CN103819736B - Expandable flame retardant carbon forming agent micro encapsulation tetramethylolmethane and preparation method thereof - Google Patents
Expandable flame retardant carbon forming agent micro encapsulation tetramethylolmethane and preparation method thereof Download PDFInfo
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000003063 flame retardant Substances 0.000 title claims abstract description 43
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 9
- 229910052799 carbon Inorganic materials 0.000 title claims description 9
- 238000005538 encapsulation Methods 0.000 title claims description 6
- 229940059574 pentaerithrityl Drugs 0.000 title claims 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 30
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003094 microcapsule Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 24
- 239000002612 dispersion medium Substances 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 239000004814 polyurethane Substances 0.000 claims abstract description 10
- 229920002635 polyurethane Polymers 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 239000011859 microparticle Substances 0.000 claims description 9
- 241001502050 Acis Species 0.000 claims 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 3
- 150000002148 esters Chemical class 0.000 claims 3
- 229910052710 silicon Inorganic materials 0.000 claims 3
- 239000010703 silicon Substances 0.000 claims 3
- 238000005253 cladding Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 238000004132 cross linking Methods 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000004531 microgranule Substances 0.000 claims 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 19
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- -1 polyol compound Chemical class 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000004114 Ammonium polyphosphate Substances 0.000 description 4
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 4
- 229920001276 ammonium polyphosphate Polymers 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 239000003995 emulsifying agent Substances 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000011527 polyurethane coating Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
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- Fireproofing Substances (AREA)
Abstract
本发明提供一种膨胀阻燃成炭剂用微胶囊化季戊四醇及其制备方法。本发明采用二氧化硅或者多异氰酸酯对季戊四醇微粒进行包覆制备耐水性的季戊四醇微胶囊。本发明将季戊四醇微粒悬浮分散在不溶季戊四醇且与正硅酸酯不发生反应的惰性有机分散介质中，然后加入正硅酸酯分散或溶解在季戊四醇微粒悬浮液中，随后加入适量水，经化学反应制得二氧化硅包覆季戊四醇微胶囊；或者，将季戊四醇微粒悬浮分散在不溶季戊四醇且与多异氰酸酯不发生反应的惰性有机分散介质中，然后加入多异氰酸酯分散或溶解在季戊四醇微粒悬浮液中，通过化学反应得到聚氨酯包覆季戊四醇微胶囊。反应温度可以在室温～惰性有机分散介质沸点之间。The invention provides a microencapsulated pentaerythritol for an intumescent flame-retardant char-forming agent and a preparation method thereof. The invention adopts silicon dioxide or polyisocyanate to coat pentaerythritol particles to prepare water-resistant pentaerythritol microcapsules. The present invention suspends and disperses pentaerythritol particles in an inert organic dispersion medium that is insoluble in pentaerythritol and does not react with orthosilicate, then adds orthosilicate to disperse or dissolve in the suspension of pentaerythritol particles, and then adds an appropriate amount of water to undergo a chemical reaction. Prepare silica-coated pentaerythritol microcapsules; or, suspend and disperse pentaerythritol particles in an inert organic dispersion medium insoluble in pentaerythritol and not react with polyisocyanate, then add polyisocyanate to disperse or dissolve in pentaerythritol particle suspension, by The chemical reaction obtains polyurethane-coated pentaerythritol microcapsules. The reaction temperature can be between room temperature and the boiling point of the inert organic dispersion medium.
Description
一、技术领域1. Technical field
本发明涉及阻燃剂及其制备方法，特别涉及膨胀阻燃成炭剂及其制备方法，属于阻燃领域。The invention relates to a flame retardant and a preparation method thereof, in particular to an intumescent flame-retardant char-forming agent and a preparation method thereof, and belongs to the field of flame retardancy.
