CN111849157A - Flame-retardant polyamide mixture for polyurethane foamed product - Google Patents
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- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J9/0038—Use of organic additives containing phosphorus
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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Abstract
The invention discloses a flame-retardant polyamide mixture for a polyurethane foaming product, wherein flame-retardant polyether is added into a flame retardant, so that the flame-retardant polyether reacts with isocyanate in isocyanate to form a polyurea component, the polyurea component is a non-combustible material with good corrosion resistance, water resistance and wear resistance, the flame-retardant property of the polyamide mixture can be enhanced, the product quality can be improved, the problem of flame-retardant attenuation can be effectively solved, equipment cannot be blocked, in order to avoid the influence of the isocyanate on the self-skinning process of the polyamide mixture, a skinning agent with a specific proportion is added into production raw materials, the skinning effect of the polyamide mixture is enhanced, the defect of poor product appearance is overcome, and the adaption of different production requirements is realized by controlling the content of the isocyanate in the cyanate.
Description
Technical Field
The invention relates to the technical field of polyamide flame retardance, and particularly relates to a flame-retardant polyamide mixture for a polyurethane foaming product.
Background
Polyamide is commonly called as nylon, and polyamide is a preferred material in the electronic and electrical industry and the automobile industry due to good mechanical property, chemical resistance, oil resistance and good electrical insulation, but because the flame retardant performance requirements of the materials in the fields are high at present, and the flame retardancy of polyamide and glass fiber reinforced polyamide products of polyamide is poor, the flame retardant is added into the polyamide, most of the existing flame retardants are phosphorus flame retardants, phosphorus is liquefied at high temperature during combustion to form an oil film to isolate air, but the traction phenomenon of the phosphorus flame retardants is serious, the flame retardant effect is gradually attenuated along with the use time, if carbon flame retardants are added, such as graphite, although no traction is generated, the flame retardant effect is good, equipment is easy to block during combustion, and the effect is poor when the precise parts of the equipment are abraded.
Disclosure of Invention
The invention aims to provide a flame-retardant polyamide mixture for polyurethane foam products, which aims to solve the problems that the phosphorus flame retardant proposed in the background art has serious traction phenomenon, the flame-retardant effect gradually attenuates along with the use time, and if a carbon flame retardant such as graphite is added, although the carbon flame retardant does not have traction, the flame-retardant effect is good, equipment is easy to block during combustion, the precision part of the equipment is abraded, and the effect is poor.
In order to achieve the purpose, the invention adopts the following technical scheme:
the flame-retardant polyamide mixture for the polyurethane foaming product comprises the following components in parts by weight: 30-75 parts of polyamide resin, 15-25 parts of phosphorus-containing flame retardant, 10-25 parts of glass fiber, 0-15 parts of titanium oxide, 0.5-6 parts of flame retardant aid, 10-20 parts of polyamide oligomer, 0-15 parts of skinning agent and 20-35 parts of isocyanate.
Preferably, the polyamide oligomer is a polyamide having a melting temperature of 224-264 ℃ and an intrinsic viscosity of 1.2 to 1.9dl/g as measured in concentrated sulfuric acid at room temperature.
Preferably, the phosphorus-containing flame retardant is a mixture of melamine-based phosphorus compound, graphite, flame-retardant polyether and white polyether, the melamine-based phosphorus compound, graphite, flame-retardant polyether and white polyether mixture are added in a ratio of 1:1.5:10:7, and the melamine-based phosphorus compound contained in the phosphorus-containing flame retardant is melamine polyphosphate.
Preferably, the sum of the parts by weight of the glass fibers and the titanium oxide in the polyamide mixture does not exceed 30% of the total part by weight of the polyamide mixture.
Preferably, the flame retardant aid is a mixture of zinc borate, ethanolamine, and calcium borate.
Preferably, the skinning agent is ethylene glycol.
Preferably, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, and the isocyanate content in the isocyanate is 23% -32%.
The invention also provides a preparation method of the flame-retardant polyamide mixture for the polyurethane foaming product, which comprises the following steps:
s1, carrying out polycondensation on 1, 6-hexamethylene diamine and 1, 6-adipic acid to form a polyamide polymer, adding a specific part of polyamide oligomer into the polyamide polymer, and forming a polyamide mixed raw material by adopting a mechanical mixing mode;
s2, adding half of the phosphorus-containing flame retardant and the flame retardant auxiliary agent in a specific part into the polyamide mixed raw material formed in the S1, mechanically mixing and stirring for 30min, adding glass fiber and titanium oxide, and continuously stirring to form a primary polyamide mixture;
s3, adding isocyanate and half of the phosphorus-containing flame retardant and the flame retardant aid in the primary polyamide mixture, and continuously stirring to form a secondary polyamide mixture;
and S4, adding a skinning agent into the secondary polyamide mixture, mechanically stirring for 15min, standing, cooling and forming.
