CN112694737B - Weather-proof flame-retardant PC composite material for antenna housing and preparation method thereof - Google Patents
Weather-proof flame-retardant PC composite material for antenna housing and preparation method thereof Download PDFInfo
- Publication number
- CN112694737B CN112694737B CN202011566636.4A CN202011566636A CN112694737B CN 112694737 B CN112694737 B CN 112694737B CN 202011566636 A CN202011566636 A CN 202011566636A CN 112694737 B CN112694737 B CN 112694737B
- Authority
- CN
- China
- Prior art keywords
- retardant
- flame
- composite material
- weather
- core
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The application relates to the field of polymer composite materials, in particular to a weather-resistant flame-retardant PC composite material for an antenna housing and a preparation method thereof. The weather-resistant flame-retardant PC composite material for the antenna housing comprises the following raw materials in parts by weight: 50-70 parts of siloxane-containing PC powder, 15-40 parts of siloxane powder, 0.3-1 part of pentaerythritol stearate, 0.8-2 parts of flame retardant, 0.6-2 parts of antioxidant, 5-8 parts of acrylic acid impact modifier with a core/shell structure and 0.5-1 part of polytetrafluoroethylene powder; the melt mass flow rate of the siloxane-containing PC powder at 300 ℃ and 1.2kg is 3.8-4.2g/10min. The weather-proof flame-retardant PC composite material for the antenna housing prepared by the application has good mechanical property, thermal property and flame retardant property, the using amount of the flame retardant is greatly reduced, the flame retardance is realized at the thickness of 0.9mm to reach V0, the corrosion to the antenna housing is reduced, the weather resistance is good, and the weather-proof and flame retardant requirements of the antenna housing of the 5G wireless base station are met.
Description
Technical Field
The application relates to the field of polymer composite materials, in particular to a weather-resistant flame-retardant PC composite material for an antenna housing and a preparation method thereof.
Background
The 5G wireless base station antenna housing is used in an outdoor environment for a long time, the material for manufacturing the antenna housing is required to have excellent weather resistance, and meanwhile, the material for the antenna housing is required to have a flame retardant function. Polycarbonate (PC) is a thermoplastic engineering plastic with excellent comprehensive performance, and has the advantages of high impact strength, high light transmittance, good dimensional stability, easy coloring, good aging resistance, excellent electrical insulation property and the like. The PC has certain flame retardance, but the requirement of the antenna housing of the 5G wireless base station on the flame retardance of the PC is still difficult to meet.
The flame retardants commonly used for PC at present include halogen-containing flame retardants, organophosphorus flame retardants, organosilicon flame retardants and sulfonate flame retardants. Wherein, the halogen-containing flame retardant causes great pollution to the environment; the phosphorus flame retardant has large addition amount and low decomposition temperature, most of the phosphorus flame retardants are easy to corrode the antenna housing, and some of the phosphorus flame retardants can influence the impact strength of PC; the cost of the organic silicon compound is high; the sulfonate flame retardant has good flame retardant effect, but has poor hydrolytic stability, and the flame retardance reaches V0 under the UL94 standard only by needing the thickness to be more than 3.2mm, so that the requirements of the antenna housing and other products on higher flame retardant performance cannot be met.
In view of the above-mentioned related technologies, the applicant believes that there is a great need for developing a weather-resistant flame-retardant PC composite material with a flame retardancy of V0 at a thickness of not more than 0.9 mm.
Disclosure of Invention
In order to improve the weather resistance and the flame retardance of the PC composite material, the application provides the weather-resistant flame-retardant PC composite material for the antenna housing and the preparation method thereof.
In a first aspect, the application provides a weather-resistant and flame-retardant PC composite material for an antenna housing, which is realized by adopting the following technical scheme:
the weather-resistant flame-retardant PC composite material for the antenna housing comprises the following preparation raw materials in parts by weight: 50-70 parts of siloxane-containing PC powder, 15-40 parts of siloxane powder, 0.3-1 part of pentaerythritol stearate, 0.8-2 parts of flame retardant, 0.6-2 parts of antioxidant, 5-8 parts of acrylic acid impact modifier with a core/shell structure and 0.5-1 part of polytetrafluoroethylene powder anti-dripping agent; the melt mass flow rate of the siloxane-containing PC powder at 300 ℃ and 1.2kg is 3.8-4.2g/10min.
By adopting the technical scheme, the mechanical property, the thermal property and the flame retardant property of the weather-resistant flame-retardant PC composite material for the antenna housing are improved by the siloxane-containing PC powder with the melt mass flow rate of 3.8-4.2g/10min at 300 ℃ and 1.2kg, and the siloxane-containing PC powder and the flame retardant property interact with a flame retardant, siloxane powder, a polytetrafluoroethylene powder anti-dripping agent and the like, so that the polytetrafluoroethylene powder anti-dripping agent can prevent melting and dripping, the using amount of the flame retardant is greatly reduced, the flame retardant property is improved, and the flame retardant degree can reach V0 at the thickness of 0.9 mm. In addition, the acrylic acid impact modifier with the core/shell structure is a high-molecular polymer generated by acrylate or methacrylate through free radical polymerization reaction, and the high-molecular polymer and pentaerythritol stearate and polytetrafluoroethylene powder anti-dripping agent act together, so that the heat stability and weather resistance of the weather-resistant flame-retardant PC composite material for the antenna housing are further improved, the compatibility among the siloxane-containing PC powder, the siloxane powder and the polytetrafluoroethylene powder anti-dripping agent is improved, and the expansion phenomenon is effectively prevented.
Preferably, the hydroxyl value of the pentaerythritol stearate is 20-35mgKOH/g; more preferably, the pentaerythritol stearate has a hydroxyl value of 25mgKOH/g.
