CN102241835A - Organic composite coating method of surfaces of inorganic metal hydroxide flame retardant - Google Patents
Organic composite coating method of surfaces of inorganic metal hydroxide flame retardant Download PDFInfo
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- CN102241835A CN102241835A CN 201010171257 CN201010171257A CN102241835A CN 102241835 A CN102241835 A CN 102241835A CN 201010171257 CN201010171257 CN 201010171257 CN 201010171257 A CN201010171257 A CN 201010171257A CN 102241835 A CN102241835 A CN 102241835A
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Abstract
The invention relates to a new technology and a new method for processing surfaces of a metal hydroxide flame retardant. In the exploitation application history of aluminum hydroxide (ATH) and magnesium hydroxide (MDH), an ATH flame retardant and an MDH flame retardant with a maleic anhydride grafted polyolefin and polyolefin random copolymerization composite coating on surfaces of inorganic particles are first prepared through the new technology and the new method of organic composite coating the inorganic particles first adopted in the invention, wherein the ATH flame retardant and the MDH flame retardant not only comprise a core (the inorganic particles), but also comprise multiple coatings of an inner layer (a coupling layer), a secondary outer layer (an organic composite coating), and an outer layer (a lubricant dispersion layer). The new technology and the new method of the organics coating the inorganic particles which are adopted allow a firm interface bond to be generated between the ATH and the MDH and high-molecular polymer matrixes of plastic, rubber and the like, so the dispersibility and the fluidity of the ATH and the MDH in a polymer melt are improved, the flame retardation is improved, and the loss of mechanical properties caused by adding inorganic flame retardants to the polymer matrixes is reduced.
Description
1, the present invention relates to a kind of mineral-type metal hydroxide combustion inhibitor surface-treated new technologies.On the Application and Development history of aluminium hydroxide (hereinafter to be referred as ATH) and magnesium hydroxide mineral-type metal hydroxide combustion inhibitors such as (hereinafter to be referred as MDH), the present invention is overlying on ATH, MDH inorganic particulate surface with maleic anhydride graft polyolefine and polyolefine random copolymers superpacket first, make ATH, MDH that a kind of surface has macromolecule organic superpacket coating first, started mineral-type oxyhydroxide fire retardant surface-treated new technologies.
2, its surface of the ATH of known all brands in the world, MDH does not have the superpacket coating that is made of different macromolecule organics, comprises the refined guarantor/LMT of internationally famous supplier
ATH, MDH Deng the trade mark.
3, owing to ATH, MDH inorganic particulate are the higher material of surface energy, difficulties in dispersion, lack of homogeneity in polymkeric substance, for improving consistency, flowability, the dispersiveness (uniformity coefficient) in ATH, MDH inorganic particulate and the polymeric matrix, strengthen ATH, MDH inorganic particulate and polymeric matrix coupling at aspects such as surface property, chemical property, soda acid performances, traditional treatment process mainly contains two big classes: a class is that inorganic particulate is carried out surface treatment, and another kind of is the super-refinement of inorganic particulate.
Surface treatment comprises that lipid acid (as stearic acid etc.) handles and various coupling agent (as vinyl silanes, aminosilane, aluminic acid ester, titanic acid ester etc.) processing, super-refinement claims process of refinement again, it adopts physical method that the particle diameter of ATH and MDH is ground to below the 1 μ m, but the meticulous more easy more cohesion of ATH, MDH, the caking of uniting, viscosity is high more during with polymeric matrix blend such as rubber, plastics, be unfavorable for the dispersion in polymer melt, and the oxygen index (L01) of measurement polymkeric substance flame-retardant standard improves limited.
Up to now, various treatment processs show as the effect on ATH, MDH surface: coupling agent+fatty acid treatment+become more meticulous＞coupling agent+become more meticulous＞become more meticulous+lipid acid＞fatty acid treatment＞non-processor, and the obtained effect of the organic compound coating method of the present invention is much better than above-mentioned various traditional method.