According to the flame-retardant polyamide mixture for the polyurethane foaming product, provided by the invention, the flame-retardant polyether with a larger proportion is added into a flame retardant, so that the flame-retardant polyether reacts with isocyanate in isocyanate to form a polyurea component, the polyurea component is a non-combustible material with good corrosion resistance, water resistance and wear resistance, the product quality can be improved while the flame-retardant property of the polyamide mixture is enhanced, the problem of flame-retardant attenuation is effectively solved, equipment cannot be blocked, in order to avoid the influence of the isocyanate on the self-skinning process of the polyamide mixture, a skinning agent with a specific proportion is added into production raw materials, the skinning effect of the polyamide mixture is enhanced, the defect of poor appearance of the product is overcome, and the adaption of different production requirements is realized by controlling the content of the isocyanate in the cyanate.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The flame-retardant polyamide mixture for the polyurethane foaming product comprises the following components in parts by weight: 30 parts of polyamide resin, 15 parts of phosphorus-containing flame retardant, 10 parts of glass fiber, 5 parts of titanium oxide, 1 part of flame retardant aid, 10 parts of polyamide oligomer, 9 parts of skinning agent and 20 parts of isocyanate, wherein the polyamide oligomer is polyamide with the melting temperature of 224-264 ℃, the intrinsic viscosity of the polyamide oligomer is 1.2-1.9dl/g measured in concentrated sulfuric acid at room temperature, the phosphorus flame retardant is a mixture of phosphorus compounds based on melamine, graphite, flame retardant polyether and white polyether, the adding ratio of the phosphorus compounds based on melamine, the graphite, the flame retardant polyether and the white polyether mixture is 1:1.5:10:7, the phosphorus compounds based on melamine in the phosphorus-containing flame retardant is melamine polyphosphate, the sum of the parts by weight of the glass fiber and the titanium oxide in the polyamide mixture is not more than 30 parts of the total weight of the polyamide mixture, and the flame retardant aid is zinc borate, The coating agent is a mixture of ethanolamine and calcium borate, the skinning agent is ethylene glycol, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, and the isocyanate content in the isocyanate is 23%.
Example 2
The flame-retardant polyamide mixture for the polyurethane foaming product comprises the following components in parts by weight: 40 parts of polyamide resin, 10 parts of phosphorus-containing flame retardant, 15 parts of glass fiber, 1 part of flame retardant auxiliary agent, 5 parts of polyamide oligomer, 9 parts of skinning agent and 20 parts of isocyanate, wherein the polyamide oligomer is polyamide with the melting temperature of 224 ℃ and 264 ℃, the intrinsic viscosity of the polyamide oligomer is 1.2-1.9dl/g when measured in concentrated sulfuric acid at room temperature, the phosphorus-containing flame retardant agent is a mixture of phosphorus compounds based on melamine, graphite, flame retardant polyether and white polyether, the adding ratio of the phosphorus compounds based on melamine, the graphite, the flame retardant polyether and the white polyether mixture is 1:1.5:10:7, the phosphorus compounds based on melamine in the phosphorus-containing flame retardant agent is melamine polyphosphate, the sum of the parts by weight of the glass fiber and titanium oxide in the polyamide mixture does not exceed 30 parts of the total weight of the polyamide mixture, and the flame retardant auxiliary agent is a mixture of zinc borate, ethanolamine and calcium borate, the skinning agent is ethylene glycol, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, and the content of the isocyanate in the isocyanate is 23%.