By adopting the technical scheme, the pentaerythritol stearate with the hydroxyl value of 20-35mgKOH/g is adopted, the dispersion effect of siloxane powder in the siloxane-containing PC powder can be improved, the internal and external lubrication effects of the pentaerythritol stearate are beneficial to maintaining the core-shell structure of the acrylic acid impact modifier with the core/shell structure, and meanwhile, the compatibility of the polytetrafluoroethylene powder anti-dripping agent with the siloxane powder and the siloxane-containing PC powder is improved, and the expansion phenomenon is prevented.
Preferably, the flame retardant is prepared from an organic silicon flame retardant and an organic phosphorus flame retardant according to the mass ratio of (0.6-1): 1, mixing; more preferably, the flame retardant is prepared from an organic silicon flame retardant and an organic phosphorus flame retardant according to a mass ratio of 0.6:1 are mixed.
By adopting the technical scheme, the organic silicon flame retardant and the organic phosphine are compounded in a flame-retardant manner, the mass ratio of the organic silicon flame retardant and the organic phosphine is regulated, the using amount of the flame retardant can be greatly reduced, the cost is reduced, and meanwhile, under the combined action of the polytetrafluoroethylene powder anti-dripping agent, the acrylic acid impact modifier with the core/shell structure, the pentaerythritol stearate and the antioxidant, the corrosion to the radome is reduced, and the impact strength of the PC composite material cannot be influenced.
Preferably, the organic silicon flame retardant is ShinEtsu KR-480 and/or X-40-9805; more preferably, the silicone flame retardant is ShinEtsu KR-480.
By adopting the technical scheme, the ShinEtsu KR-480 organic silicon flame retardant has good compatibility with siloxane-containing PC powder and siloxane powder and good high temperature resistance, improves the chemical resistance of a PC composite material, and can realize that the flame retardance reaches V0 when the thickness is not higher than 0.8mm under the combined action of the ShinEtsu KR-480 organic silicon flame retardant and the organic phosphorus flame retardant.
Preferably, the organic phosphorus flame retardant is selected from one or more of triphenylphosphine oxide, methoxymethyl (diphenyl) phosphine oxide, tris (2-methylaziridine) phosphine oxide, diethyl ethylphosphonate and phosphinic acid amide; more preferably, the organic phosphorus-based flame retardant is tris (2-methylaziridine) phosphine oxide and/or methoxymethyl (diphenyl) phosphine oxide; most preferably, the organophosphorus flame retardant is methoxymethyl (diphenyl) phosphine oxide.
By adopting the technical scheme, the cooperation of the methoxymethyl (diphenyl) phosphine oxide and the ShinEtsu KR-480 organosilicon flame retardant is adopted, so that the flame retardance of the PC composite material is further improved, the methoxymethyl (diphenyl) phosphine oxide can be introduced into the siloxane-containing PC powder substrate, the stability is remarkably improved, the seepage is avoided, and the low-temperature toughness of the PC composite material is improved under the action of the rigid benzene ring. In addition, methoxymethyl (diphenyl) phosphine oxide and ShinEtsu KR-480 replace 3-benzenesulfonyl potassium benzenesulfonate and perfluorobutyl potassium sulfonate, do not contain fluorine, better meet the requirement of environmental protection and have good stability.
Preferably, the antioxidant is prepared from dilauryl thiodipropionate and tris [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of 1:1 are mixed.
By adopting the technical scheme, the dilauryl thiodipropionate and the tris [2, 4-di-tert-butylphenyl ] phosphite are adopted in the polycarbonate composite material, so that the processing flowability of the PC composite material can be improved, the mechanical property and the flame retardant property of the radome are prevented from being greatly reduced due to the fact that the radome is aged in an outdoor environment for a long time, and when the mass ratio of the dilauryl thiodipropionate to the tris [2, 4-di-tert-butylphenyl ] phosphite is 1:1, the yellowing resistance of the PC composite material can be further improved. Meanwhile, the modified polycarbonate resin, an acrylic acid impact modifier with a core/shell structure, methoxymethyl (diphenyl) phosphine oxide and ShinEtsu KR-480 organosilicon flame retardant are acted together to improve the toughness of the PC composite material at low temperature.
Preferably, the preparation method of the acrylic impact modifier with the core/shell structure comprises the following steps:
(1) Synthesis of a silicone core emulsion: dimethyl siloxane, a cross-linking agent A, an emulsifier A, a catalyst and deionized water are mixed according to a mass ratio of 40:2:1:1:100, homogenizing and emulsifying, introducing nitrogen, stirring and reacting at 70-90 ℃ for 20-30h, and adjusting the pH to 7 to obtain polysiloxane core emulsion;
(2) Synthesizing polysiloxane modified outer core emulsion: butyl acrylate, a cross-linking agent B, an emulsifier B and distilled water are mixed according to the mass ratio of 60:0.5:1.2:120, homogenizing and emulsifying, adding the mixture into the polysiloxane core emulsion obtained in the step (1), adding sodium persulfate, and stirring and reacting at the temperature of between 60 and 80 ℃ for 1 to 3 hours to obtain polysiloxane modified outer core emulsion;
(3) Synthetic core/shell structural acrylic impact modifiers: methyl methacrylate, a cross-linking agent C, an emulsifying agent C and purified water are mixed according to the mass ratio of 50:0.3:1.3:120, homogenizing and emulsifying, adding the mixture into the polysiloxane modified outer core emulsion obtained in the step (2), adding potassium persulfate, stirring and reacting at 60-80 ℃ for 3-6h to obtain the acrylic acid composite emulsion with the core/shell structure, demulsifying, and drying to obtain the acrylic acid impact modifier with the core/shell structure.
