WO2021103082A1 - 一种耐水解、高效阻燃剂及其制备方法 - Google Patents
一种耐水解、高效阻燃剂及其制备方法 Download PDFInfo
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- flame retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 51
- 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 39
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 20
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002210 silicon-based material Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000012265 solid product Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- -1 aminopropyl Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims 1
- 229920000098 polyolefin Polymers 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000011282 treatment Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 229910052736 halogen Inorganic materials 0.000 description 7
- 150000002367 halogens Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 231100000053 low toxicity Toxicity 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- NOOYIVIUEHDMSF-PKLMIRHRSA-N (2r)-1-phenyl-n-(3-phenylpropyl)propan-2-amine;hydrochloride Chemical compound Cl.C([C@@H](C)NCCCC=1C=CC=CC=1)C1=CC=CC=C1 NOOYIVIUEHDMSF-PKLMIRHRSA-N 0.000 description 3
- 208000020369 Polymerase proofreading-related adenomatous polyposis Diseases 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- REYHEOAVVVYDDS-UHFFFAOYSA-N phosphono piperazin-1-yl hydrogen phosphate Chemical compound OP(O)(=O)OP(O)(=O)ON1CCNCC1 REYHEOAVVVYDDS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
- C08K5/5477—Silicon-containing compounds containing nitrogen containing nitrogen in a heterocyclic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/098—Esters of polyphosphoric acids or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the invention relates to a chemical flame retardant and a preparation method thereof, in particular to a hydrolysis-resistant, high-efficiency flame retardant and a preparation method thereof.
- Polyolefin is a thermoplastic synthetic resin with excellent performance. It is a colorless and translucent thermoplastic lightweight general-purpose plastic with chemical resistance, heat resistance, electrical insulation, high-strength mechanical properties, and good high wear-resistant processing properties. , So that polyolefins have been widely developed and applied in many fields such as machinery, automobiles, electronic appliances, construction, prevention, packaging and food industries. However, the biggest disadvantage in the application of polyolefins is the problem of flammability, and flammability is also a problem with most polymer materials. Due to flammability, the application range of polyolefins is greatly restricted. Therefore, the research on the flame-retardant properties of polyolefins is of great significance for expanding its applications in various fields.
- the first object of the present invention is to provide a hydrolysis-resistant, high-efficiency flame retardant;
- the second object of the present invention is a method for preparing the hydrolysis-resistant, high-efficiency flame retardant.
- the present invention adopts the following first technical solution: a hydrolysis-resistant, high-efficiency flame retardant, the molecular structure of the flame retardant is as follows:
- R 1 is an ethyl group
- R is an OC 2 H 5 group
- n is 1-200.
- the silicon-containing compound is TEOS, and R is an OC 2 H 5 group.
- the silicon-containing compound is 3-triethoxysilyl-1-propylamine KH550, ⁇ -glycidoxypropyltrimethoxysilane KH560, ⁇ -methyl
- One or more of acryloxypropyl trimethoxysilane KH570, R is an aminopropyl group or a carbonoxy group.
- the present invention adopts the following second technical solution: a method for preparing the hydrolysis-resistant, high-efficiency flame retardant in the above-mentioned first technical solution or its preferred solution, and the preparation method includes the following processes:
- Step 1 The piperazine pyrophosphate and the silicon-containing compound are reacted according to the following chemical reaction formula:
- Step 2 Filter, wash, and dry the product of the reaction in Step 1, and the obtained white powdery solid product is the hydrolysis-resistant, high-efficiency flame retardant.
- the molar ratio of the silicon-containing compound and piperazine pyrophosphate is 1:2 to 4:1.
- the solvent used in the reaction process is water and ethanol.
- the reaction temperature during the reaction is controlled at 30-70°C.
- the reaction time is 3-10 hours.
- the catalyst is ammonia water.
- the washing solvent used in the washing is water and ethanol.
- the hydrolysis-resistant, high-efficiency flame retardant and the preparation method thereof of the present invention have the following advantages:
- Hydrolysis resistant, high-efficiency flame retardant which can not only achieve the flame retardant effect, but also exist in the resin matrix in the form of covalent bonds through reaction, reducing hydrolysis, and at the same time the cured product has good mechanical properties.