二、背景技术2. Background technology
膨胀型阻燃剂以其高效、无毒和抑烟的优点，在聚合物阻燃上得到了越来越广泛的应用。膨胀型阻燃剂通常包括酸源、炭源和气源三者。酸源主要是无机酸或能在燃烧过程中生成酸的化合物，包括磷酸、硼酸、磷酸盐类和磷酸酯类。炭源在燃烧过程中可以形成炭层，通常为含碳量极高且含有大量羟基的多元醇化合物，常用的有淀粉，季戊四醇及其衍生物等。气源起膨胀发泡的作用，多为含氮量高的化合物，如三聚氰胺、三聚氰胺氰尿酸盐等。Intumescent flame retardants have been more and more widely used in polymer flame retardancy due to their advantages of high efficiency, non-toxicity and smoke suppression. Intumescent flame retardants usually include acid source, carbon source and gas source. Acid sources are mainly inorganic acids or compounds that can generate acids during combustion, including phosphoric acid, boric acid, phosphates and phosphate esters. The charcoal source can form a charcoal layer during the combustion process. It is usually a polyol compound with a very high carbon content and a large number of hydroxyl groups. The commonly used ones are starch, pentaerythritol and its derivatives. The gas source plays the role of expansion and foaming, and most of them are compounds with high nitrogen content, such as melamine, melamine cyanurate, etc.
膨胀型阻燃剂的酸源和炭源通常容易受潮，特别是具有较高的水溶性，因此其阻燃聚合物的阻燃耐水性较差。提高耐水性成为目前膨胀型阻燃剂的研究热点。常用的方法是对膨胀型阻燃剂进行表面改性和微胶囊化。研究较多的是提高酸源(聚磷酸铵)的耐水性，技术手段有偶联剂表面改性和微胶囊化处理。但是，仅提高酸源的耐水性，对阻燃聚合物整体的阻燃耐水性改进较局限。然而，目前很少有针对炭源耐水性的改性研究，比如季戊四醇是易溶于水的化合物，提高其耐水性，对膨胀阻燃聚合物整体的阻燃耐水性具有改进效果，但是其微胶囊化不易实施。The acid source and carbon source of intumescent flame retardants are usually susceptible to moisture, especially with high water solubility, so the flame retardant and water resistance of the flame retardant polymer is poor. Improving water resistance has become a research hotspot of intumescent flame retardants. The commonly used methods are surface modification and microencapsulation of intumescent flame retardants. More research is to improve the water resistance of the acid source (ammonium polyphosphate), and the technical means include surface modification of the coupling agent and microencapsulation treatment. However, only improving the water resistance of the acid source is limited to the improvement of the flame retardant and water resistance of the flame retardant polymer as a whole. However, there are few studies on the modification of carbon source water resistance. For example, pentaerythritol is a compound that is easily soluble in water, and improving its water resistance can improve the overall flame retardancy and water resistance of intumescent flame retardant polymers, but its slight Encapsulation is not easy to implement.
三、发明内容3. Contents of the invention
本发明目的是提供一种膨胀阻燃成炭剂用微胶囊化季戊四醇及制备方法。The object of the invention is to provide a microencapsulated pentaerythritol for an intumescent flame-retardant char-forming agent and a preparation method thereof.
实现本发明目的的技术解决方案为：一种膨胀阻燃成炭剂用微胶囊化季戊四醇是采用二氧化硅对季戊四醇微粒进行包覆制备得到的二氧化硅包覆季戊四醇微胶囊或者采用多异氰酸酯对季戊四醇微粒进行包覆制备得到的聚氨酯包覆季戊四醇微胶囊。The technical solution to realize the purpose of the present invention is: a microencapsulated pentaerythritol for an intumescent flame-retardant char-forming agent is a silica-coated pentaerythritol microcapsule prepared by coating pentaerythritol particles with silica or using polyisocyanate to The polyurethane-coated pentaerythritol microcapsules prepared by coating the pentaerythritol particles.
一种膨胀阻燃成炭剂用微胶囊化季戊四醇的制备方法是：将季戊四醇微粒悬浮分散在不溶季戊四醇且与正硅酸酯不发生反应的惰性有机分散介质中，然后加入正硅酸酯分散或溶解在季戊四醇微粒悬浮液中，随后加入适量水，通过正硅酸酯发生水解及交联反应，而在季戊四醇微粒表面形成二氧化硅包覆膜层以制得二氧化硅包覆季戊四醇微胶囊。A preparation method of microencapsulated pentaerythritol for an intumescent flame-retardant char-forming agent is: suspending and dispersing pentaerythritol particles in an inert organic dispersion medium that is insoluble in pentaerythritol and does not react with orthosilicate, and then adds orthosilicate to disperse or Dissolve in pentaerythritol microparticle suspension, then add appropriate amount of water, hydrolyze and cross-link through orthosilicate, and form a silicon dioxide coating film layer on the surface of pentaerythritol microparticles to prepare silica-coated pentaerythritol microcapsules.