By adopting the technical scheme, the application of the siloxane-containing PC powder is limited due to higher melting point, poor processing fluidity and low notch impact strength at low temperature. The acrylic acid impact modifier with the core/shell structure prepared by copolymerizing acrylic ester and siloxane by adopting the method has extremely low surface energy, si-O bond energy is far greater than C-C bond energy and C-O bond energy, si-O-Si has strong flexibility, and the impact resistance and chemical resistance of the PC composite material are improved. Meanwhile, the acrylic acid impact modifier with the core/shell structure prepared by the method has a three-layer structure, and uses polybutyl acrylate and poly [ dimethylsiloxy ] silane as cores and polymethyl methacrylate as shells, so that the compatibility of the acrylic acid impact modifier with silicone-containing PC powder and silicone powder is improved, and the low-temperature resistance stability of the PC composite material is improved.
Preferably, the crosslinking agent A is selected from one or more of vinyl trimethoxy silane, divinyl benzene, 1,4 butanediol diacrylate, 3- (methacryloxy) propyl trimethoxy silane, tetramethoxy silane and methylene bisacrylamide; more preferably, the cross-linking agent A is a mixture of 3- (methacryloyloxy) propyl trimethoxy silane and methylene bisacrylamide; most preferably, the mass ratio of the 3- (methacryloyloxy) propyl trimethoxy silane to the methylene bisacrylamide is 1:0.8.
by adopting the technical scheme, 3- (methacryloyloxy) propyl trimethoxy silane and methylene bisacrylamide are compounded to serve as a cross-linking agent, and reactive double bonds are introduced, so that the cross-linking structure is improved, the compatibility is improved, and the impact strength of the PC composite material at-60 ℃ is remarkably improved.
Preferably, the raw materials for preparing the weather-resistant flame-retardant PC composite material for the antenna housing further comprise 1-2 parts of an ultraviolet absorbent.
By adopting the technical scheme, the ultraviolet absorbent is added in the PC composite material, so that the weather resistance of the PC composite material is further improved, and the 5G antenna housing prepared by the PC composite material can be used in an outdoor environment for a long time.
In a second aspect, the application provides a preparation method of a weather-resistant flame-retardant PC composite material for an antenna housing, which adopts the following technical scheme:
a preparation method of a weather-resistant flame-retardant PC composite material for an antenna housing comprises the following steps:
s1: adding silicone PC powder, silicone powder, pentaerythritol stearate, a flame retardant and an acrylic acid impact modifier with a core/shell structure into a mixer, and uniformly stirring;
s2: and adding an antioxidant, a polytetrafluoroethylene powder anti-dripping agent and an ultraviolet absorbent, uniformly stirring, melting and blending in a double-screw extruder, extruding, drawing strips, cooling, granulating and drying to obtain the weather-resistant flame-retardant PC composite material for the antenna housing.
By adopting the technical scheme, the weather-resistant flame-retardant PC composite material for the antenna housing prepared by the application has good plasticity, good flame retardance and weather resistance, and can meet the application requirements of the 5G antenna housing.
In summary, the present application has the following beneficial effects:
1. according to the application, the siloxane-containing PC powder is added, so that the mechanical property, the thermal property and the flame retardant property of the weather-resistant flame-retardant PC composite material for the antenna housing are improved, the polytetrafluoroethylene powder anti-dripping agent can prevent melting and dripping, the using amount of a flame retardant is greatly reduced, the flame retardant property is improved, and the flame retardant degree reaches V0 at the thickness of 0.9 mm;
2. the pentaerythritol stearate with the hydroxyl value of 20-35mgKOH/g is adopted, so that the dispersing effect of siloxane powder in the siloxane-containing PC powder can be improved, the internal and external lubricating effects of the pentaerythritol stearate are beneficial to keeping the core-shell structure of the acrylic acid impact modifier with the core/shell structure, and simultaneously, the compatibility of the polytetrafluoroethylene powder anti-dripping agent with the siloxane powder and the siloxane-containing PC powder is improved, and the expansion phenomenon is prevented;
3. according to the application, the organic silicon flame retardant and the organic phosphine are compounded in a flame-retardant manner, the mass ratio of the organic silicon flame retardant and the organic phosphine is regulated and controlled, the using amount of the flame retardant can be greatly reduced, the cost is reduced, the organic silicon flame retardant and the other components are coordinated, the corrosion to an antenna housing is reduced, and the impact strength of the PC composite material cannot be influenced.
4. The flame retardant PC composite material is compounded by methoxy methyl (diphenyl) phosphine oxide and ShinEtsu KR-480 organic silicon flame retardant, so that the flame retardance of the PC composite material is further improved, and the low-temperature toughness of the PC composite material is improved;
5. the dilauryl thiodipropionate and the tris [2, 4-di-tert-butylphenyl ] phosphite are compounded, so that the processing fluidity of the PC composite material can be improved, the antenna housing is prevented from being aged in an outdoor environment for a long time to greatly reduce the mechanical property and the flame retardant property, and the yellowing resistance of the PC composite material is improved;
6. according to the preparation method, acrylic ester and siloxane are copolymerized into the acrylic acid impact modifier with the core/shell structure, so that the impact resistance and chemical resistance of the PC composite material are improved, the compatibility of a system is obviously improved, and the low-temperature resistance stability of the PC composite material is improved.
Detailed Description
The present application is described in further detail below with reference to preparation examples and examples.
Preparation example
Preparation examples 1 to 6
The following description will be made by taking preparation example 1 as an example.
