WO2018014443A1 - Matériau ignifuge au silicium contenant du phosphore exempt d'halogène, matériau de polycarbonate transparent ignifuge, préparation et utilisation de celui-ci - Google Patents

Matériau ignifuge au silicium contenant du phosphore exempt d'halogène, matériau de polycarbonate transparent ignifuge, préparation et utilisation de celui-ci Download PDF

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WO2018014443A1
WO2018014443A1 PCT/CN2016/099238 CN2016099238W WO2018014443A1 WO 2018014443 A1 WO2018014443 A1 WO 2018014443A1 CN 2016099238 W CN2016099238 W CN 2016099238W WO 2018014443 A1 WO2018014443 A1 WO 2018014443A1
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flame retardant
retardant composition
silica sol
silica
dopo derivative
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PCT/CN2016/099238
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Chinese (zh)
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秦舒浩
龙丽娟
何文涛
于杰
李娟�
向宇姝
何敏
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江林（贵州）高科发展股份有限公司
贵州省材料产业技术研究院
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Publication of WO2018014443A1 publication Critical patent/WO2018014443A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • the invention relates to the field of flame retardants, in particular to a phosphorus-silicon-containing flame retardant and a transparent flame-retardant polycarbonate (PC) material containing the flame retardant, and to a flame retardant and a transparent resistor. Preparation methods and applications of burning PC materials.
  • PC polycarbonate
  • PC polycarbonate
  • PC polycarbonate
  • flame retardancy is an important property.
  • the flame retardancy of the unmodified PC resin can only reach UL94V-2 level, which limits its use in these fields to some extent.
  • halogen flame retardant PC materials often require the addition of cerium oxide as a synergist, and this synergist can easily cause degradation of the main chain in the PC resin, resulting in degradation of PC material properties and gas embossing on the surface of PC materials.
  • the defect, and the halogen flame-retardant PC material completely loses the light transmittance of the PC resin, and the resulting PC material has low light transmittance.
  • Phosphorus-nitrogen flame retardants also make PCs opaque due to their large amount, and have a great influence on the mechanical properties of materials. Boron compounds will form a three-dimensional network structure during processing, which will also affect the transparency of PC and be flame retardant. It is not efficient and usually only works with polysiloxane to achieve better results.
  • Organic phosphate ester flame retardants are widely used in the flame retardant modification of PC materials because of their low price, good flame retardant effect and halogen-free environmental protection.
  • organic phosphate flame retardants are mostly liquid or have a very high melting point. Low solids, the amount of addition should reach 15%-25% to obtain the desired flame retardant effect.
  • a large number of organophosphate flame retardants have obvious plasticizing effect on PC materials, thus greatly reducing the PC material. Heat resistance level; at the same time, PC materials prepared with organic phosphate flame retardants are not toughened with additional In the case of the agent, its toughness is not satisfactory, which seriously affects the mechanical properties and transparency of the PC material.
  • phosphonate halogen-free flame retardants have been used.
  • dialkyl phosphinates are used as flame retardants for nylons and polyesters.
  • the dialkyl phosphinate makes the PC completely opaque.
  • the phosphonate flame retardant mainly contains a derivative of a phosphorus-carbon bond bridge 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), which contains 2 molecules in one molecule. Phosphorus center (DiDOPO) with good thermal stability and flame retardancy.
  • DOPO 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide
  • Patent CN201410333261.5 discloses the application of a class of bridge chain DOPO derivatives in PC, but the PC is rendered translucent due to the large amount of addition.
  • the technical problem solved by the invention is to overcome the defects in the prior art, and to provide a transparent flame-retardant PC material which is convenient to add, flame-retardant, efficient, safe, advantageous for dispersing and maintaining good mechanical properties and a preparation method thereof.
  • a phosphorus-carbon bridged DOPO derivative is recrystallized on the surface of a nanosilica powder or a silica sol by a solution blending or supercritical carbon dioxide method to prepare a flame retardant composition.