这里所述制备方法中反应温度可以在室温～所采用惰性有机分散介质沸点之间。In the preparation method described here, the reaction temperature can be between room temperature and the boiling point of the inert organic dispersion medium used.
一种膨胀阻燃成炭剂用微胶囊化季戊四醇的制备方法是：将季戊四醇微粒悬浮分散在不溶季戊四醇且与多异氰酸酯不发生反应的惰性有机分散介质中，然后加入多异氰酸酯分散或溶解在季戊四醇微粒悬浮液中，通过多异氰酸酯与季戊四醇微粒表面的季戊四醇之间发生化学反应，而在季戊四醇微粒表面形成聚氨酯包覆膜层以制得聚氨酯包覆季戊四醇微胶囊。A preparation method of microencapsulated pentaerythritol for an intumescent flame-retardant char-forming agent is as follows: suspending and dispersing pentaerythritol particles in an inert organic dispersion medium in which pentaerythritol is insoluble and does not react with polyisocyanate, and then adding polyisocyanate to disperse or dissolve in the pentaerythritol particles In the suspension, the polyisocyanate reacts with the pentaerythritol on the surface of the pentaerythritol particles to form a polyurethane coating film layer on the surface of the pentaerythritol particles to prepare the polyurethane-coated pentaerythritol microcapsules.
这里所述制备方法中反应温度可以在室温～所采用惰性有机分散介质沸点之间。In the preparation method described here, the reaction temperature can be between room temperature and the boiling point of the inert organic dispersion medium used.
与现有技术相比，本发明具有显著的优点。本发明采用正硅酸酯或多异氰酸酯为原料对季戊四醇进行微胶囊化制备耐水性微胶囊化季戊四醇，所制备的季戊四醇微胶囊耐水性明显提高，其所组成的膨胀型阻燃剂阻燃聚合物具有较好的耐水性。Compared with the prior art, the present invention has significant advantages. The present invention uses orthosilicate or polyisocyanate as raw materials to microencapsulate pentaerythritol to prepare water-resistant microencapsulated pentaerythritol, and the water resistance of the prepared pentaerythritol microcapsules is significantly improved, and the intumescent flame retardant flame-retardant polymer composed of Has good water resistance.
四、具体实施方式4. Specific implementation
本发明膨胀阻燃成炭剂用微胶囊化季戊四醇是采用二氧化硅对季戊四醇微粒进行包覆制备得到的二氧化硅包覆季戊四醇微胶囊或者采用多异氰酸酯对季戊四醇微粒进行包覆制备得到的聚氨酯包覆季戊四醇微胶囊。The microencapsulated pentaerythritol for the intumescent flame retardant char forming agent of the present invention is a silica-coated pentaerythritol microcapsule prepared by coating pentaerythritol particles with silicon dioxide or a polyurethane coating prepared by coating pentaerythritol particles with polyisocyanate. Covered with pentaerythritol microcapsules.
本发明膨胀阻燃成炭剂用微胶囊化季戊四醇的制备方法是：将季戊四醇微粒悬浮分散在不溶季戊四醇且与正硅酸酯不发生反应的惰性有机分散介质中，然后加入正硅酸酯分散或溶解在季戊四醇微粒悬浮液中，随后加入适量水，通过正硅酸酯发生水解及交联反应，而在季戊四醇微粒表面形成二氧化硅包覆膜层以制得二氧化硅包覆季戊四醇微胶囊。The preparation method of microencapsulated pentaerythritol for intumescent flame-retardant char-forming agent of the present invention is: suspending and dispersing pentaerythritol particles in an inert organic dispersion medium insoluble in pentaerythritol and not reacting with orthosilicate, and then adding orthosilicate to disperse or Dissolve in pentaerythritol microparticle suspension, then add appropriate amount of water, hydrolyze and cross-link through orthosilicate, and form a silicon dioxide coating film layer on the surface of pentaerythritol microparticles to prepare silica-coated pentaerythritol microcapsules.