- the preparation method provided by the invention is simple, the conditions are mild, the control is easy, the obtained product has high purity, and the post-processing is convenient.
- Figure 1 is a comparison diagram of electron micrographs of the raw material piperazine pyrophosphate and the white solid obtained in Example 1;
- Figure 2 is a comparison diagram of the electron microscope photographs of the raw material piperazine pyrophosphate and the white solid obtained in Example 2.
- the raw material piperazine pyrophosphate is compounded with MPP, the compounding ratio is 1:2, and then 22 parts of the compound and 78 parts of polypropylene (commodity model 7926) are used to make the composite material by a twin screw extruder at 190°C .
- the above composite materials are made into UL94 1.6mm standard specimens in an injection molding machine, and standard tests are performed on the horizontal and vertical combustion tester and the oxygen index tester. After testing, the flame retardant grade of the sample is: UL94 1.6mm V-2 grade, oxygen index 32.
- the obtained white solid is compounded with MPP in a compounding ratio of 1:2, and then 22 parts of the compound and 78 parts of polypropylene (commodity model 7926) are used to make a composite material with a twin screw extruder at 190°C.
- the above composite materials are made into UL94 1.6mm standard sample strips in an injection molding machine, and standard tests are performed on a horizontal and vertical combustion meter and an oxygen index tester. After testing, the flame retardant grade of the sample is: UL94 1.6mm V-0 grade, oxygen index 34.
- the hydrolysis-resistant, high-efficiency flame retardant in this case because it contains three flame-retardant elements of silicon, phosphorus, and nitrogen, can not only participate in the curing of polyolefins, but also has high flame-retardant efficiency, good electrical properties, halogen-free, low-smoke, and low-toxicity. And other characteristics, in line with today's concept of protecting the ecological environment, this flame retardant reduces the generation of toxic and corrosive gases during the combustion process, and improves the hydrolysis performance of piperazine pyrophosphate.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