The preparation example 1 provides an acrylic acid impact modifier with a core/shell structure, which comprises the following preparation steps:
(1) Synthesis of a polysiloxane core emulsion: mixing 40g of tetra [ dimethylsiloxy ] silane, 2g of cross-linking agent A, 1g of emulsifying agent A, 1g of concentrated hydrochloric acid (36 wt%) and 100g of deionized water, homogenizing and emulsifying for 10min, introducing 30min of nitrogen, stirring and reacting for 20h at 85 ℃ (the stirring speed is 300 r/min), and adjusting the pH value to 7 by using 5wt% of sodium hydroxide aqueous solution to obtain polysiloxane core emulsion;
(2) Synthesizing polysiloxane modified outer core emulsion: mixing 60g of n-butyl acrylate, 0.5g of cross-linking agent B, 1.2g of emulsifier B and 120g of distilled water, homogenizing and emulsifying for 10min, adding into the polysiloxane core emulsion obtained in the step (1), adding 0.22g of sodium persulfate, and stirring and reacting for 1.5h at 75 ℃ (the stirring speed is 250 r/min) to obtain polysiloxane modified outer core emulsion;
(3) Synthetic core/shell structural acrylic impact modifiers: 50g of methyl methacrylate, 0.3g of a cross-linking agent C, 1.3g of an emulsifying agent C and 120g of purified water are mixed according to a mass ratio of 50:0.3:1.3:120, homogenizing and emulsifying for 10min, adding the mixture into the polysiloxane modified outer core emulsion obtained in the step (2), adding 0.18g of potassium persulfate, stirring and reacting for 5h at 70 ℃ (the stirring speed is 250 r/min), obtaining acrylic composite emulsion with a core/shell structure, demulsifying, and drying to obtain acrylic impact modifier with the core/shell structure;
wherein the tetra [ dimethylsiloxy ] silane has a CAS number of 17082-47-2; the cross-linking agent A is prepared from 3- (methacryloyloxy) propyl trimethoxy silane and methylene bisacrylamide in a mass ratio of 1:0.8, the CAS number of the 3- (methacryloyloxy) propyltrimethoxysilane is 2530-85-0, and the CAS number of the methylenebisacrylamide is 110-26-9; the emulsifier A is prepared from sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene OP-7 in a mass ratio of 1:0.7, wherein the alkylphenol polyoxyethylene OP-7 is purchased from Jinan Yun Baihui Biotech limited; the crosslinking agent B is 1, 4-butanediol diacrylate (CAS number is 1070-70-8); the emulsifier B is fatty alcohol polyoxyethylene ether AEO-5 which is purchased from Nantong Rendada chemical Co., ltd; the cross-linking agent C is 3- (methacryloyloxy) propyl trimethoxy silane; the emulsifier C is prepared from sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene OP-10 in a mass ratio of 1:0.3, and the alkylphenol polyoxyethylene OP-10 is purchased from Jinan Yun Baihui Biotech limited.
Preparation examples 2 to 6
Preparation examples 2 to 6, the same as preparation example 1, were different only in that: the preparation raw materials of the acrylic acid impact modifier with the core/shell structure are different:
preparation example 2, except that: the crosslinking agent A is 1, 4-butanediol diacrylate.
Preparation example 3, except that: the cross-linking agent A is 3- (methacryloyloxy) propyl trimethoxy silane.
Preparation example 4, except that: the crosslinking agent A is methylene bisacrylamide.
Preparation example 5, except that: the emulsifier C is prepared from sodium dodecyl benzene sulfonate and fatty alcohol-polyoxyethylene ether AEO-5 in a mass ratio of 1:0.3, and mixing.
Preparation example 6, except that: the emulsifier C is prepared from sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene OP-7 in a mass ratio of 1:0.3, and mixing.
The acrylic acid impact modifier with the core/shell structure prepared in the preparation examples 1-6 is applied to preparation of weather-resistant flame-retardant PC composite material for antenna housing.
Examples
Examples 1 to 6
The following description will be given by taking example 1 as an example, wherein the acrylic impact modifier with a core/shell structure prepared in preparation example 1 is applied to the weather-resistant and flame-retardant PC composite material for antenna housing prepared in example 1; the trademark of the siloxane-containing PC powder is TRIREX ST6-3022PJ (1), and the siloxane-containing PC powder is purchased from Korea three-year old people; the siloxane powder is tetramethyldisiloxane, has a CAS number of 3277-26-7, and is purchased from Wuhan Wooxuan science and technology Limited; the pentaerythritol stearate is PETS-AP, and is purchased from Yino chemical technology, inc., guangzhou; the flame retardant is prepared from 3-benzenesulfonyl potassium benzene sulfonate (CAS number is 63316-43-8) and perfluorobutyl potassium sulfonate (CAS number is 29420-49-3) in a mass ratio of 1:1, mixing; the antioxidant is prepared from beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (CAS number is 2082-79-3) and tris [2, 4-di-tert-butylphenyl ] phosphite (CAS number is 31570-04-4) according to a mass ratio of 1:1, mixing; the polytetrafluoroethylene powder anti-dripping agent is sold under the brand name FA-500 and purchased from Japan Dajin company; the ultraviolet absorbent is UV-234 (CAS number is 70321-86-7);
the embodiment 1 provides a preparation method of a weather-resistant flame-retardant PC composite material for an antenna housing, which comprises the following steps:
s1: adding 50g of siloxane-containing PC powder, 15g of siloxane powder, 0.3g of pentaerythritol stearate, 0.8g of flame retardant and 5g of the acrylic impact modifier with the core/shell structure in the preparation example 1 into a mixer, and uniformly stirring;
s2: and then adding 0.6g of antioxidant, 0.5g of polytetrafluoroethylene powder anti-dripping agent and 1g of ultraviolet absorbent, uniformly stirring, melting and blending in a double-screw extruder, extruding, bracing, cooling, granulating and drying to obtain the weather-resistant flame-retardant PC composite material for the radome.
As shown in table 1, the weather-resistant flame-retardant PC composite materials for radomes of examples 1 to 6 are different only in the acrylic impact modifier of core/shell structure.