Example 3
The flame-retardant polyamide mixture for the polyurethane foaming product comprises the following components in parts by weight: 40 parts of polyamide resin, 10 parts of phosphorus-containing flame retardant, 15 parts of glass fiber, 1 part of flame retardant auxiliary agent, 5 parts of polyamide oligomer, 9 parts of skinning agent and 20 parts of isocyanate, wherein the polyamide oligomer is polyamide with the melting temperature of 224 ℃ and 264 ℃, the intrinsic viscosity of the polyamide oligomer is 1.2-1.9dl/g when measured in concentrated sulfuric acid at room temperature, the phosphorus-containing flame retardant agent is a mixture of phosphorus compounds based on melamine, graphite, flame retardant polyether and white polyether, the adding ratio of the phosphorus compounds based on melamine, the graphite, the flame retardant polyether and the white polyether mixture is 1:1.5:10:7, the phosphorus compounds based on melamine in the phosphorus-containing flame retardant agent is melamine polyphosphate, the sum of the parts by weight of the glass fiber and titanium oxide in the polyamide mixture does not exceed 30 parts of the total weight of the polyamide mixture, and the flame retardant auxiliary agent is a mixture of zinc borate, ethanolamine and calcium borate, the skinning agent is ethylene glycol, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, and the isocyanate content in the isocyanate is 28%.
Example 4
The flame-retardant polyamide mixture for the polyurethane foaming product comprises the following components in parts by weight: 40 parts of polyamide resin, 10 parts of phosphorus-containing flame retardant, 10 parts of glass fiber, 1 part of flame retardant auxiliary agent, 5 parts of polyamide oligomer, 14 parts of skinning agent and 20 parts of isocyanate, wherein the polyamide oligomer is polyamide with the melting temperature of 224 ℃ and 264 ℃, the intrinsic viscosity of the polyamide oligomer is 1.2-1.9dl/g when measured in concentrated sulfuric acid at room temperature, the phosphorus-containing flame retardant agent is a mixture of phosphorus compounds based on melamine, graphite, flame retardant polyether and white polyether, the adding ratio of the phosphorus compounds based on melamine, the graphite, the flame retardant polyether and the white polyether mixture is 1:1.5:10:7, the phosphorus compounds based on melamine in the phosphorus-containing flame retardant agent is melamine polyphosphate, the sum of the parts by weight of the glass fiber and titanium oxide in the polyamide mixture does not exceed 30 parts of the total weight of the polyamide mixture, and the flame retardant auxiliary agent is a mixture of zinc borate, ethanolamine and calcium borate, the skinning agent is ethylene glycol, the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, the isocyanate content in the isocyanate is 32%, the isocyanate content is higher at the moment, the polyamide mixture is non-combustible, the problem that self-skinning is difficult to carry out due to the fact that the isocyanate content is increased is solved by increasing the adding amount of the skinning agent, and the produced polyamide mixture is suitable for being used as a non-appearance structure.
The invention also provides a preparation method of the flame-retardant polyamide mixture for the polyurethane foaming product, which comprises the following steps:
s1, carrying out polycondensation on 1, 6-hexamethylene diamine and 1, 6-adipic acid to form a polyamide polymer, adding a specific part of polyamide oligomer into the polyamide polymer, and forming a polyamide mixed raw material by adopting a mechanical mixing mode;
s2, adding half of the phosphorus-containing flame retardant and the flame retardant auxiliary agent in a specific part into the polyamide mixed raw material formed in the S1, mechanically mixing and stirring for 30min, adding glass fiber and titanium oxide, and continuously stirring to form a primary polyamide mixture;
s3, adding isocyanate and half of the phosphorus-containing flame retardant and the flame retardant aid in the primary polyamide mixture, continuously stirring to form a secondary polyamide mixture, and adding the flame retardant and the flame retardant aid in batches to improve the mixing efficiency of the flame retardant and the flame retardant aid with the primary polyamide mixture;
and S4, adding a skinning agent into the secondary polyamide mixture, mechanically stirring for 15min, standing, cooling and forming.
According to the flame-retardant polyamide mixture for the polyurethane foaming product, provided by the invention, the flame-retardant polyether with a larger proportion is added into the flame retardant, so that the flame-retardant polyether reacts with the isocyanate in the isocyanate to form a polyurea component, the polyurea component is a non-combustible material with good corrosion resistance, water resistance and wear resistance, the flame-retardant property of the polyamide mixture can be enhanced, the product quality can be improved, the influence of the isocyanate on the self-skinning process of the polyamide mixture is avoided, the skinning agent with a specific proportion is added into the production raw materials, the skinning effect of the polyamide mixture is enhanced, the defect of poor appearance of the product is improved, and the adaptation of different production requirements is realized by controlling the content of the isocyanate in the isocyanate.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A flame-retardant polyamide compound for polyurethane foam products, which is characterized in that: the flame-retardant polyamide mixture for the polyurethane foaming product comprises the following components in parts by weight: 30-75 parts of polyamide resin, 15-25 parts of phosphorus-containing flame retardant, 10-25 parts of glass fiber, 0-15 parts of titanium oxide, 0.5-6 parts of flame retardant aid, 10-20 parts of polyamide oligomer, 0-15 parts of skinning agent and 20-35 parts of isocyanate.