这里所述不溶季戊四醇且与正硅酸酯不发生反应的惰性有机分散介质，比如可以是丙酮、苯、甲苯、二甲苯、四氯化碳、乙醚和石油醚等中的一种或一种以上，当然可以是其他合适的惰性有机分散介质。所用惰性有机分散介质可以不溶正硅酸酯，此时正硅酸酯可以借助乳化剂乳化分散在季戊四醇悬浮液的分散介质中；所用惰性有机分散介质最好是正硅酸酯的溶剂，此时正硅酸酯溶解在季戊四醇悬浮液的分散介质中，更有利于较好地包覆。The inert organic dispersion medium that is insoluble in pentaerythritol and does not react with orthosilicate, for example, can be one or more of acetone, benzene, toluene, xylene, carbon tetrachloride, ether and petroleum ether, etc. , of course, can be other suitable inert organic dispersion media. The inert organic dispersion medium used can be insoluble orthosilicate, and now the orthosilicate can be emulsified and dispersed in the dispersion medium of the pentaerythritol suspension by means of an emulsifier; the inert organic dispersion medium used is preferably the solvent of the orthosilicate, at this time Silicate is dissolved in the dispersion medium of pentaerythritol suspension, which is more conducive to better coating.
这里所述制备方法中反应温度可以在室温～所采用惰性有机分散介质沸点之间。比如，采用丙酮为溶剂时，反应温度可以为室温～56℃。In the preparation method described here, the reaction temperature can be between room temperature and the boiling point of the inert organic dispersion medium used. For example, when acetone is used as the solvent, the reaction temperature can be from room temperature to 56°C.
反应体系中加入适量水的作用是使正硅酸酯发生水解并进而发生脱水交联反应形成二氧化硅。水的加入摩尔数以能够完全水解正硅酸酯为宜，水与正硅酸酯的摩尔比最好为(2∶1)～(6∶1)之间。为了使正硅酸酯能够较快发生水解进而发生脱水交联反应形成二氧化硅，可以采用碱性化合物调节体系呈碱性，比如可以采用氨水调节体系PH值至碱性，PH值最好为8.5～12。当然，也可以采用酸性化合物调节体系呈酸性，比如可以采用盐酸、硫酸等调节体系PH值至酸性，PH值最好为5.5～1。The effect of adding an appropriate amount of water in the reaction system is to hydrolyze the orthosilicate and further dehydrate and cross-link to form silicon dioxide. The number of moles of water added is suitable to be able to completely hydrolyze the orthosilicate, and the molar ratio of water to orthosilicate is preferably between (2:1)-(6:1). In order to make orthosilicate hydrolyze quickly and then dehydrate and cross-link to form silica, alkaline compounds can be used to adjust the system to be alkaline. For example, ammonia water can be used to adjust the pH value of the system to alkaline. The pH value is preferably 8.5～12. Of course, acidic compounds can also be used to adjust the system to be acidic. For example, hydrochloric acid, sulfuric acid, etc. can be used to adjust the pH value of the system to acidity, and the pH value is preferably 5.5-1.
这里所述二氧化硅包覆季戊四醇微胶囊的二氧化硅包覆质量分数不宜太低，否则包覆不完全；但二氧化硅包覆质量分数也不宜太高，否则包覆成本过高。本发明所制得的二氧化硅包覆季戊四醇微胶囊的二氧化硅包覆质量分数最好为3％～20％。The silica-coated mass fraction of the silica-coated pentaerythritol microcapsules described here should not be too low, otherwise the coating will not be complete; but the silica-coated mass fraction should not be too high, otherwise the coating cost will be too high. The silica-coated mass fraction of the silica-coated pentaerythritol microcapsules prepared in the present invention is preferably 3% to 20%.
本发明膨胀阻燃成炭剂用微胶囊化季戊四醇的制备方法是：将季戊四醇微粒悬浮分散在不溶季戊四醇且与多异氰酸酯不发生反应的惰性有机分散介质中，然后加入多异氰酸酯分散或溶解在季戊四醇微粒悬浮液中，通过多异氰酸酯与季戊四醇微粒表面的季戊四醇之间发生化学反应，而在季戊四醇微粒表面形成聚氨酯包覆膜层以制得聚氨酯包覆季戊四醇微胶囊。The preparation method of the microencapsulated pentaerythritol used in the expansion flame retardant char forming agent of the present invention is: suspending and dispersing the pentaerythritol particles in an inert organic dispersion medium insoluble in pentaerythritol and not reacting with polyisocyanate, and then adding polyisocyanate to disperse or dissolve in the pentaerythritol particles In the suspension, the polyisocyanate reacts with the pentaerythritol on the surface of the pentaerythritol particles to form a polyurethane coating film layer on the surface of the pentaerythritol particles to prepare the polyurethane-coated pentaerythritol microcapsules.