TABLE 1
| Examples | Core/shell acrylic impact modifiers |
| Example 1 | Preparation example 1 core/Shell-structured acrylic impact modifier |
| Example 2 | Preparation example 2 core/Shell-structured acrylic impact modifier |
| Example 3 | Preparation example 3 core/Shell-structured acrylic impact modifier |
| Example 4 | Preparation example 4 core/Shell-structured acrylic impact modifier |
| Example 5 | Preparation example 5 core/Shell-structured acrylic impact modifier |
| Example 6 | Preparation example 6 core/Shell-structured acrylic impact modifier |
Examples 7 to 10
Examples 7 to 10, like example 1, differ only in the quality of the raw materials for the preparation of the weather-resistant flame-retardant PC composite material for antenna covers, see table 2.
TABLE 2
| Components | Example 1 | Example 7 | Example 8 | Example 9 | Example 10 |
| Silicone-containing PC powder (g) | 50 | 70 | 60 | 60 | 60 |
| Silicone powder (g) | 15 | 40 | 30 | 30 | 30 |
| Pentaerythritol stearate (g) | 0.3 | 1 | 0.6 | 0.6 | 0.3 |
| Flame retardant (g) | 0.8 | 2 | 1.4 | 1.4 | 1.4 |
| Acrylic impact modifier of core/Shell Structure (g) | 5 | 8 | 7 | 7 | 5 |
| Antioxidant (g) | 0.6 | 2 | 1.3 | 1.3 | 1.3 |
| Polytetrafluoroethylene powder anti-dripping agent (g) | 0.5 | 1 | 0.7 | 0.7 | 0.7 |
| Ultraviolet absorber (g) | 1 | 2 | 1.5 | 0 | 1.5 |
Example 11
Example 11 differs from example 8 only in that the pentaerythritol stearate was PETS-AHS, available from Yino chemical technology, inc., guangzhou.
Examples 12 to 15
Examples 12-15, like example 11, differ only in the flame retardant:
example 12, except that: the flame retardant is prepared from an organic silicon flame retardant X-40-9805 and tris (2-methylaziridine) phosphine oxide (CAS number 57-39-6) in a mass ratio of 1:1, and the organosilicon flame retardant X-40-9805 was purchased from Kyoto chemical industries, ltd.
Example 13, except that: the flame retardant is prepared from ShinEtsu KR-480 and methoxymethyl (diphenyl) phosphine oxide (CAS number is 4455-77-0) in a mass ratio of 0.6:1, said ShinEtsu KR-480 was purchased from seiki chemical industries co.
Example 14, except that: the flame retardant is ShinEtsu KR-480.
Example 15, except that: the flame retardant is methoxymethyl (diphenyl) phosphine oxide.
Examples 16 to 18
Examples 16-18, like example 13, differ only in the antioxidants:
example 16, except that: the antioxidant is prepared from dilauryl thiodipropionate (CAS number is 123-28-4) and tris [2, 4-di-tert-butylphenyl ] phosphite in a mass ratio of 1:1 are mixed.
Example 17, except that: the antioxidant is dilauryl thiodipropionate.
Example 18, except that: the antioxidant is tris [2, 4-di-tert-butylphenyl ] phosphite.
Example 19
Example 19 differs from example 16 only in that the polytetrafluoroethylene powder anti-drip agent is sold under the trademark Flontech FT-1-10, available from Australian flourishing materials science and technology, inc. in Huangshan.
Example 20, like example 16, except that the ultraviolet absorber was UV-0 (CAS number 131-56-6).
Comparative example
Comparative examples 1 to 4
Comparative examples 1 to 4, like example 2, differ only in the kind of raw materials of the weather-resistant flame-retardant PC composite material for radome:
comparative example 1, except that: preparation example 2 the acrylic impact modifier of core/shell structure was replaced with a hongcheng ACR401 impact modifier, which was purchased from qing ai realy ltd, hannan.
Comparative example 2, except that: the silicone-containing PC powder TRIREX ST6-3022PJ (1) is replaced by TRIREX 3030PJ, and the TRIREX 3030PJ is purchased from Korea.
Comparative example 3, except that: the pentaerythritol stearate is replaced by glyceryl stearate, the glyceryl stearate is TEGIN 4100 Pelles, and the glyceryl stearate is purchased from Shanghai Hengchen industry Co., ltd.
Comparative example 4, except that: the acrylic acid impact modifier with the core/shell structure is replaced by methyl methacrylate-butadiene-styrene copolymer, the mark of the methyl methacrylate-butadiene-styrene copolymer is DL-535, and the acrylic acid impact modifier is purchased from Yangtze river plastic additives Co.
Comparative example 5
The preparation method of the weather-resistant flame-retardant PC composite material for the antenna housing, which is provided by the comparative example 5, comprises the following steps:
s1: adding 50g of polycarbonate, 15g of siloxane powder, 0.3g of pentaerythritol stearate and 1g of flame retardant into a mixer, and uniformly stirring;
s2: then adding 0.6g of antioxidant and 0.5g of polytetrafluoroethylene powder anti-dripping agent, uniformly stirring, melting and blending in a double-screw extruder, extruding, bracing, cooling, granulating and drying to obtain the weather-resistant flame-retardant PC composite material for the radome;
wherein the polycarbonate is SABIC 4704 which is purchased from Tongguan company Yi plastic materials Co.Ltd; the silicone powder, pentaerythritol stearate, flame retardant, antioxidant, polytetrafluoroethylene powder anti-dripping agent were the same as in example 1.
Performance test
Aiming at the weather-resistant flame-retardant PC composite material for the antenna housing provided by the embodiments 1-20 and the comparative examples 1-5 of the application, the following performance tests are carried out:
1. flame retardance: the weather-resistant flame-retardant PC composite material for the antenna housing provided in examples 1 to 20 and comparative examples 1 to 5 was prepared into a sheet, and the thickness of the sheet prepared from the weather-resistant flame-retardant PC composite material for the antenna housing, when the flame retardancy was VO, was measured with reference to the UL94 standard, and the test results are shown in Table 3.
2. Chemical resistance: the weather-resistant flame-retardant PC composite materials for radomes provided in examples 1 to 20 and comparative examples 1 to 5 were immersed in a 10wt% carbon tetrachloride ethanol solution, and whether cracking occurred or not was observed, and the time when cracking started was recorded, and the test results are shown in table 3.