2. A flame-retardant polyamide compound for polyurethane foam products according to claim 1, characterized in that: the polyamide oligomer is a polyamide with a melting temperature of 224-264 ℃ and has an intrinsic viscosity of 1.2-1.9dl/g measured in concentrated sulfuric acid at room temperature.
3. A flame-retardant polyamide compound for polyurethane foam products according to claim 1, characterized in that: the phosphorus-containing flame retardant is a mixture of melamine-based phosphorus compound, graphite, flame-retardant polyether and white polyether, the addition ratio of the melamine-based phosphorus compound to the mixture of graphite, flame-retardant polyether and white polyether is 1:1.5:10:7, and the melamine-based phosphorus compound contained in the phosphorus-containing flame retardant is melamine polyphosphate.
4. A flame-retardant polyamide compound for polyurethane foam products according to claim 1, characterized in that: the sum of the weight parts of the glass fiber and the titanium oxide in the polyamide mixture is not more than 30 percent of the total weight part of the polyamide mixture.
5. A flame-retardant polyamide compound for polyurethane foam products according to claim 1, characterized in that: the flame-retardant auxiliary agent is a mixture of zinc borate, ethanolamine and calcium borate.
6. A flame-retardant polyamide compound for polyurethane foam products according to claim 1, characterized in that: the skinning agent is ethylene glycol.
7. A flame-retardant polyamide compound for polyurethane foam products according to claim 1, characterized in that: the isocyanate is one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate and lysine diisocyanate, and the content of the isocyanate in the isocyanate is 23-32%.
8. A method for producing a flame-retardant polyamide compound for a polyurethane foam product according to claim 1, characterized in that: the method comprises the following steps:
s1, carrying out polycondensation on 1, 6-hexamethylene diamine and 1, 6-adipic acid to form a polyamide polymer, adding a specific part of polyamide oligomer into the polyamide polymer, and forming a polyamide mixed raw material by adopting a mechanical mixing mode;
s2, adding half of the phosphorus-containing flame retardant and the flame retardant auxiliary agent in a specific part into the polyamide mixed raw material formed in the S1, mechanically mixing and stirring for 30min, adding glass fiber and titanium oxide, and continuously stirring to form a primary polyamide mixture;
s3, adding isocyanate and half of the phosphorus-containing flame retardant and the flame retardant aid in the primary polyamide mixture, and continuously stirring to form a secondary polyamide mixture;
and S4, adding a skinning agent into the secondary polyamide mixture, mechanically stirring for 15min, standing, cooling and forming.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101175821A (en) * | 2005-05-16 | 2008-05-07 | 三井化学株式会社 | Flame retardant polyamide composition |
| CN104231553A (en) * | 2014-09-24 | 2014-12-24 | 上海徽海化工科技有限公司 | Low-corrosivity flame-retardant thermoplastic resin composition |
| CN105377989A (en) * | 2013-08-05 | 2016-03-02 | 东洋纺株式会社 | Flame-retardant polyamide resin composition |
| CN106519663A (en) * | 2016-11-21 | 2017-03-22 | 上海金发科技发展有限公司 | Flame-retardant and high temperature-resistant polyimide compound and preparation method thereof |
| CN109251521A (en) * | 2017-07-14 | 2019-01-22 | 科莱恩塑料和涂料有限公司 | Fire-retardant black daiamid composition and application thereof |
-
2020
- 2020-07-30 CN CN202010752589.6A patent/CN111849157A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101175821A (en) * | 2005-05-16 | 2008-05-07 | 三井化学株式会社 | Flame retardant polyamide composition |
| CN105377989A (en) * | 2013-08-05 | 2016-03-02 | 东洋纺株式会社 | Flame-retardant polyamide resin composition |
| CN104231553A (en) * | 2014-09-24 | 2014-12-24 | 上海徽海化工科技有限公司 | Low-corrosivity flame-retardant thermoplastic resin composition |
| CN106519663A (en) * | 2016-11-21 | 2017-03-22 | 上海金发科技发展有限公司 | Flame-retardant and high temperature-resistant polyimide compound and preparation method thereof |
| CN109251521A (en) * | 2017-07-14 | 2019-01-22 | 科莱恩塑料和涂料有限公司 | Fire-retardant black daiamid composition and application thereof |
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Application publication date: 20201030 |
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