  • the present invention provides the following technical solutions:
  • a halogen-free flame retardant composition comprising a double phosphorus-carbon bond bridge chain DOPO derivative and a nano silica or silica sol, wherein the double phosphorus-carbon bond bridge chain DOPO derivative is dispersed in nano silica or Silica sol surface.
  • the mass ratio of the double phosphorus-carbon bond bridge chain DOPO derivative to the nano silica or silica sol is (3-5):1.
  • DOPO derivative represented by the following structural formula (I):
  • R1 is a C6-C18 aryl group, preferably selected from the group consisting of phenethyl, naphthylethyl, p-phenylethyl, phenylpropyl.
  • C6-C18 means that the number of carbon atoms is 6-18.
  • the nano silica or silica sol has an average particle diameter of 10 nm to 100 nm.
  • the present invention also provides a halogen-free flame-retardant transparent polycarbonate material characterized by comprising the following components:
  • the flame retardant composition is obtained by the following preparation method:
  • Dissolving the DOPO derivative in an organic solvent to form a solution adding nano silica or silica sol, mixing the solution with nano silica or silica sol, heating to evaporate the solvent, thereby recrystallizing the DOPO derivative Dispersion on the surface of the nanosilica or silica sol thereby obtaining a flame retardant composition.
  • the flame retardant composition or the polycarbonate material wherein the flame retardant composition is obtained by the following preparation method:
  • the DOPO derivative is recrystallized and dispersed on the surface of the nano silica or silica sol to thereby obtain a flame retardant composition.
  • the polycarbonate material is obtained by the following production method, and the PC resin and the flame retardant composition are mixed and then subjected to melt blend extrusion molding.
  • the preparation method comprises the following steps:
  • step (b) the raw material obtained in step (a) is added to a twin-screw extruder for melt blending extrusion, the temperature of each zone of the twin-screw extruder is from 250 ° C to 280 ° C;
  • step (c) melt-blending the extruded material is subjected to drawing and pelletizing to obtain a halogen-free flame-retardant transparent polycarbonate material.
  • the preparation method further comprises the step (i) before the step (a): drying the PC resin at 120 ° C to 140 ° C.
  • the twin-screw extruder has five different temperature control zones.
  • the present invention also provides a method for preparing a flame retardant composition, which is obtained by the following preparation method: dissolving a phosphorus-carbon bridged DOPO derivative in an organic solvent to form a solution, adding nano silica or a silica sol, the solution is mixed with nano silica or silica sol, heated to 50-120 ° C to evaporate the solvent, whereby the DOPO derivative is recrystallized and dispersed on the surface of the nano silica or silica sol to thereby obtain flame retardant Composition.
  • the present invention also provides a method for preparing a flame retardant composition, which is obtained by the following preparation method: dissolving a phosphorus-carbon bridged DOPO derivative in an organic solvent to form a solution, adding nano silica or a silica sol, which is blended with nano silica or silica sol in the presence of supercritical carbon dioxide to evaporate the solvent, whereby the DOPO derivative is recrystallized and dispersed on the surface of the nano silica or silica sol A flame retardant composition is obtained.
  • the method for preparing a flame retardant composition wherein the supercritical carbon dioxide pressure is 10-30 MPa, preferably 20 MPa, and the temperature is 20 when the solution is blended with nano silica or silica sol. -60 ° C.