3. Low temperature resistance stability: the weather-resistant flame-retardant PC composite materials for antenna covers provided in examples 1 to 20 and comparative examples 1 to 5 were left to stand in an environment of-30 ℃ for 2 years, and notched impact strength before and after the leaving was tested with reference to the method of D256, test conditions: 1/8', -60 deg.C, the results are shown in Table 3.
4. Yellowing resistance: the weather-resistant flame-retardant PC composite materials for radomes provided in examples 1 to 20 and comparative examples 1 to 5 were irradiated with a 50W ultraviolet lamp for 1 month, and whether yellowing occurred or not was observed, and the test results are shown in Table 3.
TABLE 3
| Examples | Flame retardancy | Chemical resistance | Stability against Low temperatures | Resistance to yellowing |
| Example 1 | 0.8mm | 7min | 40KJ/m 2 | Slight yellowing |
| Example 2 | 0.9mm | 5min | 39KJ/m 2 | Slight yellowing |
| Example 3 | 0.9mm | 6min | 39KJ/m 2 | Slight yellowing |
| Example 4 | 0.9mm | 5min | 40KJ/m 2 | Yellow stain |
| Example 5 | 0.9mm | 6min | 40KJ/m 2 | Slight yellowing |
| Example 6 | 0.9mm | 6min | 40KJ/m 2 | Slight yellowing |
| Example 7 | 0.8mm | 7min | 40KJ/m 2 | Slight yellowing |
| Example 8 | 0.8mm | 8min | 42KJ/m 2 | Slight yellowing |
| Example 9 | 0.9mm | 8min | 42KJ/m 2 | Yellow stain |
| Example 10 | 0.9mm | 7min | 41KJ/m 2 | Slight yellowing |
| Example 11 | 0.8mm | 10min | 43KJ/m 2 | Slight yellowing |
| Example 12 | 0.8mm | 13min | 45KJ/m 2 | Slight yellowing |
| Example 13 | 0.7mm | 14min | 48KJ/m 2 | Slight yellowing |
| Example 14 | 0.8mm | 13min | 45KJ/m 2 | Slight yellowing |
| Example 15 | 0.8mm | 10mim | 46KJ/m 2 | Slight yellowing |
| Example 16 | 0.6mm | 18min | 56KJ/m 2 | No yellowing |
| Example 17 | 0.7mm | 15min | 54KJ/m 2 | No yellowing |
| Example 18 | 0.7mm | 15min | 49KJ/m 2 | Slight yellowing |
| Example 19 | 0.6mm | 16min | 55KJ/m 2 | No yellowing |
| Example 20 | 0.6mm | 17min | 54KJ/m 2 | No yellowing |
| Comparative example 1 | 1.4mm | 4min | 38KJ/m 2 | Slight yellowing |
| Comparative example 2 | 1.5mm | 4min | 37KJ/m 2 | Slight yellowing |
| Comparative example 3 | 1.3mm | 3min | 37KJ/m 2 | Slight yellowing |
| Comparative example 4 | 1.4mm | 3min | 36KJ/m 2 | Slight yellowing |
| Comparative example 5 | 1.5mm | 3min | 36KJ/m 2 | Yellow stain |
The present application is described in detail below with reference to the test data provided in table 3.
From examples 1 to 4 of the present application, it can be seen that the effect of the cross-linking agent A for preparing the acrylic impact modifier with a core/shell structure on the overall performance of the PC composite material is superior, wherein the cross-linking agent A is a compound of 3- (methacryloyloxy) propyltrimethoxysilane and methylenebisacrylamide, and the chemical resistance and yellowing resistance of the PC composite material are superior.
From examples 1 and 5 to 6 of the present application, it can be seen that when the emulsifier C for preparing the acrylic impact modifier with the core/shell structure is a compound of sodium dodecyl benzene sulfonate and alkylphenol ethoxylates OP-10, the particle size of the composite emulsion of the acrylic impact modifier with the core/shell structure is uniform, and the chemical resistance of the PC composite material is excellent.
From examples 1 and 7-10 of the application, it can be seen that changing the content of the raw materials for preparing the PC composite material affects the flame retardancy, chemical resistance and low temperature stability of the PC composite material, wherein increasing the amount of the flame retardant and the silicone-containing PC powder significantly improves the flame retardancy, but the chemical resistance and low temperature stability are reduced, and the ultraviolet absorber can greatly reduce the yellowing phenomenon, and example 8 is better in comprehensive consideration.
From examples 8 and 11 herein, it is known that the hydroxyl value of pentaerythritol stearate affects the chemical resistance and low temperature stability of the PC composite.
From examples 11 to 15 of the present application, it is known that the flame retardant is a compound of ShinEtsu KR-480 and methoxymethyl (diphenyl) phosphine oxide, which not only improves the flame retardancy of the PC composite material, but also improves the chemical resistance and low temperature stability of the PC composite material.
It is understood from examples 13 and 16 to 18 of the present application that when the antioxidant is a mixture of dilauryl thiodipropionate and tris [2, 4-di-t-butylphenyl ] phosphite, the yellowing resistance of the PC composite material is improved, and the chemical resistance, low-temperature stability, and flame retardancy of the PC composite material are also improved.
From the example 2 and the comparative examples 1 to 4, the flame retardant property of the PC composite material is improved by the combined action of the siloxane-containing PC powder, the acrylic acid impact modifier with the core/shell structure and the pentaerythritol stearate, the flame retardant degree reaches V0 at the thickness of 0.9mm, and the chemical resistance and the low temperature resistance stability are also improved.
