.
However, the above-mentioned solutions do not solve the problem of agglomeration and uniform dispersion when PAPP is provided in a single form.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of modified piperazine pyrophosphate and the modified piperazine pyrophosphate.
In order to achieve the above object, the present invention provides a method for preparing modified piperazine pyrophosphate, comprising:
providing a first mixture of a surface treating agent and water, uniformly mixing piperazine pyrophosphate and the first mixture, and filtering to obtain a first modified intermediate; and treating the first modified intermediate by a water-resistant agent to obtain modified piperazine pyrophosphate.
Preferably, the surface treatment agent comprises an aqueous silane coupling agent or an aqueous phthalate coupling agent, and the phthalate coupling agent comprises isopropyl tri (dioctyl pyrophosphato) ethylene titanate.
Preferably, the aqueous silane coupling agent comprises one or more of an aminosilane aqueous coupling agent, a vinyl silane aqueous coupling agent and an epoxy silane aqueous coupling agent.
Preferably, the aqueous silane coupling agent comprises one or more of gamma-aminopropyltriethoxysilane, aminosilane hydrolysate, epoxysilane hydrolysate, gamma-aminopropyltrimethoxysilane, (gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane, gamma-aminopropylsilantriol and octyltriethoxysilane).
Preferably, the water and surface treatment agent are present in a ratio of 20:1-200:1, and mixing.
As a better alternative, the water and the surface treatment agent are mixed in a ratio of 100.
Preferably, the piperazine pyrophosphate and the first mixture are mixed in a ratio of 1.
Preferably, the mixing time of the piperazine pyrophosphate and the first mixture is 5-30min.
Preferably, the water-resistant agent comprises hydrosilane, chlorosilane, alkoxyalkyl silane, alkoxy polysiloxane, alkyl hydrosilicone oil, halogenated polysiloxane, halogenated alkyl polysiloxane or carboxyl alkyl polysiloxane.
As a better selection, the water resisting agent comprises one or more of methyl hydrogen silicone oil, alkyl silane and oxygen-containing silane.
Preferably, the water-resistant agent and the first modified intermediate are mixed in a ratio of 1:50-1:1000 in proportion.
The invention also provides the modified piperazine pyrophosphate prepared by the preparation method.
The invention has the following beneficial effects:
according to the invention, the surface treatment is carried out on the piperazine pyrophosphate flame retardant, so that the surface performance of piperazine pyrophosphate is improved, the problem that piperazine pyrophosphate is easy to agglomerate is reduced, the performance stability of the flame retardant material is improved, and the problems of low yield, high cost and high defective rate of the flame retardant material are solved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.
According to one embodiment of the present invention, the present invention provides a method for preparing modified piperazine pyrophosphate, comprising: providing a first mixture of a surface treating agent and water, uniformly mixing piperazine pyrophosphate and the first mixture, and filtering to obtain a first modified intermediate; and treating the first modified intermediate by a water-resistant agent to obtain modified piperazine pyrophosphate.
Example 1
The mass ratio of the surface treating agent to the deionized water to the piperazine pyrophosphate to the water resisting agent to the first modified intermediate is 1: 0.5;
adding a surface treating agent into deionized water, uniformly blending for 3min at the speed of 100rad/min at room temperature to obtain a first mixture, then adding piperazine pyrophosphate into the first mixture, and uniformly blending for 5min at the speed of 100rad/min at room temperature to obtain a first modified intermediate;
and uniformly blending the first modified intermediate and the water-resistant agent for 5min at the speed of 500rad/min to obtain the modified piperazine pyrophosphate.
The surface treating agent is gamma-aminopropyl triethoxysilane.
The water-resistant agent is methyl hydrogen-containing silicone oil.
Example 2
The mass ratio of the surface treating agent to the deionized water to the piperazine pyrophosphate to the water resisting agent to the first modified intermediate is 1: 0.5;
adding a surface treating agent into deionized water, uniformly blending for 5min at the speed of 400rad/min at room temperature to obtain a first mixture, then adding piperazine pyrophosphate into the first mixture, and uniformly blending for 5min at the speed of 100rad/min at room temperature to obtain a first modified intermediate;
and uniformly blending the first modified intermediate and a water-resistant agent at the speed of 1500rad/min for 8min to obtain the modified piperazine pyrophosphate.
The surface treating agent is gamma-aminopropyl triethoxysilane.
The water-resistant agent is methyl hydrogen-containing silicone oil.
Example 3
The mass ratio of the surface treating agent to the deionized water to the piperazine pyrophosphate to the water-resistant agent to the first modified intermediate is 2: 1;
adding a surface treating agent into deionized water, uniformly blending for 3min at the speed of 100rad/min at room temperature to obtain a first mixture, then adding piperazine pyrophosphate into the first mixture, and uniformly blending for 5min at the speed of 100rad/min at room temperature to obtain a first modified intermediate;
and uniformly blending the first modified intermediate and the water-resistant agent for 5min at the speed of 500rad/min to obtain the modified piperazine pyrophosphate.
The surface treating agent is gamma-aminopropyl triethoxysilane.
The water-resistant agent is methyl hydrogen-containing silicone oil.