本发明公开一种耐水解、高效阻燃剂及其制备方法,该耐水解、高效阻燃剂的制备原料包括含硅化合物和焦磷酸哌嗪,制备该阻燃剂仅需将含硅化合物和焦磷酸哌嗪在一定条件下反应一定时间,产物经过滤、洗涤、干燥等处理,所得的白色固体产物即为该阻燃剂。由于该阻燃剂该与聚烯烃等具有很好的相容性,在一定温度下可以完全溶于聚烯烃等基体的固化体系中,可以随聚烯烃等基体一起固化为一体、对固化物的力学性能影响较小,可以有效提高聚烯烃等的阻燃性能和电学性能;本发明工艺生产条件简单、产品纯度及产率较高、后处理过程简便。
Description
本发明涉及一种化学阻燃剂及其制备方法,特别是涉及一种耐水解、高效阻燃剂及其制备方法。
聚烯烃是一种性能优良的热塑性合成树脂,为无色半透明的热塑性轻质通用塑料,具有耐化学性、耐热性、电绝缘性、高强度机械性能和良好的高耐磨加工性能等,使得聚烯烃在机械、汽车、电子电器、建筑、防止、包装和食品工业等众多领域得到广泛的开发应用。然而,在聚烯烃的应用中存在的最大缺点就是易燃问题,易燃性也是大多数高分子材料所具有的问题。由于易燃,聚烯烃的应用范围受到很大的限制。因此,对聚烯烃的阻燃性能的研究对于扩大其在各个领域的应用有着重要的意义。
近些年来,阻燃学术界最为热门的课题就是含卤材料所引发的环境污染的问题,以及寻找合适的新型阻燃剂来替代含卤阻燃剂。随着对材料燃烧产物的研究分析,大量的学者认为,含卤阻燃剂在燃烧时将有少量二
英或二苯并呋喃释放,这也是含卤阻燃剂的塑料制品无法回收或销毁的重要原因。由于目前没有足够的替代品来替代全部的含卤阻燃剂,与此同时,欧洲和日本已全面禁止含卤阻燃剂的使用,这导致一些生产商处于对“环境问题”和成本问题的双重考虑,已停止阻燃剂的使用。因此,生产商这种为降低生产成本与“响应环保法规”的做法已导致严重的火灾隐患,使得极小的点火源就可使未经阻燃的器件持续燃烧。欧洲已颁布了有关电子电器废气设备的处理规范,规定含卤废物需要进行特殊的处理,这一方面推广了无卤阻燃剂的使用。
聚烯烃的阻燃研究日益趋向于阻燃剂的无卤化。用其他阻燃元素取代卤素,研制高效、低毒、低烟的无卤环保型阻燃剂及新型阻燃聚烯烃材料成为了国内外学者的研究热点,膨胀型阻燃剂(IFR)因其无卤、燃烧时低烟、低毒、无溶滴等优点成为新的阻燃研究方向之一,其中,焦磷酸哌嗪基IFR相比APP基IFR,具 有更好的阻燃作用、耐热稳定性,且应用范围更广,是极具发展潜力的无卤阻燃剂。但是焦磷酸哌嗪的耐水析出性和电学性能较差的特性也制约其的应用。
发明内容
为了解决上述技术问题,本发明的第一个目的是提供一种耐水解、高效阻燃剂;本发明的第二个目的是制备该耐水解、高效阻燃剂的方法。
为了实现上述发明的第一个目的,本发明采用如下第一技术方案:一种耐水解、高效阻燃剂,该阻燃剂的分子结构式如下:
其中,R
1为乙基,R为OC
2H
5基团、R氨丙基或碳氧基团,n为1-200。
上述第一技术方案中,优选的,所述的含硅化合物为TEOS,R为OC
2H
5基团。
上述第一技术方案中,优选的,所述的含硅化合物为3-三乙氧基甲硅烷基-1-丙胺KH550、γ-缩水甘油醚氧丙基三甲氧基硅烷KH560、γ-甲基丙烯酰氧基丙基三甲氧基硅烷KH570中的一种或多种,R为氨丙基或碳氧基团。
为了实现上述发明的第二个目的,本发明采用如下第二技术方案:一种制备上述第一技术方案或其优选方案中的耐水解、高效阻燃剂的方法,该制备方法包括以下过程:
步骤一、将焦磷酸哌嗪和含硅化合物按照如下化学反应式反应:
步骤二、将所述步骤一反应的产物经过过滤、洗涤、干燥处理,所得的白色粉末状固体产物即为所述的耐水解、高效阻燃剂。
上述第二技术方案中,优选的,所述步骤一中,所述含硅化合物和焦磷酸哌嗪的投料摩尔比为1∶2到4∶1。
上述第二技术方案中,优选的,所述步骤一中,反应过程中所用的溶剂为水和乙醇。
上述第二技术方案中,优选的,所述步骤一中,反应过程中的反应温度控制在30-70℃。
上述第二技术方案中,优选的,所述步骤一中,反应时间为3-10h。
上述第二技术方案中,优选的,所述步骤一中,所述的催化剂为氨水。