这里所述本发明膨胀阻燃成炭剂用微胶囊化季戊四醇的制备方法中，季戊四醇微粒表面的包覆囊材聚氨酯层是由多异氰酸酯(比如，多苯基多亚甲基多异氰酸酯PAPI)与季戊四醇微粒表面的季戊四醇分子发生化学反应而形成，被包覆的季戊四醇微粒本身参与了包覆囊层的形成。这里所述多异氰酸酯是指异氰酸酯官能度为2或2以上的异氰酸酯，包括二异氰酸酯、三异氰酸酯和更高官能度的多异氰酸酯。In the preparation method of microencapsulated pentaerythritol for the expansion flame-retardant char-forming agent of the present invention described here, the coated capsule material polyurethane layer on the surface of pentaerythritol particles is made of polyisocyanate (for example, polyphenyl polymethylene polyisocyanate PAPI) and The pentaerythritol molecules on the surface of the pentaerythritol particles are formed by a chemical reaction, and the coated pentaerythritol particles themselves participate in the formation of the coating capsule. The polyisocyanate mentioned here refers to the isocyanate with an isocyanate functionality of 2 or more, including diisocyanate, triisocyanate and polyisocyanate with higher functionality.
这里所述不溶季戊四醇且与多异氰酸酯不发生反应的惰性有机分散介质，比如可以是丙酮、苯、甲苯、二甲苯、四氯化碳、乙醚和石油醚等中的一种或一种以上，当然可以是其他合适的惰性有机分散介质。所用惰性有机分散介质也可以不溶多异氰酸酯，此时多异氰酸酯可以借助乳化剂乳化分散在季戊四醇悬浮液的分散介质中；所用惰性有机分散介质最好是多异氰酸酯的溶剂，此时多异氰酸酯溶解在季戊四醇悬浮液的分散介质中，更利于包膜的有效形成。The inert organic dispersion medium that is insoluble in pentaerythritol and does not react with polyisocyanate described here can be, for example, one or more of acetone, benzene, toluene, xylene, carbon tetrachloride, ether and sherwood oil, etc., of course It can be other suitable inert organic dispersion medium. The used inert organic dispersing medium can also be insoluble polyisocyanate, at this moment polyisocyanate can emulsify and disperse in the dispersing medium of pentaerythritol suspension by means of emulsifier; used inert organic dispersing medium is preferably the solvent of polyisocyanate, at this moment polyisocyanate is dissolved in pentaerythritol In the dispersion medium of the suspension, it is more conducive to the effective formation of the coating.
这里所述制备方法中反应温度可以在室温～所采用惰性有机分散介质沸点之间。当然，为了提高多异氰酸酯与季戊四醇之间的反应活性和速度，可以添加合适的催化剂。In the preparation method described here, the reaction temperature can be between room temperature and the boiling point of the inert organic dispersion medium used. Of course, in order to increase the reactivity and speed between polyisocyanate and pentaerythritol, a suitable catalyst can be added.
这里所述聚氨酯包覆季戊四醇微胶囊的多异氰酸酯质量用量不宜太低，否则包覆不完全；但多异氰酸酯质量用量也不宜太高，否则包覆成本过高。多异氰酸酯质量用量最好是季戊四醇质量的3％～20％。The amount of polyisocyanate used to coat the polyurethane-coated pentaerythritol microcapsules should not be too low, otherwise the coating will not be complete; but the amount of polyisocyanate should not be too high, otherwise the cost of coating will be too high. The mass dosage of polyisocyanate is preferably 3% to 20% of the mass of pentaerythritol.