4, the purpose of this invention is to provide a kind of efficient, environmental protection, of fine quality, inexpensive ATH, MDH fire retardant, make the present consumption maximum of this class of ATH, MDH, the widest maximum usefulness of mineral-type fire retardant performance of application surface.The fire-retardant of polymer materials is the focus of being paid close attention to deeply at present, business-like fire retardant mainly divides organic and inorganic two big classes, divide addition type and response type again by using method, the inorganic additive flame retardant of this class of ATH and MDH is to human body and environmentally friendly and inexpensive, aboundresources and be widely used, but the fire retardant effect of ATH, MDH can not show a candle to halogenated flame retardant (as bromine system, chlorine system), in polymkeric substance, be added to more than 60% and could embody its flame retardant effect, so just damaged the mechanical property of polymeric matrixs such as rubber, plastics.
The present invention is overlying on ATH, MDH inorganic particulate surface with maleic anhydride graft polyolefine and polyolefine random copolymers superpacket, thereby has improved ATH, MDH consistency, flowability and the dispersiveness (uniformity coefficient) in high molecular polymer matrixes such as plastic, rubber significantly; Reduce high molecular polymers such as plastics, rubber to greatest extent because of adding the mechanical property loss of energy that a large amount of mineral-type fire retardants cause, improved the flame retardant effect of ATH, MDH effectively.
5, the present invention realizes like this: selecting for use maleic anhydride to connect skill polyolefine (PO-g-MAH) is organic compound coating material one, polyolefine random copolymers (ethylene-ethyl acetate copolymer: EVA or ethylene-ethyl acrylate copolymer: EEA) be organic compound coating material two, during production with polyolefine (high-pressure polyethylene: LDPE or ethene one octene copolymer: POE) with maleic anhydride (MAH) grafting in high-temperature fusion, make maleic anhydride graft polyolefine (PO-g-MAH) and solution thereof, ATH about fineness 5000-6000 order (the about 2-2.8 μ of particle diameter m) or MDH are joined among the coating specific equipment A by the production requirement, add vinyl silicane coupling agent earlier by proportioning, stirring fully, the back adds other coupling agents (as aminosilane), because of ATH, the molecular structure and the physical aspect of inorganicss such as MDH and organic polymer are far from it, both can not be closely linked, and a part of group of coupling agent can form strong chemical bonding with the chemical group reaction on inorganics surface, part group can twine with organism reaction or physics, so at ATH, MDH inorganic particulate surface should at first form coupling layer (internal layer), be metered into organic coating material one (PO-g-MAH) then and carry out the solution coating, discharge enters among the special purpose packet coating equipment B again, be metered into organic coating material two (EEA or EVA), finishing fusion under 120-170 ℃ of condition coats, make organic coating material one (PO-g-MAH) and organic coating material two (EVA or EEA) form organic superpacket coating (inferior skin), add lubricant again, dispersion aidss etc. form dispersion layer (skin), after discharge, aftertreatment, operations such as collection promptly get finished product.
Owing to adopted above-mentioned new technologies, thereby made the ATH that a kind of surface has the organic superpacket coating of polymer, MDH, it is respectively by kernel (inorganic particulate), internal layer, inferior skin and outer the composition, internal layer is the coupling layer that coupling agent forms, the coupling layer molecule has two kinds of active groups of different nature, on the one hand can with ATH, chemical reaction takes place in MDH inorganic particulate (kernel) surface, form chemical bond (si-o-si), on the other hand can with inferior outer field organic superpacket coating bonding, become the significant part of polymkeric substance, physical adsorption and chemical bond are together acted between inorganic particulate and the organism, organic phase and inorganic interfacial adhesion have mutually been strengthened, kernel (inorganic particulate) and polymeric matrix are effectively combined; And inferior skin not only has firm interfacial adhesion with kernel (inorganic particulate) and internal layer (coupling layer), and excellent compatibility is arranged with most of nonpolar and polarity high molecular polymers, thereby significantly reduced the infringement of the mechanical property that ATH, MDH cause to polymeric matrix, improved the flowability of inorganic particulate in polymeric matrix, dispersiveness.