For the weather-resistant flame-retardant PC composite material for antenna covers provided in embodiment 16 and comparative example 5 of the present application, the performance tests shown in table 4 were performed:
TABLE 4
| Performance test items | Test standard | Test conditions | Unit of |
| Tensile strength | D638 | 50mm/min | Mpa |
| Elongation at break | D638 | 50mm/min | % |
| Flexural strength | D790 | 10mm/min | Mpa |
| Flexural modulus | D790 | 10mm/min | Mpa |
| Hardness of pencil | D-3363 | 23℃，750g | H |
| Notched impact strength | D256 | 1/8",23℃ | KJ/m 2 |
| Melt index | D1238 | 260℃,2.16kg | g/10min |
| Molding shrinkage ratio | D955 | / | % |
| Density of | D792 | 23℃ | g/cm 2 |
| Heat distortion temperature | D648 | 1.82MPa | ℃ |
| Volume resistance | D257 | / | ohm-cm |
The results of the performance tests corresponding to Table 4 above are shown in Table 5 for example 16 and comparative example 5 of the present application.
TABLE 5
| Performance test items | Example 16 | Comparative example 5 |
| Tensile strength | 63 | 58 |
| Elongation at break | 120 | 110 |
| Bending strength | 94 | 88 |
| Flexural modulus | 2060 | 2,000 |
| Hardness of pencil | 76 | 70 |
| Notched impact strength | 56 | 40 |
| Melt index | 11 | 10 |
| Molding shrinkage ratio | 0.5-0.7 | 0.5-0.7 |
| Density of | 1.2 | 1.2 |
| Heat distortion temperature | 125 | 124 |
| Volume resistance | 1E+15 | 1E+15 |
The effects of example 16 and comparative example 5 of the present application are described in detail below in conjunction with the data provided in tables 3-5:
as can be seen from table 3, the PC composite material provided in example 16 is significantly superior in flame retardancy, chemical resistance, low temperature stability resistance and yellowing resistance to the PC composite material provided in comparative example 5. As is apparent from tables 4 and 5, the PC composite material provided in example 16 of the present application has higher tensile strength, elongation at break, flexural strength, flexural modulus, pencil hardness, notched impact strength (23 ℃), melt index, and heat distortion temperature than those of comparative example 5.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (4)
1. The weather-resistant flame-retardant PC composite material for the antenna housing is characterized by comprising the following raw materials in parts by weight: 50-70 parts of siloxane-containing PC powder, 15-40 parts of tetramethyldisiloxane, 0.3-1 part of pentaerythritol stearate, 0.8-2 parts of flame retardant, 0.6-2 parts of antioxidant, 5-8 parts of acrylic acid impact modifier with a core/shell structure and 0.5-1 part of polytetrafluoroethylene powder;
the melt mass flow rate of the siloxane-containing PC powder at 300 ℃ and 1.2kg is 3.8-4.2g/10min;
the flame retardant is prepared from an organic silicon flame retardant and an organic phosphorus flame retardant according to the mass ratio of (0.6-1): 1, mixing;
the organic silicon flame retardant is ShinEtsu KR-480 and/or X-40-9805;
the organic phosphorus flame retardant is selected from one or more of triphenylphosphine oxide, methoxymethyl (diphenyl) phosphine oxide, tris (2-methyl aziridine) phosphine oxide, diethyl ethylphosphonate and phosphinic acid amide;
the antioxidant is prepared from dilauryl thiodipropionate and tris [2, 4-di-tert-butylphenyl ] phosphite according to a mass ratio of 1:1, mixing;
the preparation method of the acrylic acid impact modifier with the core/shell structure comprises the following steps:
(1) Synthesis of a silicone core emulsion: the preparation method comprises the following steps of (1) mixing tetra [ dimethylsiloxy ] silane, a cross-linking agent A, an emulsifying agent A, a catalyst and deionized water in a mass ratio of 40:2:1:1:100, homogenizing and emulsifying, introducing nitrogen, stirring and reacting at 70-90 ℃ for 20-30h, and adjusting the pH to 7 to obtain polysiloxane core emulsion;
(2) Synthesizing polysiloxane modified outer core emulsion: butyl acrylate, a cross-linking agent B, an emulsifier B and distilled water are mixed according to the mass ratio of 60:0.5:1.2:120, homogenizing and emulsifying, adding the mixture into the polysiloxane core emulsion obtained in the step (1), adding sodium persulfate, and stirring and reacting at the temperature of between 60 and 80 ℃ for 1 to 3 hours to obtain polysiloxane modified outer core emulsion;
(3) Synthetic core/shell structural acrylic impact modifiers: methyl methacrylate, a cross-linking agent C, an emulsifying agent C and purified water are mixed according to the mass ratio of 50:0.3:1.3:120, homogenizing and emulsifying, adding the mixture into the polysiloxane modified outer core emulsion obtained in the step (2), adding potassium persulfate, stirring and reacting at 60-80 ℃ for 3-6h to obtain acrylic acid composite emulsion with a core/shell structure, and demulsifying and drying to obtain acrylic acid impact modifier with a core/shell structure;
the cross-linking agent A is prepared from 3- (methacryloyloxy) propyl trimethoxy silane and methylene bisacrylamide in a mass ratio of 1:0.8, mixing;
the emulsifier A is prepared from sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene OP-7 in a mass ratio of 1:0.7 mixing;
the crosslinking agent B is 1, 4-butanediol diacrylate;
the emulsifier B is fatty alcohol polyoxyethylene ether AEO-5;
the cross-linking agent C is 3- (methacryloyloxy) propyl trimethoxy silane;
the emulsifier C is prepared from sodium dodecyl benzene sulfonate and alkylphenol polyoxyethylene OP-10 according to the mass ratio of 1:0.3, and mixing.
2. The weather-resistant flame-retardant PC composite material for a radome of claim 1, wherein the hydroxyl value of the pentaerythritol stearate is 20-35mgKOH/g.