实施例1称取50g季戊四醇粉末，搅拌悬浮分散在100ml丙酮中，然后加入12g正硅酸四乙酯，加入2gTX-10乳化剂，充分乳化分散在季戊四醇微粉悬浮分散体中，加入正硅酸酯摩尔数4倍的去离子水，用28％氨水调节PH值为9.5，在40℃反应3h，反应结束后用布氏漏斗抽滤，滤饼用丙酮洗涤3到4次，经干燥后即制得二氧化硅包覆的粉末状季戊四醇微胶囊。所制得的季戊四醇微胶囊样品取10g加入到50℃的50mL水中搅拌30min后溶解率低于40％，而取10g未包覆季戊四醇加入到50℃的50mL水中搅拌仅2分钟即全部溶解。将季戊四醇微胶囊样品与改性聚磷酸铵按3∶1复配成膨胀阻燃剂，膨胀阻燃剂用量30％时，阻燃聚丙烯的阻燃级别为UL94-V0，即使50℃热水浸泡24h后，阻燃级别仍为UL94-V0。Example 1 Weigh 50g of pentaerythritol powder, stir, suspend and disperse in 100ml of acetone, then add 12g of tetraethyl orthosilicate, add 2g of TX-10 emulsifier, fully emulsify and disperse in pentaerythritol fine powder suspension dispersion, add orthosilicate Deionized water with 4 times the number of moles, adjust the pH value to 9.5 with 28% ammonia water, react at 40°C for 3 hours, filter with Buchner funnel after the reaction, wash the filter cake with acetone for 3 to 4 times, and dry it to prepare Powdered pentaerythritol microcapsules coated with silicon dioxide were obtained. 10 g of the prepared pentaerythritol microcapsule sample was added to 50 mL of water at 50 °C and stirred for 30 minutes, and the dissolution rate was lower than 40%, while 10 g of uncoated pentaerythritol was added to 50 mL of water at 50 °C and stirred for only 2 minutes to completely dissolve. Compound pentaerythritol microcapsule samples and modified ammonium polyphosphate in a ratio of 3:1 to form an intumescent flame retardant. When the amount of intumescent flame retardant is 30%, the flame-retardant grade of flame-retardant polypropylene is UL94-V0, even if hot water at 50°C After soaking for 24 hours, the flame retardant grade is still UL94-V0.
实施例2称取50g季戊四醇粉末，搅拌悬浮分散在100mL甲苯中，升温至70℃，边搅拌边用滴加用50mL甲苯稀释的8g多苯基多亚甲基多异氰酸酯(PAPI)，30min滴加完毕，继续反应2h。反应结束后抽滤，滤饼用丙酮洗涤3到4次，再经干燥后即制得聚氨酯包覆的粉末状季戊四醇微胶囊。所制得的季戊四醇微胶囊样品取10g加入到50℃的50mL水中搅拌30min后溶解率低于35％，而取10g未包覆季戊四醇加入到50℃的50mL水中搅拌仅2分钟即全部溶解。将季戊四醇微胶囊样品与改性聚磷酸铵按3∶1复配成膨胀阻燃剂，膨胀阻燃剂用量30％时，阻燃聚丙烯的阻燃级别为UL94-V0，即使50℃热水浸泡24h后，阻燃级别仍为UL94-V0。Example 2 Weigh 50g of pentaerythritol powder, stir, suspend and disperse in 100mL of toluene, raise the temperature to 70°C, add 8g of polyphenylpolymethylene polyisocyanate (PAPI) diluted with 50mL of toluene dropwise while stirring, and add dropwise Completed, continue to react for 2h. After the reaction is finished, filter with suction, wash the filter cake with acetone for 3 to 4 times, and then dry to obtain polyurethane-coated powder pentaerythritol microcapsules. 10 g of the prepared pentaerythritol microcapsule sample was added to 50 mL of water at 50 °C and stirred for 30 minutes, and the dissolution rate was lower than 35%, while 10 g of uncoated pentaerythritol was added to 50 mL of water at 50 °C and stirred for only 2 minutes to completely dissolve. Compound pentaerythritol microcapsule samples and modified ammonium polyphosphate in a ratio of 3:1 to form an intumescent flame retardant. When the amount of intumescent flame retardant is 30%, the flame retardant grade of flame retardant polypropylene is UL94-V0, even if 50 ℃ hot water After soaking for 24 hours, the flame retardant grade is still UL94-V0.
比较例1直接采用季戊四醇粉末与改性聚磷酸铵按3∶1复配成膨胀阻燃剂，膨胀阻燃剂用量30％时，阻燃聚丙烯的阻燃级别为UL94-V0，但50℃热水浸泡24h后，阻燃级别降低为无级别。Comparative example 1 directly adopts pentaerythritol powder and modified ammonium polyphosphate to compound intumescent flame retardant in 3: 1. When the amount of intumescent flame retardant is 30%, the flame retardant level of flame retardant polypropylene is UL94-V0, but the 50 ℃ After soaking in hot water for 24 hours, the flame retardant level is reduced to no level.
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