  • the method for preparing the flame retardant composition wherein the organic solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, acetone, ethylene glycol, propylene glycol, dimethyl ether, diethyl ether, and ethylene
  • the organic solvent is selected from the group consisting of methanol, ethanol, propanol, isopropanol, acetone, ethylene glycol, propylene glycol, dimethyl ether, diethyl ether, and ethylene
  • alcohol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol monoethyl ether is selected from the group consisting of methanol, ethanol, propanol, isopropanol, acetone, ethylene glycol, propylene glycol, dimethyl ether, diethyl ether, and ethylene
  • alcohol monomethyl ether propylene glycol monomethyl ether
  • the present invention also provides a method for preparing a halogen-free flame-retardant transparent polycarbonate material, which comprises the following steps:
  • step (b) the raw material obtained in step (a) is added to a twin-screw extruder for melt blending extrusion, the temperature of each zone of the twin-screw extruder is from 250 ° C to 280 ° C;
  • step (c) melt-blending the extruded material is subjected to drawing and pelletizing to obtain a halogen-free flame-retardant transparent polycarbonate material.
  • the invention also provides the use of the flame retardant composition or the polycarbonate material described in an electrical device housing or automotive plastic component.
  • the invention utilizes supercritical carbon dioxide to separate the nano silica or silica sol particles to reduce agglomeration; or to recrystallize the bridged DOPO derivative on the surface of the nanoparticle by volatilizing the solvent by heating the solvent, and using the large ratio of the nano silica particles
  • the surface area increases the flame retardant efficiency of the bridged DOPO derivative.
  • nano-silica also acts as a synergistic flame retardant.
  • Figure 1 is a 1 H NMR spectrum of the DOPO derivative of the formula (I) when R is a phenethyl group synthesized in the examples;
  • Figure 2 is a 31 P NMR spectrum of the DOPO derivative of the formula (I) when R is a phenethyl group synthesized in the examples;
  • Figure 3 is an infrared spectrum diagram of the DOPO derivative of the formula (I) when R is a phenethyl group synthesized in the examples;
  • Figure 4 is a mass spectrum of the DOPO derivative of the formula (I) when R is a phenethyl group synthesized in the examples;
  • Figure 5 is a 31 P NMR spectrum of the DOPO derivative of the formula (I) when R is a naphthylethyl group synthesized in the examples;
  • Figure 6 is a mass spectrum of the DOPO derivative of the formula (I) when R is a naphthylethyl group synthesized in the examples;
  • Figure 7 is an infrared spectrum of the DOPO derivative of the formula (I) when R synthesized in the examples is a naphthylethyl group.
  • the halogen-free transparent flame-retardant PC material of the present invention comprises a PC resin and a flame retardant composition, and the PC resin accounts for 85% to 95% by mass percentage.
  • the fuel composition is 5% to 15%.
  • the flame retardant composition is a composite composition of a phosphorus-carbon bridged DOPO derivative and a nano silica or a silica sol, and has a mass ratio of 3 to 5:1.
  • the flame retardant composition of the present invention is prepared by dissolving a phosphorus-carbon bridged DOPO derivative in an organic solvent and then blending conditions in supercritical carbon dioxide or solution.
  • the lower recrystallized on the surface of the nano silica or silica sol forms a nanocomposite flame retardant composition.
  • the nano silica used is a nanosilica solid powder, which is commercially available.
  • the specific preparation method of the polycarbonate material is as follows:
  • a silica sol surface thereby obtaining a flame retardant composition, wherein the ratio of the bridged DOPO derivative to the nano silica is 3 to 5:1, the supercritical carbon dioxide blending pressure is 20 MPa, and the time is 2 to 6 hours;
  • the raw material extruded through the step (4) is subjected to drawing, cooling, and pelletizing processes to obtain a transparent flame-retardant PC material.
  • the temperature is from 250-280 ° C from the feeding section to the head, and the screw speed is 300-400 rpm.
  • Twin-screw extruder sold by Coperion Koya (Nanjing) Machinery Manufacturing Co., Ltd., model CTE35; operating parameter control: temperature from the feeding section to the head is 250-280 ° C, screw speed is 300-400 rpm.