Be basic components of the present invention below:
Supplementary material title weight part (proportioning)
A. metal hydroxides (ATH or MDH) 87 (86-88)
B. polyolefine (POE or LDPE) 4 (3.5-4.5)
C. polyolefine random copolymers (EVA or EEA) 3 (3.5-4.5)
D. vinyl silicane coupling agent 1.0 (0.9-1.2)
E. amino silicane coupling agent 0.8 (0-1.0)
F. lubricant (containing dispersion aids) 2 (1.7-2.1)
G. maleic anhydride or toxilic acid (MAH or MA) 0.2 (0.15-0.25)
H. other Synergist S-421 95s 2 (1.8-2.0)
Add up to: 100
The invention will be further described in conjunction with the accompanying drawings and embodiments more below:
Accompanying drawing 1 is technological process of production figure of the present invention, has intactly shown the technological process of production of the compound coating ATH of macromolecule organic, MDH.
Accompanying drawing 2 is microtexture synoptic diagram of the ATH, the MDH that have organic superpacket coating:
(1) kernel: ATH or MDH inorganic particulate in shown in the accompanying drawing 2.
(2) internal layer: coupling layer, form by single or two kinds of silane coupling agents, act between inorganic phase and the organic phase, give inorganic kernel and the good avidity of organic skin.
(3) inferior skin: the organic superpacket coating of polymer, form by maleic anhydride graft polyolefine and polyolefine random copolymers, give the excellent compatibility between kernel (inorganic particulate) and polymeric matrix.(4) skin: dispersion layer, form by lubricant and dispersion aids, give inorganic particulate better mobile, dispersed (raising uniformity coefficient) in polymer melt.
Claims (3)
1. an inorganic particulate surface has the aluminium hydroxide (ATH) and magnesium hydroxide (MDH) fire retardant of the organic superpacket coating of polymer, and it has internal layer (coupling layer), inferior skin (organic superpacket coating) and outer (lubricant film) multiple coating.
2. according to right 1; the component structure of organic superpacket coating (skin) of claimed ATH, MDH: it is characterized in that organic coating layer is made up of maleic anhydride graft polyolefine (PO-g-MAH) and polyolefine random copolymerization (EEA or EVA), the polyolefine that connects skill with maleic anhydride is high-pressure polyethylene (LDPE) or ethylene-octene copolymer (POE).
3. according to right 1; claimed organic compound coating ATH; the preparation technology of MTH inorganic particulate: prepare maleic anhydride graft polyolefine (PO-g-MAH) solution when it is characterized in that producing in advance; the ATH that in specific equipment A, adds 5000-6000 order fineness; MDH; in high-speed stirring, add coupling agent earlier and form internal layer (coupling layer); add PO-g-MAH again and under high-speed stirring, finish the solution coating; discharge enters among the specific equipment B then; add the polyolefine random copolymers; finishing fusion under 120 ℃-170 ℃ high temperature coats; add lubricant again after making two kinds of different organism form superpacket coating (inferior skin); dispersion aids forms skin, through aftertreatment; collect; promptly get finished product.
