CN111995747B - 一种聚酰胺用反应型阻燃剂的制备方法及其应用 - Google Patents
一种聚酰胺用反应型阻燃剂的制备方法及其应用 Download PDFInfo
- Publication number
- CN111995747B CN111995747B CN202010968701.XA CN202010968701A CN111995747B CN 111995747 B CN111995747 B CN 111995747B CN 202010968701 A CN202010968701 A CN 202010968701A CN 111995747 B CN111995747 B CN 111995747B
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- polyamide
- chloroacetate
- dopo
- reactive flame
- 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
- 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 56
- 239000003063 flame retardant Substances 0.000 title claims abstract description 52
- 239000004952 Polyamide Substances 0.000 title claims abstract description 33
- 229920002647 polyamide Polymers 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- FOCAUTSVDIKZOP-UHFFFAOYSA-M chloroacetate Chemical compound [O-]C(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229940089960 chloroacetate Drugs 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 claims description 6
- QABLOFMHHSOFRJ-UHFFFAOYSA-N methyl 2-chloroacetate Chemical compound COC(=O)CCl QABLOFMHHSOFRJ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- QJZNRCWAXUGABH-UHFFFAOYSA-N propyl 2-chloroacetate Chemical compound CCCOC(=O)CCl QJZNRCWAXUGABH-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- -1 chloroacetic ester Chemical class 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000835 fiber Substances 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- CNPURSDMOWDNOQ-UHFFFAOYSA-N 4-methoxy-7h-pyrrolo[2,3-d]pyrimidin-2-amine Chemical compound COC1=NC(N)=NC2=C1C=CN2 CNPURSDMOWDNOQ-UHFFFAOYSA-N 0.000 description 1
- UFFRSDWQMJYQNE-UHFFFAOYSA-N 6-azaniumylhexylazanium;hexanedioate Chemical class [NH3+]CCCCCC[NH3+].[O-]C(=O)CCCCC([O-])=O UFFRSDWQMJYQNE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- LJUXFZKADKLISH-UHFFFAOYSA-N benzo[f]phosphinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=P1 LJUXFZKADKLISH-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
-
- 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
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Biochemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Molecular Biology (AREA)
- Manufacturing & Machinery (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Polyamides (AREA)
Abstract
本发明涉及到一种聚酰胺用反应型阻燃剂的制备方法及其应用。该方法包括下述步骤:将一定量的DOPO‑HQ与相应比例的缚酸剂投入三口烧瓶中,加入溶剂溶解,在50~140摄氏度的条件下滴加一定量氯乙酸酯,反应4~24小时后旋蒸除去溶剂与未反应的氯乙酸酯,加入DOPO‑HQ 2.5倍摩尔质量氢氧化钠的乙醇溶液将得到的中间体的酯键水解后加入盐酸调节pH=1,过滤,二次水洗涤3次,烘干即可得上述聚酰胺用反应型阻燃剂。产物产率为52~68%。
Description
技术领域
本发明属于一种聚酰胺用反应型阻燃剂的制备技术领域,具体涉及一种聚酰胺用反应型阻燃剂及其制备方法及其在聚酰胺中的应用。
背景技术
聚酰胺纤维具有断裂强度高、耐磨好、密度低、吸湿高、染色好等优点,在高端服饰、军***和工业丝等领域具有不可替代的地位。然而作为化学纤维主要品种的聚酰胺纤维却难以达到理想的阻燃效果,这是由于:通常需要添加高含量的阻燃剂才能达到满足要求的阻燃性能,而酰胺键较活泼,在高约260-320℃的纺丝温度时,易与阻燃剂发生化学反应、致分子链降解。因此阻燃改性易导致聚酰胺可纺性及其纤维物理机械性能恶化,所以阻燃聚酰胺纤维制备技术要求高、控制难度大,目前国内外对阻燃聚酰胺研发大多集中于树脂领域,未见阻燃聚酰胺纤维商品化产品成功开发的实例。
10-(2,5-二羟基苯基)-10-氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO-HQ)是一种磷杂菲类反应型阻燃剂,常用作覆铜板、半导体封装等高端环氧树脂的阻燃剂和固化剂,具有添加量低、阻燃效果好、不影响材料力学性能等优点。不仅如此,DOPO-HQ在聚氨酯、聚乳酸等其它聚合物中也展示出其优异的阻燃性能。然而,将DOPO-HQ引入聚酰胺时却存在明显的问题:将其作为添加型阻燃剂加入时会明显恶化聚酰胺的力学性能;酚羟基活性较低,不能作为共聚结构引入聚酰胺主链中。
发明内容
本发明的目的是针对现有技术存在的问题,首先提供一种聚酰胺用反应型阻燃剂。
本发明的另一目的是提供一种上述反应型阻燃剂的制备方法。
本发明提供的一种聚酰胺用反应型阻燃剂,其特征在于该聚酰胺用阻燃剂的结构如下:
本发明提供的上述聚酰胺用反应型阻燃剂的制备方法,其特征在于该方法的工艺步骤和条件如下:
将一定量的DOPO-HQ与相应比例的缚酸剂投入三口烧瓶中,加入溶剂溶解,在50~140摄氏度的条件下滴加一定量氯乙酸酯,反应4~24小时后旋蒸除去溶剂与未反应的氯乙酸酯,加入DOPO-HQ 2.5倍摩尔质量氢氧化钠的乙醇溶液将得到的中间体的酯键水解后加入盐酸调节pH=1,过滤,二次水洗涤3次,烘干即可得上述聚酰胺用反应型阻燃剂。
以上方法中所用的缚酸剂为三乙胺、碳酸钠、碳酸钾或吡啶中的一种或多种。
以上方法中所用的溶剂为乙醇、乙二醇***、1,4-二氧六环、甲苯、乙腈或丙酮中的一种或多种。
以上方法中所用的氯乙酸酯为氯乙酸甲酯、氯乙酸乙酯或氯乙酸丙酯中的任一种。
以上方法中所用的DOPO-HQ与氯乙酸酯的摩尔比为1:2~5。
本发明与现有技术相比,具有以下有益效果:
1、本发明提供的阻燃剂解决了DOPO-HQ不能用于聚酰胺阻燃的问题。
2、添加了本发明阻燃剂的聚酰胺纤维具有阻燃性能好、力学性能优异、可纺性强等优点。
3、本发明提供的阻燃剂是一种反应型阻燃剂,不含卤素,符合环保要求。
4、本发明提供的制备方法简单,易于控制,便于推广使用。
附图说明
图1为本发明实施2所制备的聚酰胺用反应型阻燃剂的核磁共振氢谱图。
具体实施方式
下面通过实施例对本发明作进一步说明。值得指出的是,给出的实施例不能理解为对本发明保护范围的限制,该领域的技术人员根据本发明的内容对本发明作出的一些非本质的改进和调整仍应属于本发明保护范围。
实施例1
将0.4mol的DOPO-HQ、0.8mol的三乙胺与足量的甲苯加入三口烧瓶中,升温至110℃,待DOPO-HQ完全溶解后滴加1mol的氯乙酸丙酯,1小时滴加完毕后保温反应8小时,旋蒸除去溶剂与多余的氯乙酸丙酯。加入含有1mol氢氧化钠的乙醇溶液,搅拌水解2小时后滴入盐酸调节pH=1,过滤,使用二次水洗涤三次,烘干即得上述阻燃剂,产率84%。
实施例2
将0.4mol的DOPO-HQ、0.4mol的碳酸钾与足量的乙腈加入三口烧瓶中,升温至90℃,待DOPO-HQ完全溶解后滴加2mol的氯乙酸甲酯,2小时滴加完毕后保温反应14小时,旋蒸除去溶剂与多余的氯乙酸甲酯。加入含有1mol氢氧化钠的乙醇溶液,搅拌水解2小时后滴入盐酸调节pH=1,过滤,使用二次水洗涤三次,烘干即得上述阻燃剂,产率89%。
图1为本发明实施2所制备的聚酰胺用反应型阻燃剂的核磁共振氢谱图。图中,4.0~5.0ppm的峰归属于氯乙酸酯中亚甲基的H,6.5~8.5ppm处为DOPO-HQ中芳香环上的C-H,13ppm左右为COOH的吸收峰,以上结果证明了上述阻燃剂的成功制备。
实施例3
将0.4mol的DOPO-HQ、0.4mol的碳酸钠与足量的乙二醇***加入三口烧瓶中,升温至140℃,待DOPO-HQ完全溶解后滴加1.5mol的氯乙酸乙酯,1.5小时滴加完毕后保温反应4小时,旋蒸除去溶剂与多余的氯乙酸乙酯。加入含有1mol氢氧化钠的乙醇溶液,搅拌水解2小时后滴入盐酸调节pH=1,过滤,使用二次水洗涤三次,烘干即得上述阻燃剂,产率72%。
实施例4
将0.4mol的DOPO-HQ、0.8mol的吡啶与足量的丙酮加入三口烧瓶中,升温至50℃,待DOPO-HQ完全溶解后滴加1.2mol的氯乙酸乙酯,1小时滴加完毕后保温反应23小时,旋蒸除去溶剂与多余的氯乙酸乙酯。加入含有1mol氢氧化钠的乙醇溶液,搅拌水解2小时后滴入盐酸调节pH=1,过滤,使用二次水洗涤三次,烘干即得上述阻燃剂,产率88%。
实施例5
将0.4mol的DOPO-HQ、0.8mol的三乙胺与足量的乙醇加入三口烧瓶中,升温至80℃,待DOPO-HQ完全溶解后滴加1.8mol的氯乙酸甲酯,2小时滴加完毕后保温反应16小时,旋蒸除去溶剂与多余的氯乙酸甲酯。加入含有1mol氢氧化钠的乙醇溶液,搅拌水解2小时后滴入盐酸调节pH=1,过滤,使用二次水洗涤三次,烘干即得上述阻燃剂,产率74%。
应用例1
将实施例2的阻燃剂和己二胺以1:1.5的摩尔比混合,再加入占体系总质量30wt%的去离子水作为反应溶剂,氮气保护时进行升温和搅拌,搅拌转速为50r/min;温度升至200℃后保持压力为1.5MPa,保温保压1h;0.5h内将压力降至常压,将搅拌转速降至30r/min,抽真空至-0.05MPa保持0.5h;停止搅拌,静置10~15min,氮气保护时出料制得阻燃剂盐。
按重量份数计,将97份己二酸己二胺盐和3份阻燃剂盐混合后,加入适量的己二酸,使得体系中端氨基与端羧基的摩尔比为1:1.01,再加入占体系总质量60%的去离子水,氮气保护时进行升温和搅拌,搅拌转速为200r/min;温度升至210℃后保持压力在1.85MPa,保温保压1h;将搅拌转速降至100r/min,2h内将压力降至常压;将搅拌速度降至50r/min,抽真空至0.08MPa保持1h;停止搅拌,静置10~15min,氮气保护时出料制得阻燃聚酰胺66,极限氧指数为28%。
应用例2
将实施例2的阻燃剂和戊二酸等摩尔比混合,再加入占体系总质量30wt%的去离子水作为反应溶剂,氮气保护时进行升温和搅拌,搅拌转速为50r/min;温度升至200℃后保持压力为1.5MPa,保温保压1h;0.5h内将压力降至常压,将搅拌转速降至30r/min,抽真空至-0.07MPa保持1h;停止搅拌,静置10~15min,氮气保护时出料制得阻燃剂盐。
按重量份数计,将95份己内酰胺和5份阻燃剂盐混合后,加入适量的己二胺,使得体系中端氨基与端羧基的摩尔比为1.1:1,再加入占体系总质量5%的去离子水,氮气保护时进行升温和搅拌,搅拌转速为100r/min;温度升至200℃后保持压力为0.6MPa,保温保压1h;0.5h内将压力降至常压;将搅拌转速降至50r/min,通氮气反应3h;抽真空至-0.05MPa保持1.5h;停止搅拌,静置10~15min,氮气保护时出料制得阻燃聚酰胺6,极限氧指数为29%。
Claims (7)
2.根据权利要求1所述的聚酰胺用反应型阻燃剂的制备方法,其特征在于,该方法的工艺步骤和条件如下:
将DOPO-HQ与缚酸剂投入容器中,加入溶剂溶解,在50~140℃的条件下滴加氯乙酸酯,反应4~24小时后旋蒸除去溶剂与未反应的氯乙酸酯,加入相对于DOPO-HQ 2.5倍摩尔量的氢氧化钠的乙醇溶液,将得到的中间体的酯键水解后加入盐酸调节pH=1,过滤,二次水洗涤3次,烘干即可得上述聚酰胺用反应型阻燃剂。
3.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法,其特征在于,缚酸剂为三乙胺、碳酸钠、碳酸钾或吡啶中的一种或多种。
4.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法,其特征在于,溶剂为乙醇、乙二醇***、1,4-二氧六环、甲苯、乙腈或丙酮中的一种或多种。
5.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法,其特征在于,氯乙酸酯为氯乙酸甲酯、氯乙酸乙酯或氯乙酸丙酯中的任一种。
6.根据权利要求2所述的聚酰胺用反应型阻燃剂的制备方法,其特征在于,DOPO-HQ与氯乙酸酯的摩尔比为1:2~5。
7.采用权利要求1所述的阻燃剂在制备聚酰胺中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010968701.XA CN111995747B (zh) | 2020-09-15 | 2020-09-15 | 一种聚酰胺用反应型阻燃剂的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010968701.XA CN111995747B (zh) | 2020-09-15 | 2020-09-15 | 一种聚酰胺用反应型阻燃剂的制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111995747A CN111995747A (zh) | 2020-11-27 |
CN111995747B true CN111995747B (zh) | 2022-12-02 |
Family
ID=73469375
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010968701.XA Active CN111995747B (zh) | 2020-09-15 | 2020-09-15 | 一种聚酰胺用反应型阻燃剂的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111995747B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112679538B (zh) * | 2020-12-29 | 2022-10-04 | 湖北省兴发磷化工研究院有限公司 | 一种二元酸酯类齐聚物阻燃剂的合成方法及应用 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1075848A (en) * | 1975-10-14 | 1980-04-15 | Takao Kashihara | New-phosphorus-containing compounds |
JPS61118393A (ja) * | 1984-11-15 | 1986-06-05 | Nippon Ester Co Ltd | ホスフイン酸の低級脂肪族ジカルボン酸エステル及びその製造法 |
WO2004111121A1 (ja) * | 2003-06-12 | 2004-12-23 | Fuji Electric Holdings Co., Ltd. | 反応性難燃剤及びそれを用いた難燃性樹脂加工品 |
CN102875982A (zh) * | 2012-10-15 | 2013-01-16 | 宁波优科泰科技发展有限公司 | 原位改性无卤阻燃热塑性树脂组合物及其制备方法 |
CN106832911A (zh) * | 2017-01-06 | 2017-06-13 | 东华大学 | 一种阻燃聚酰胺66及其制备方法 |
-
2020
- 2020-09-15 CN CN202010968701.XA patent/CN111995747B/zh active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1075848A (en) * | 1975-10-14 | 1980-04-15 | Takao Kashihara | New-phosphorus-containing compounds |
JPS61118393A (ja) * | 1984-11-15 | 1986-06-05 | Nippon Ester Co Ltd | ホスフイン酸の低級脂肪族ジカルボン酸エステル及びその製造法 |
WO2004111121A1 (ja) * | 2003-06-12 | 2004-12-23 | Fuji Electric Holdings Co., Ltd. | 反応性難燃剤及びそれを用いた難燃性樹脂加工品 |
CN102875982A (zh) * | 2012-10-15 | 2013-01-16 | 宁波优科泰科技发展有限公司 | 原位改性无卤阻燃热塑性树脂组合物及其制备方法 |
CN106832911A (zh) * | 2017-01-06 | 2017-06-13 | 东华大学 | 一种阻燃聚酰胺66及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CN111995747A (zh) | 2020-11-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104231262A (zh) | 一种有机磷共聚阻燃聚酰胺材料的制备方法 | |
CN111995747B (zh) | 一种聚酰胺用反应型阻燃剂的制备方法及其应用 | |
CN107501492B (zh) | 席夫碱式磷氮膨胀型阻燃剂及其制备方法和用途 | |
CN101333304B (zh) | 橡胶防老剂及其制备方法 | |
CN102911366A (zh) | 一种高吸湿染色、高弹性尼龙6的制备方法 | |
CN113336938A (zh) | 一种低熔点共聚尼龙树脂及其制备方法和应用 | |
CN104479127A (zh) | 一种己内酰胺水解聚合物及其水解聚合方法 | |
CN116622065A (zh) | 一种含呋喃环结构的生物基尼龙及其制备方法 | |
EP3763769B1 (en) | Method for preparing copolyamide resin and copolyamide hot-melt yarn | |
CN104746168A (zh) | 一种阻燃尼龙66纤维及其制备方法 | |
CN114196011A (zh) | 一种长效抗菌生物基尼龙树脂及其制备方法 | |
CN101880235A (zh) | 一种长链半芳香族尼龙盐的制备方法 | |
CN106750302B (zh) | 一种耐热、耐腐蚀的高分子量聚芳硫醚砜的制备方法 | |
CN116145279A (zh) | 一种低温溶液缩聚法制备的高阻燃芳纶纤维及其制备方法 | |
CN116693477A (zh) | 一种呋喃基尼龙盐及其制备方法 | |
CN103387665A (zh) | 一种阻燃聚酰胺材料的制备方法 | |
CN114773591A (zh) | 聚呋喃二甲酰丁二胺的制备方法 | |
CN111704715B (zh) | 一种全对位芳香族聚酰胺的制备方法 | |
CN103408752A (zh) | 一种聚间苯二甲酰间苯二胺沉析纤维胶体聚合物的制备方法 | |
CN113087885A (zh) | 一种循环再生聚酯切片的生产方法 | |
CN102190794A (zh) | 一种刚性链聚酰胺的合成方法及其合成产物 | |
CN109553770B (zh) | 一种生物基阻燃聚酰胺56及其制备方法 | |
CN106866980B (zh) | 一种半芳香族聚酰胺树脂及其制备方法 | |
CN110551284A (zh) | 一种聚对苯撑苯并二噁唑纤维的制备方法 | |
CN110951415A (zh) | 一种多异氰酸酯粘合剂及其制备方法和应用 |
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 |