  • Injection molding machine sold by Zhende Plastic Machinery Factory, model CJ80MZ2NCII
  • Cantilever beam notched impact strength test instrument Shenzhen SANS Vertical and Horizontal Technology Co., Ltd. PTM1000
  • Flame-retardant performance test method UL-94 vertical burning test is adopted. When testing, the end of the sample is clamped vertically, and the Bunsen burner (flame height 20 ⁇ 1mm) is applied to the free end of the sample for 10s, and the flame is removed. After recording the sample with flame burning time, if the sample has a flame burning time of less than 30s, continue to apply the second flame for 10s, remove the flame and record the first flaming burning time t1 of the sample, the second flaming combustion Time t2.
  • PC resin Mitsubishi s-2001r;
  • PCPO chain-containing DOPO derivative a compound represented by the formula (I), wherein the specific R1 is H or an aryl group or the like, and specifically, R1 used in all the following examples is a phenethyl group or a naphthylethyl group.
  • the DOPO derivative represented by (I) is prepared by the following preparation method:
  • DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide)
  • acetophenone was added to xylene in a molar ratio of 2:1, heated to 150 ° C to dissolve, and then slowly A 1/3 molar ratio of acetophenone to phosphorus oxychloride was added, and the mixture was reacted for 20 hours, cooled, and isopropanol was added thereto, followed by stirring under reflux. After standing for a while, the product was largely precipitated, suction filtered, and washed to give a white powder product.
  • FIG. 1 is the 1 H NMR hydrogen spectrum of the DOPO derivative in which R is phenethyl
  • Figure 3 is an infrared spectrum of the DOPO derivative in which R is phenethyl. From this figure, it can be seen that 3000 to 2800 cm -1 is the bridge group in the molecular structure of the product. The CH 2 characteristic absorption peak indicates that the bridging group has been successfully introduced into the molecular structure of the product; FIG.
  • FIG. 4 is a mass spectrum of the DOPO derivative in which R is a phenethyl group, from which it can be seen that m/z 534 is molecular mass peak phenethyl DOPO derivatives, synthetic molecules can be clearly successful structure;
  • FIG. 6 is a mass spectrum of the DOPO derivative in which R is naphthylethyl, from which it can be seen that m/z 584 is a naphthylethyl DOPO derivative.
  • NMR nuclear magnetic resonance spectrum Bruker Avance 400 NMR tester, deuterated chloroform as a solvent.
  • NMR nuclear magnetic phosphorus spectrum Bruker Avance 400 NMR tester, deuterated chloroform as solvent, 85% phosphoric acid as a positioning standard.
  • Nano-silica nanometer particle size range of 10-100nm, Shenzhen Crystal Chemicals for sale;
  • Silica Sol sold by DuPont, USA, with a particle size of 15-30 nm.
  • the raw material after the step (3) is fed into a twin-screw extruder for melt blending extrusion; wherein the twin-screw extruder has a 5-stage temperature control zone, wherein the temperature of each zone is 250 ° C, 260 °C, 265 ° C, 270 ° C, 275 ° C, the head temperature was 275 ° C, and the screw speed was 300 rpm.
  • the raw material extruded through the step (4) is subjected to drawing, cooling, and pelletizing to obtain a transparent flame-retardant PC material.
  • the obtained transparent PC material was injection molded under an injection molding machine (injection temperature was 265 ° C) into mechanical splines having thicknesses of 1.5 mm and 3.0 mm, and performance tests were performed.
  • Example 1 The unextended commercial PC material in the step (1) of Example 1 was subjected to the same extrusion and post-treatment methods as the sample obtained in Comparative Example 1 in the steps (4) and (5) of Example 1. The performance test was performed in comparison with the sample performance test results of Example 1 in Table 1 below.
  • the raw material after the step (3) is fed into a twin-screw extruder for melt blending extrusion; wherein the twin-screw extruder has a 5-stage temperature control zone, wherein the temperature of each zone is 255 ° C, 265 °C, 270 ° C, 275 ° C, 280 ° C, the head temperature was 275 ° C, and the screw speed was 300 rpm.