Example 4
The mass ratio of the surface treating agent to the deionized water to the piperazine pyrophosphate to the water resisting agent to the first modified intermediate is (2): 1;
adding a surface treating agent into deionized water, uniformly blending for 5min at the speed of 100rad/min at room temperature to obtain a first mixture, then adding piperazine pyrophosphate into the first mixture, and uniformly blending for 5min at the speed of 400rad/min at room temperature to obtain a first modified intermediate;
and uniformly blending the first modified intermediate and the water-resistant agent at the speed of 1500rad/min for 8min to obtain the modified piperazine pyrophosphate.
The surface treating agent is gamma-aminopropyl triethoxysilane.
The water-resistant agent is methyl hydrogen-containing silicone oil.
In examples 1 to 4, the room temperature is usually 25 ℃ and may be adjusted as the case may be, but it is preferably in the range of 10 to 30 ℃.
Comparative example 1
The comparative examples were compared to examples 1-4 for performance index using piperazine pyrophosphate without surface treatment, and the results are shown in Table 1:
TABLE 1 examination results of examples 1 to 4
| Index (es) | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example |
| Solubility (%) | 1.10 | 1.15 | 1.0 | 0.9 | 1.26 |
| 1% temperature of thermal weight loss (. Degree.C.) | 278.6 | 275 | 277 | 270.3 | 273.3 |
| Particle diameter D50 | 10.8 | 8.5 | 7.4 | 9.3 | 8-9 |
| Particle diameter D90 | 25.1 | 20.4 | 19.2 | 21.5 | 17 |
As can be seen from the table, the 1% thermogravimetric temperature change before and after the surface treatment of piperazine pyrophosphate of the present invention was not large, that is, the heat resistance was not greatly affected. Moreover, the solubility is reduced after the surface treatment, the average particle size is slightly increased, and the agglomeration condition is obviously improved.
According to the invention, the surface treatment is carried out on the piperazine pyrophosphate flame retardant, so that the surface performance of piperazine pyrophosphate is improved, the problem that piperazine pyrophosphate is easy to agglomerate is reduced, the performance stability of the flame retardant material is improved, and the problems of low yield, high cost and high defective rate of the flame retardant material are solved.
It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific to implementations of the present disclosure and that various changes in form and detail may be made therein without departing from the spirit and scope of the present disclosure in practice.
Claims (11)
1. A method for preparing modified piperazine pyrophosphate is characterized by comprising the following steps:
providing a first mixture of a surface treating agent and water, uniformly mixing piperazine pyrophosphate and the first mixture, and filtering to obtain a first modified intermediate; and treating the first modified intermediate by a water-resistant agent to obtain modified piperazine pyrophosphate.
2. The method of claim 1, wherein the surface treatment agent comprises an aqueous silane coupling agent or an aqueous phthalate ester coupling agent, and the phthalate ester coupling agent comprises isopropyl tris (dioctylpyrophosphate) ethylene titanate.
3. The method according to claim 2, wherein the aqueous silane coupling agent comprises one or more of an aqueous aminosilane coupling agent, an aqueous vinylsilane coupling agent, and an aqueous epoxysilane coupling agent.
4. The method according to claim 3, wherein the aqueous silane coupling agent comprises one or more of gamma-aminopropyltriethoxysilane, aminosilane hydrolysate, epoxysilane hydrolysate, gamma-aminopropyltrimethoxysilane, (gamma- (2, 3-glycidoxy) propyltrimethoxysilane, gamma-aminopropylsilanetriol, octyltriethoxysilane).
5. The method of claim 1, wherein the water and surface treatment agent are mixed in a ratio of 20:1-200:1, and mixing.
6. The method of claim 1, wherein the piperazine pyrophosphate and the first mixture are mixed in a ratio of 1.
7. The method of claim 1, wherein the piperazine pyrophosphate and the first mixture are mixed for a time period of 5 to 30min.
8. The method of claim 1, wherein the water-resistant agent comprises a hydrosilane, a chlorosilane, an alkoxyalkyl silane, an alkoxy polysiloxane, an alkyl hydrosilicone oil, a halogenated polysiloxane, a halogenated hydrocarbyl polysiloxane, or a carboxyhydrocarbyl polysiloxane.
9. The method of claim 8, wherein the water-resistant agent comprises one or more of methyl hydrogen silicone oil, alkyl silane, and oxygen-containing silane.
10. The method of claim 1, wherein the water-resistant agent and first modified intermediate are present in a ratio of 1:50-1:1000 in proportion.
11. The modified piperazine pyrophosphate prepared by the preparation method of any one of claims 1 to 10.
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| CN114539618A (en) * | 2022-02-15 | 2022-05-27 | 东莞市宏泰基阻燃材料有限公司 | Silicon rubber halogen-free flame retardant and preparation method and application thereof |
| WO2022110392A1 (en) * | 2020-11-26 | 2022-06-02 | 浙江旭森非卤消烟阻燃剂有限公司 | Halogen-free flame retardant having good flame retardancy and processibility, and flame-retardant resin composition |
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2022
- 2022-12-12 CN CN202211596218.9A patent/CN115772285A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2239507A1 (en) * | 1995-12-27 | 1997-07-10 | Sumitomo Bakelite Company Limited | Process for producing flame-retardant, silane-crosslinked polyolefin |
| CN1922260A (en) * | 2004-02-24 | 2007-02-28 | 株式会社艾迪科 | Flame retardant composition with enhanced fluidity, flame retardant resin composition and molding thereof |
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