上述第二技术方案中,优选的,在所述步骤二中,所述的洗涤中所用的洗涤溶剂为水和乙醇。
本发明的耐水解、高效阻燃剂及其制备方法,具有如下优点:
1.耐水解、高效阻燃剂,既可以起到阻燃的效果,又可以通过反应以共价键的形式存在于树脂基体中,降低水解,同时固化物的力学性能良好。
2.耐水解、高效阻燃剂,具有低毒、高效环保的有点,有利于持续发展。
本发明提供的制备方法简单,条件温和,易于控制,所得的产品纯度高,后处理方便。
附图1为原料焦磷酸哌嗪与实施例1所得白色固体的电镜照片对比图;
附图2为原料焦磷酸哌嗪与实施例2所得白色固体的电镜照片对比图。
为详细说明发明的技术内容、构造特征、所达成目的及功效,下面将结合实施例并配合附图予以详细说明。
实施例1:
向装有回流冷凝管、温度计、搅拌棒的100ml三口烧瓶中加入25ml乙醇作为溶剂,再加入30ml的水,加热至40℃搅拌均匀后再加入12.3g的焦磷酸哌嗪PPAP、27.7g的TEOS和5ml氨水,保持50℃反应5h。反应结束后将混合物进行过滤、洗涤、干燥后,得到白色固体。所得固体与原料焦磷酸哌嗪SEM电镜照片对比如附图1。
实施例2:
向装有回流冷凝管、温度计、搅拌棒的250ml三口烧瓶中加入62.5ml乙醇作为溶剂,再加入75ml的水,加热至40℃搅拌均匀后再加入30.8g的PPAP焦磷酸哌嗪、62.3g的TEOS和12.5ml氨水,保持50℃反应5h。反应结束后将混合物进行过滤、洗涤、干燥后,得到白色固体。所得固体与原料样品SEM电镜照片对比如附图2。
实施例3:
向装有回流冷凝管、温度计、搅拌棒的1000ml三口烧瓶中加入250ml乙醇作为溶剂,再加入300ml的水,加热至40℃搅拌均匀后再加入123g的PPAP、277g的TEOS和125ml氨水,保持50℃反应5h。反应结束后将混合物进行过滤、洗涤、干燥后,得到白色固体。
测试对比原料样品和所得白色固体的粒径,原料样品的d(0.5)为6.908um,所得白色固体d(0.5)为27.968um
对比例:
将5g原料焦磷酸哌嗪和5g白色固体分别溶于50ml水中,搅拌均匀,10分钟后测试其电导率,原料焦磷酸哌嗪的电导率为4200uS/cm,白色固体为1200uS/cm。
将原料焦磷酸哌嗪与MPP进行复配,复配比例为1∶2,再使用22份的复配物与78份的聚丙烯(商品型号7926),190℃双螺杆挤出机制成复合材料。
将上述复合材料于注塑机中制成UL94 1.6mm标准样条,在水平垂直燃烧仪和氧指数测试仪上进行标准测试。经测试,样条的阻燃等级为:UL94 1.6mm V-2 等级,氧指数32。
将所得白色固体与MPP进行复配,复配比例为1∶2,再使用22份的复配物与78份的聚丙烯(商品型号7926),190℃双螺杆挤出机制成复合材料。
将上述复合材料于注塑机中制成UL94 1.6mm标准样条,在水平垂直燃烧仪和氧指数测试仪上进行标准测试。经测试,样条的阻燃等级为:UL94 1.6mm V-0等级,氧指数34。
本案的耐水解、高效阻燃剂,由于含有硅、磷、氮三种阻燃元素,既可以参与聚烯烃的固化,同时具有阻燃效率高、电学性能好和无卤、低烟、低毒等特点,符合当今保护生态环境的理念,这种阻燃剂在燃烧过程中减少了有毒气体和腐蚀性气体的产生,并且改善了焦磷酸哌嗪的水解性能。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
发明概述
问题的解决方案
发明的有益效果
Claims (10)
- 根据权利要求1所述的耐水解、高效阻燃剂,其特征在于,所述的含硅化合物为TEOS,R为OC 2H 5基团。
- 根据权利要求1所述的耐水解、高效阻燃剂,其特征在于,所述的含硅化合物为3-三乙氧基甲硅烷基-1-丙胺KH550、γ-缩水甘油醚氧丙基三甲氧基硅烷KH560、γ-甲基丙烯酰氧基丙基三甲氧基硅烷KH570中的一种或多种,R为氨丙基。
- 根据权利要求4所述的制备方法,其特征在于,所述步骤一中,所述含硅化合物和焦磷酸哌嗪的投料摩尔比为1∶2到1∶4。
- 根据权利要求4所述的制备方法,其特征在于,所述步骤一中,反应过程中所用的溶剂为水和乙醇。
- 根据权利要求4所述的制备方法,其特征在于,所述步骤一中,反应过程中的反应温度控制在30-70℃。
- 根据权利要求4所述的制备方法,其特征在于,所述步骤一中,反应时间为3-10h。
- 根据权利要求4所述的制备方法,其特征在于,所述步骤一中,所述的催化剂为氨水。
- 根据权利要求4所述的制备方法,其特征在于,在所述步骤二中,所述的洗涤中所用的洗涤溶剂为水和乙醇。
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