  • the raw material extruded through the step (4) is subjected to drawing, cooling, and pelletizing to obtain a transparent flame-retardant PC material.
  • the obtained transparent PC material was injection-molded under an injection molding machine (injection temperature of 250 ° C) into mechanical splines having thicknesses of 1.5 mm and 3.0 mm, and performance tests were performed.
  • Example 1 The unextended commercial PC material in the step (1) of Example 1 was subjected to the same extrusion and post-treatment methods as the sample obtained in Comparative Example 1 in the steps (4) and (5) of Example 1. The performance test was performed in comparison with the sample performance test results of Example 2 in Table 2 below.
  • the raw material after the step (3) is fed into a twin-screw extruder for melt blending extrusion; wherein the twin-screw extruder has a 5-stage temperature control zone, wherein the temperature of each zone is 255 ° C, 265 °C, 270 ° C, 275 ° C, 280 ° C, the head temperature was 275 ° C, and the screw speed was 300 rpm.
  • the raw material extruded through the step (4) is subjected to drawing, cooling, and pelletizing to obtain a transparent flame-retardant PC material.
  • the obtained transparent PC material was injection molded under an injection molding machine (injection temperature of 245 ° C) into mechanical splines having thicknesses of 1.5 mm and 3.0 mm, and performance tests were performed.
  • Example 1 The unextended commercial PC material in the step (1) of Example 1 was subjected to the same extrusion and post-treatment methods as the sample obtained in Comparative Example 1 in the steps (4) and (5) of Example 1. The performance test was performed in comparison with the sample performance test results of Example 3 in Table 3 below.
  • the raw material after the step (3) is fed into a twin-screw extruder for melt blending extrusion; wherein the twin-screw extruder has a 5-stage temperature control zone, wherein the temperature of each zone is 255 ° C, 265 °C, 270 ° C, 275 ° C, 280 ° C, the head temperature was 275 ° C, and the screw speed was 300 rpm.
  • the raw material extruded through the step (4) is subjected to drawing, cooling, and pelletizing to obtain a transparent flame-retardant PC material.
  • the obtained transparent PC material was injection molded under an injection molding machine (injection temperature was 265 ° C) into mechanical splines having thicknesses of 1.5 mm and 3.0 mm, and performance tests were performed.
  • Example 1 The unextended commercial PC material in the step (1) of Example 1 was subjected to the same extrusion and post-treatment methods as the sample obtained in Comparative Example 1 in the steps (4) and (5) of Example 1. The performance test was performed in comparison with the sample performance test results of Example 3 in Table 4 below.
  • Example 5 The same reagents and method steps as in Example 1 were employed except that the mass ratio of DOPO to nanosilica was changed to 2:1 and 6:1 in step (2), respectively, in the same manner as in Example 1.
  • the PC material was modified, and the obtained sample was tested in the same manner as in Example 1.
  • the test results are shown in Table 5 below:
  • the ratio of the ratio of the DOPO derivative to the silica in the flame retardant composition of the present invention is in the range of (3-5):1, and its performance is optimal.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Une composition ignifuge exempte d'halogène est préparée à partir d'un dérivé ponté de DOPO par l'intermédiaire de deux liaisons phosphore-carbone et de silice nanométrique ou d'un sol de silice au moyen d'un mélange en solution ou d'un mélange de dioxyde de carbone supercritique.
PCT/CN2016/099238 2016-07-18 2016-09-18 Matériau ignifuge au silicium contenant du phosphore exempt d'halogène, matériau de polycarbonate transparent ignifuge, préparation et utilisation de celui-ci WO2018014443A1 (fr)

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CN201610564840.XA CN106009038B (zh) 2016-07-18 2016-07-18 无卤含磷硅阻燃剂、阻燃透明聚碳酸酯材料及制备和应用
CN201610564840.X 2016-07-18

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