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| CN 201010171257 CN102241835A (en) | 2010-05-11 | 2010-05-11 | Organic composite coating method of surfaces of inorganic metal hydroxide flame retardant |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107001736A (en) * | 2014-12-03 | 2017-08-01 | J.M.休伯有限公司 | Metal composite core compoboard and its manufacturing process |
| CN107892959A (en) * | 2017-10-23 | 2018-04-10 | 宁波广昌达新材料有限公司 | Vanadium-inhibiting agent, the preparation method of vanadium-inhibiting agent, suppression vanadium composition and its application, the preparation method for pressing down vanadium composition |
| CN108384058A (en) * | 2018-03-26 | 2018-08-10 | 苏州纳绎博纳米科技有限公司 | Microcapsules flame retardant of magnesium hydroxide and preparation method thereof |
| CN110128726A (en) * | 2019-06-11 | 2019-08-16 | 广讯检测（广东）有限公司 | A kind of staged fire-retardant rubber material and preparation method thereof |
| CN111116991A (en) * | 2020-02-11 | 2020-05-08 | 江苏艾特克阻燃材料有限公司 | Composite hydroxide smoke-suppression type flame retardant and preparation method and application thereof |
| CN111138716A (en) * | 2019-12-31 | 2020-05-12 | 安徽科居新材料科技有限公司 | Flame retardant and wood-plastic composite material |
| CN111138768A (en) * | 2019-12-05 | 2020-05-12 | 常州聚焦橡塑新材料有限公司 | Non-vulcanized flame-retardant butyl rubber |
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| CN1880407A (en) * | 2005-06-15 | 2006-12-20 | 大连圣迈化学有限公司 | Polymerized cladded modified inorganic fire retardant and technology for processing same |
| CN101638501A (en) * | 2008-07-29 | 2010-02-03 | 比亚迪股份有限公司 | Flame retardant composite and thermoplastic elastomer containing same |
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| CN1880407A (en) * | 2005-06-15 | 2006-12-20 | 大连圣迈化学有限公司 | Polymerized cladded modified inorganic fire retardant and technology for processing same |
| CN101638501A (en) * | 2008-07-29 | 2010-02-03 | 比亚迪股份有限公司 | Flame retardant composite and thermoplastic elastomer containing same |
Cited By (13)
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| TWI707894B (en) * | 2014-12-03 | 2020-10-21 | 美商Ｊ Ｍ 胡伯公司 | Metal composite core composition panels and process for making same |
| CN107001736A (en) * | 2014-12-03 | 2017-08-01 | J.M.休伯有限公司 | Metal composite core compoboard and its manufacturing process |
| US10414912B2 (en) * | 2014-12-03 | 2019-09-17 | J.M. Huber Corporation | Metal composite core composition panels and process for making same |
| CN107892959A (en) * | 2017-10-23 | 2018-04-10 | 宁波广昌达新材料有限公司 | Vanadium-inhibiting agent, the preparation method of vanadium-inhibiting agent, suppression vanadium composition and its application, the preparation method for pressing down vanadium composition |
| CN107892959B (en) * | 2017-10-23 | 2020-03-27 | 宁波广昌达新材料有限公司 | Vanadium inhibitor, preparation method of vanadium inhibitor, vanadium-inhibiting composition and application thereof, and preparation method of vanadium-inhibiting composition |
| CN108384058A (en) * | 2018-03-26 | 2018-08-10 | 苏州纳绎博纳米科技有限公司 | Microcapsules flame retardant of magnesium hydroxide and preparation method thereof |
| CN110128726A (en) * | 2019-06-11 | 2019-08-16 | 广讯检测（广东）有限公司 | A kind of staged fire-retardant rubber material and preparation method thereof |
| CN110128726B (en) * | 2019-06-11 | 2021-06-01 | 广讯检测（广东）有限公司 | Stepped flame-retardant rubber material and preparation method thereof |
| CN111138768A (en) * | 2019-12-05 | 2020-05-12 | 常州聚焦橡塑新材料有限公司 | Non-vulcanized flame-retardant butyl rubber |
| CN111138716A (en) * | 2019-12-31 | 2020-05-12 | 安徽科居新材料科技有限公司 | Flame retardant and wood-plastic composite material |
| CN111138716B (en) * | 2019-12-31 | 2020-12-04 | 安徽科居新材料科技有限公司 | Flame retardant and wood-plastic composite material |
| CN111116991A (en) * | 2020-02-11 | 2020-05-08 | 江苏艾特克阻燃材料有限公司 | Composite hydroxide smoke-suppression type flame retardant and preparation method and application thereof |
| CN111116991B (en) * | 2020-02-11 | 2022-03-18 | 江苏艾特克阻燃材料有限公司 | Composite hydroxide smoke-suppression type flame retardant and preparation method and application thereof |
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Application publication date: 20111116 |