3. The preparation method of the weather-resistant and flame-retardant PC composite material for the radome, which is characterized in that the raw materials for preparing the weather-resistant and flame-retardant PC composite material for the radome comprise 1-2 parts of an ultraviolet absorber.
4. The preparation method of the weather-resistant flame-retardant PC composite material for the radome, which is characterized by comprising the following steps:
s1: adding silicone-containing PC powder, tetramethyldisiloxane, pentaerythritol stearate, a flame retardant and an acrylic acid impact modifier with a core/shell structure into a mixer, and uniformly stirring;
s2: and adding the antioxidant, the polytetrafluoroethylene powder anti-dripping agent and the ultraviolet absorbent, uniformly stirring, melting and blending in a double-screw extruder, extruding, drawing into strips, cooling, granulating and drying to obtain the weather-resistant flame-retardant PC composite material for the radome.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011566636.4A CN112694737B (en) | 2020-12-25 | 2020-12-25 | Weather-proof flame-retardant PC composite material for antenna housing and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011566636.4A CN112694737B (en) | 2020-12-25 | 2020-12-25 | Weather-proof flame-retardant PC composite material for antenna housing and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112694737A CN112694737A (en) | 2021-04-23 |
| CN112694737B true CN112694737B (en) | 2022-10-28 |
Family
ID=75510847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011566636.4A Active CN112694737B (en) | 2020-12-25 | 2020-12-25 | Weather-proof flame-retardant PC composite material for antenna housing and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112694737B (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100544904B1 (en) * | 2002-12-24 | 2006-01-24 | 주식회사 엘지화학 | Impact-reinforcing agent having multilayered structure, method for preparing the same, and thermoplastic resin comprising the same |
| CN101456936B (en) * | 2007-12-10 | 2012-05-09 | 华南理工大学 | Flame-retardant interfacial modifier and preparation method and flame retardant polycarbonate composition |
| DE102008024672A1 (en) * | 2008-05-21 | 2009-11-26 | Bayer Materialscience Ag | Low-temperature polycarbonate blends |
| US9309407B2 (en) * | 2013-05-02 | 2016-04-12 | Sabic Global Technologies B.V. | Polycarbonate-siloxane copolymer flame retarded with a silicone based core shell modifier |
| CN106398234B (en) * | 2016-09-06 | 2019-05-07 | 广州市聚赛龙工程塑料股份有限公司 | A kind of Halogenless flaming retarding cold resistant PC material and preparation method thereof suitable for charging pile charging gun |
| CN106866971B (en) * | 2017-04-10 | 2020-05-05 | 广东优科艾迪高分子材料有限公司 | Weather-resistant low-temperature-resistant organic silicon impact modifier and preparation method and application thereof |
| CN111073248B (en) * | 2019-12-16 | 2021-12-03 | 上海长伟锦磁工程塑料有限公司 | Hydrolysis-resistant, illumination-resistant and low-temperature-resistant halogen-free flame-retardant polycarbonate composite material and preparation method thereof |
-
2020
- 2020-12-25 CN CN202011566636.4A patent/CN112694737B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112694737A (en) | 2021-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111073248B (en) | Hydrolysis-resistant, illumination-resistant and low-temperature-resistant halogen-free flame-retardant polycarbonate composite material and preparation method thereof | |
| CN101475706B (en) | Rear earth organic phosphonate flame retardant, synthesizing method and use thereof | |
| CN112538252B (en) | Transparent hydrolysis-resistant weather-resistant halogen-free flame-retardant polycarbonate composite material | |
| CN111072973A (en) | Phosphorus-containing POSS, preparation method thereof and application thereof in flame retardant | |
| CN108752593B (en) | A kind of preparation method and applications of polysiloxane-polycarbonate | |
| CN110922518B (en) | Water-resistant intumescent flame retardant and preparation method and application thereof | |
| CN112280027A (en) | Phosphorus-silicon-containing copolymerized polycarbonate, preparation method and composition thereof, and preparation method and application of composition | |
| CN112694737B (en) | Weather-proof flame-retardant PC composite material for antenna housing and preparation method thereof | |
| CN113637307B (en) | Hydrolysis-resistant halogen-free flame-retardant high-toughness PC/ASA alloy material and preparation method and application thereof | |
| CN111961198B (en) | Halogen-free flame-retardant toughening agent and preparation method and application thereof | |
| CN114479407B (en) | Thin-wall flame-retardant polycarbonate material and preparation method thereof | |
| CN100506914C (en) | Smoke-inhibition type halogen-free flame-proof polycarbonate | |
| CN105860545B (en) | Siliceous polycarbonate and preparation method thereof | |
| CN113897045A (en) | Flame-retardant polycarbonate alloy composition and preparation method and application thereof | |
| CN111334017B (en) | Fibrous filler modified polycarbonate compound and preparation method thereof | |
| CN113788947A (en) | Organic silicon modified toughening agent, and preparation method and application thereof | |
| CN114031779A (en) | Phosphorus-containing ladder-shaped polysiloxane, preparation method thereof and application of phosphorus-containing ladder-shaped polysiloxane as flame-retardant synergist | |
| CN112708135A (en) | Degradable organic silicon elastomer and synthesis method thereof | |
| CN112480373A (en) | Flame-retardant epoxy resin composition and preparation method and application thereof | |
| CN111138824B (en) | Impact-resistant halogen-free flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) blend alloy and preparation method thereof | |
| CN114539754B (en) | Weather-resistant halogen-free flame-retardant bio-based polycarbonate material and preparation method thereof | |
| CN113336993B (en) | Preparation method of anti-dripping nylon plate based on surface structured flame-retardant technology | |
| CN110607103B (en) | Anti-doodling transparent flame-retardant coating and preparation method thereof | |
| CN116285287A (en) | Flame-retardant PC/ABS material and preparation method thereof | |
| CN117801282A (en) | Modified POSS-based nitrogen and silicon composite flame retardant and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |