CN103881333A - 一种dopo基的无卤阻燃pbt树脂制备方法 - Google Patents
一种dopo基的无卤阻燃pbt树脂制备方法 Download PDFInfo
- Publication number
- CN103881333A CN103881333A CN201410117798.8A CN201410117798A CN103881333A CN 103881333 A CN103881333 A CN 103881333A CN 201410117798 A CN201410117798 A CN 201410117798A CN 103881333 A CN103881333 A CN 103881333A
- Authority
- CN
- China
- Prior art keywords
- pbt
- ddpo
- dopo
- blend
- flame retardant
- 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.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 239000011347 resin Substances 0.000 title claims abstract description 21
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract 10
- 238000002360 preparation method Methods 0.000 title abstract description 5
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title abstract description 3
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 title abstract 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 title abstract 2
- XXHSFOMKJAVUID-KRWDZBQOSA-N (2s)-5-amino-2-[[4-[(2-amino-4-oxo-1h-quinazolin-6-yl)methylamino]benzoyl]amino]pentanoic acid Chemical compound C1=CC(C(=O)N[C@@H](CCCN)C(O)=O)=CC=C1NCC1=CC=C(NC(N)=NC2=O)C2=C1 XXHSFOMKJAVUID-KRWDZBQOSA-N 0.000 claims abstract description 69
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 31
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 12
- 150000002367 halogens Chemical class 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000012360 testing method Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 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 abstract description 25
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 abstract 1
- QAVDVRLUAPCCRQ-UHFFFAOYSA-N 2-[(5-oxo-6h-phosphanthridin-5-yl)methyl]butanedioic acid Chemical compound C1=CC=C2P(CC(CC(=O)O)C(O)=O)(=O)CC3=CC=CC=C3C2=C1 QAVDVRLUAPCCRQ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 49
- 229910052698 phosphorus Inorganic materials 0.000 description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 11
- 239000011574 phosphorus Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- -1 Polybutylene terephthalate Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000005935 nucleophilic addition reaction Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000010197 meta-analysis Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/50—Details of extruders
- B29C48/505—Screws
- B29C48/625—Screws characterised by the ratio of the threaded length of the screw to its outside diameter [L/D ratio]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
- B29C48/405—Intermeshing co-rotating screws
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
一种DOPO基的无卤阻燃PBT树脂制备方法，涉及一种阻燃PBT/DDPO共混物的装备方法，首先合成DDPO：装有机械搅拌、冷凝器、温度计、氮气导管的四口烧瓶中，加入DOPO、二甲苯，在氮气保护情况下，升温将衣康酸用二氧六环溶解好后，随后升高温度回流反应，过滤，用四氢呋喃重结晶，干燥8小时；制备PBT/DDPO共混物：PBT和DDPO按配比充分混合后加入到同向双螺杆挤出机中熔融共混，拉出造粒即可。该方法采用合成了9，10-二氢-10-（2，3-二羧基）丙基-10-磷杂菲-10-氧化物（DOPO），确定了最优合成条件，方法简单易行、收率高、易于工业化。
Description
技术领域
本发明涉及一种阻燃PBT/DDPO共混物的装备方法，特别是涉及一种DOPO基的无卤阻燃PBT树脂制备方法。
背景技术
聚对苯二甲酸丁二酯（PBT）是一个重要的热塑性工程塑料，具有高耐热性，较好的机械性能，优良的电气绝缘性能和良好的耐化学腐蚀性，因此广泛应用于汽车、电气和电子等行业，而这些应用都要求PBT具有良好的阻燃性。许多含有卤素的添加剂已经应用到PBT树脂中，主要是多溴联苯化合物，这些含卤阻燃剂对PBT树脂的阻燃效果非常明显，但是他们在燃烧或高温加工时会放出有毒、腐蚀性气体和烟雾。造成环境污染，危害人类健康，自欧盟2003年公布WEEE和RoHS两个指令以来，各种环保指令陆续出台，因此未来高分子阻燃材料将以无卤为主。在众多的无卤阻燃剂中，磷系阻燃剂已成为阻燃领域的研究热点。
含磷杂环化合物9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）是一种新型的阻燃剂，具有磷杂菲基团特有的含磷特点和活泼的P—H键，可以与其他不饱和化合物发生加成反应，或与醇发生脱水反应，与酯发生酯交换反应等，从而构建新型的小分子和聚合物，使其获得阻燃特性。由DOPO及其衍生物合成的阻燃剂具有优良的热稳定性、较高的阻燃效果，而且对环境友好，因此广泛的应用于高分子材料来改善其阻燃性，特别是可作为反应型阻燃剂来用于阻燃环氧树脂的合成。
衣康酸（IA）是一种天然的化合物，无毒，易生物降解，且廉价易得。衣康酸分子内部含有两个活泼的羧基和一个双键，双键和羧基呈共轭和超共轭结构，使得衣康酸的性质非常活泼，除可自身聚合外，也可以和不同数目的其他单体聚合，形成聚合高分子，因此广泛应用于化学合成工业。衣康酸可作为共聚单体用于苯乙烯－丁二烯－丙烯腈和丙烯酸酯乳液的生产，它也可以与DOPO发生亲核加成反应生成带有两个二个羧基的DOPO衍生物，该化合物可进一步与多羟基化合物发生共聚反应合成阻燃聚酯。
发明内容
本发明的目的在于提供一种DOPO基的无卤阻燃PBT树脂制备方法，该方法采用“一步法”用DOPO和衣康酸合成了9，10-二氢-10-（2，3-二羧基）丙基-10-磷杂菲-10-氧化物（DOPO），确定了最优合成条件，方法简单易行、收率高、易于工业化。
本发明的目的是通过以下技术方案实现的：
一种DOPO基的无卤阻燃PBT树脂制备方法，所述方法包括以下过程：
a. 首先合成DDPO：装有机械搅拌、冷凝器、温度计、氮气导管的四口烧瓶中，加入 DOPO、二甲苯，开启搅拌，在氮气保护情况下，升温到100℃，将衣康酸用二氧六环溶解好后，加入到恒压滴液漏斗中，在1小时内滴加到四口烧瓶中，随后升高温度回流反应，冷却到室温，过滤，用四氢呋喃重结晶，100℃真空干燥8小时，得DDPO白色粉末；
DDPO的合成反应式：
熔点为193.6℃，收率为90.7%；
b. 制备PBT / DDPO共混物：PBT和DDPO在110℃真空干燥8小时，按配比充分混合后加入到同向双螺杆挤出机中熔融共混，拉出造粒即可。
所述的一种DOPO基的无卤阻燃PBT树脂制备方法，其所述同向双螺杆挤出机螺杆直径为35mm，长径比为32，螺杆转速为150rpm，加工温度为200～250℃。
所述的一种DOPO基的无卤阻燃PBT树脂制备方法，其所述PBT / DDPO共混物在120℃真空干燥6小时，而后加入注射机中注塑成标准试样，注塑温度210～250℃，模具温度30℃。
本发明的优点与效果是：
1.本发明采用“一步法”用DOPO和衣康酸合成了9，10-二氢-10-（2，3-二羧基）丙基-10-磷杂菲-10-氧化物（DOPO），确定了最优合成条件。并采用傅立叶变换红外光谱、核磁共振氢谱、磷谱和元素分析对其结构进行了表征。这种方法简单易行，收率高；产品环境友，并带有两个活泼的羧基。然后将其用作阻燃剂与聚对苯二甲酸丁二酯（PBT）熔融共混以制备阻燃PBT/DDPO共混物，这种工艺过程简单，易于工业化，并且未见报道。对PBT/DDPO共混物的阻燃性、热性能和机械性能等进行了研究。最终得到了一种具有良好综合性能的无卤阻燃聚合物材料。
2.本发明以9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）和衣康酸（ITA）为原料合成了新型含磷阻燃剂9，10-二氢-10-（2，3-二羧基）丙基-10-磷杂菲-10-氧化物（DDPO），确定了最佳合成条件，并采用傅立叶变换红外光谱、核磁共振氢谱、磷谱和元素分析对其结构进行了表征。然后将其用作阻燃剂与聚对苯二甲酸丁二酯（PBT）熔融共混以制备阻燃PBT/DDPO共混物，并对PBT/DDPO共混物的阻燃性、热性能和机械性能进行了研究。随着DDPO的加入量的逐渐增加，PBT树脂的极限氧指数（LOI）不断增加，从纯PBT的21.0%增加到31.2%；当DDPO的含量为15%时，共混物的阻燃性即可达到UL 94V-0级。DOPO的加入，也使PBT树脂的拉伸强度和弯曲强度得到明显改善。结果表明：DDPO对PBT基体树脂有很好有阻燃效果，起到了阻燃和增强的双重作用，所制得的阻燃PBT树脂是一种综合性能优良、很有应用前景的材料。
附图说明
图1为本发明图1 DDPO的合成反应式；
图2 DDPO的红外光谱图；
图3a DOPO的核磁共振谱(氢谱)；
图3b DOPO的核磁共振谱(磷谱)；
图4 PBT/DDPO共混物的热重曲线；
图5 DDPO对PBT/DDPO共混物熔融指数的影响。
具体实施方式
下面结合附图所示实施例，对本发明作进一步详述。
实施例1：
DDPO的合成：在装有机械搅拌、冷凝器、温度计、氮气导管的四口烧瓶中，加入108.0g（0.5mol）DOPO、250ml二甲苯，开启搅拌，在氮气保护的情况下，升温到100℃，将65.0g衣康酸用一定量的二氧六环溶解好后，加入到恒压滴液漏斗中，在1小时内滴加到四口烧瓶中，随后升高到一定温度回流反应一定的时间，冷却到室温，过滤，用四氢呋喃重结晶，100℃真空干燥8小时，得DDPO白色粉末。熔点为193.6℃，收率为90.7%。其合成反应如图1所示 DDPO的合成反应式。
PBT / DDPO共混物的制备：PBT和DDPO在110℃真空干燥8小时，按一定的配比充分混合后加入到同向双螺杆挤出机中熔融共混，拉出造粒。螺杆直径为35mm，长径比为32，螺杆转速为150rpm，加工温度为200～250℃。
试样PBT / DDPO共混物在120℃真空干燥6小时，而后加入注射机中注塑成标准试样，注塑温度210～250℃，模具温度30℃。
其：
PBT(L2100)，中石化仪征化纤有限公司；DOPO，山东铭彬化工有限公司；衣康酸，上海实验试剂有限公司；甲苯，分析纯，国药集团化学试剂有限公司；四氢呋喃，分析纯，国药集团化学试剂有限公司；二氧六环，分析纯，国药集团化学试剂有限公司。
美国热电公司NEXUS-470型傅里叶变换红外光谱仪；德国Bruker公司Advance- 600型核磁共振波谱仪；瑞士BUCHI公司B-540型熔点仪；德国元素分析公司Vario EL Ⅲ型元素分析仪；德国耐驰公司STA449C / 41G热重分析仪；南京江宁分析仪器公司HC-2型极限的氧指数仪；南京上元分析仪器公司CZF-3型水平垂直燃烧仪；台湾高铁公司GT-7100-MI 熔融指数仪；台湾高铁公司TCS-2000型电脑系统拉力试验机；南京瑞亚高聚物装备公司TSE-35A型双螺杆挤出机；无锡格兰机械有限公司NG-120A型注塑机。
DDPO的合成与表征：DDPO是由DOPO和衣康酸在一下的条件下发生反应而得到的（如图1所示）。衣康酸的两个羧基与碳碳双键形成了共轭结构和超共轭结构，对电子有很强的吸引，使碳碳双键上的电子云密度降低，此外，双键上的电子还与羰基发生共振，所以有得于亲核体接近烯碳原子；DOPO具有磷杂环结构，具有活泼的P—H键，磷原子具有孤对电子，因此易与衣康酸发生亲核加成反应。
采用傅立叶变换红外光谱、核磁共振氢谱、磷谱和元素分析对DDPO的结构进行了表征。图2为DDPO的红外光谱，位于1708 cm– 1处的吸收峰为C = O的吸收峰，位于918 cm– 1附近的为P–O–C伸缩振动，P–C的伸缩振动在1429 cm-1处，P＝O有吸收峰在1201 cm-1附近，位于3061cm-1处的芳环上C–H的吸收峰。图3为DDPO的核磁共振谱。1H NMR：化学位移δ(ppm)：7.19～8.24(a)，2.41～2.48 (b)，2.63～2.69（c），3.40～3.45 (d)，12.39～12.45 (e)。31P NMR：化学位移δ(ppm)为 36.02 ppm（单峰）。质谱分析：计算值：C, 58.97%；H, 4.37%；实际值: C, 59.19%；H, 4.36%。其结果与所要合成的分子吻合的很好。因此，根据以上所有特征可以确定目标分子被成功的合成。图2 DDPO的红外光谱图；图3a DOPO的核磁共振谱(氢谱)；图3b DOPO的核磁共振谱(磷谱)。
影响收率的因素：在投料配比DOPO：IA=1：1（摩尔比）时，反应温度和反应时间对DDPO的收率有很大的影响。在反应温度为140℃时，反应时间对收率的影响如表1所示，随着反应时间的逐渐增加，收率逐渐增大，当反就时间为14小时，收率可达90.7%。在反应时间为14小时，反应温度对收率的影响如表2所示，随着温度的逐渐增加，收率逐渐增大。虽然此反应的进行需要较高的温度和较长的反应时间，但是该反应可以一步合成，纯化简单，收率较高。
表1 反应时间对收率的影响
| 反应时间 (h) | 6 | 8 | 10 | 12 | 14 |
| 收率 (%) | 42.5 | 68.3 | 83.1 | 87.5 | 90.7 |
表2 反应温度对收率的影响
| 反应温度(oC) | 100 | 110 | 120 | 130 | 140 |
| 收率 (%) | 62.6 | 73.3 | 82.0 | 85.4 | 90.7 |
阻燃性：采用极限氧指数（LOI）和垂直燃烧实验（UL-94）对PBT / DDPO共混物的阻燃性进行了评价，如表上所示。从表3中可以清楚的看到，随着DDPO含量的增加，材料的LOI值不断增大，从21.0%（DDPO的加入量为0份时）增加到31.2%（DDPO的加入量为25份时），共混物变得极难燃烧。阻燃性的提高也可以从垂直燃烧试验测试结果得以印证。PBT是一种易燃的材料，极限氧指数为21.0%，属UL- 94 HB级。而当DDPO的加入量增加到15份时（此时的磷含量1.35%），共混物就可以过到UL- 94 V0级，试样离火自熄。这些充分说明DDPO对PBT基体树脂有很好的阻燃作用。
表3 采用极限氧指数（LOI）和垂直燃烧实验（UL-94）对PBT / DDPO共混物的阻燃性
热稳定性：PBT/DDPO的热降解行为，其热失重结果如图4所示。纯PBT和PBT / DDPO共混物都是单级分解的，DDPO的加入使起始分解温度降低了，是因为DDPO的热稳定性较差，DDPO的热分解先于PBT基体树脂。通过分解得到聚乳酸复合材料进行。DDPO的热分解可以产生保护层来阻碍燃烧，所以随着DDPO含量的增加，共混物的阻燃性能得到提高。并且DDPO的引入可以增加残碳量，纯PBT的残碳量较低（为14.6 %），当DDPO的加入量为20%和25%时，残碳量分别增加到19.2%和20.3%，从中可以看到其很强的阻燃能力，图4 PBT/DDPO共混物的热重曲线。
机械性能：除了聚合物的阻燃性外，材料能否使用，其力学性能也起着重要的作用。添加阻燃剂后不应使材料的力学性能受到太大的影响，共混物抗拉和弯曲强度结果如表4所示。随着DDPO含量的增加，共混物的抗拉强度和弯曲强度增加，断裂伸长率下降。当DDPO的加入量为25%时，材料的抗拉强度和弯曲强度分别增加到78 MPa和95 MPa，比纯PBT增加了约38.6%和31.9%。这是因为DDPO与PBT化学结构相类似，有较好的相容性，并且其具有活性的二羧基可以与PBT的端羟基反应。在熔融共混时可以发生扩链反应，这可以用熔融指数试验来证明。
图5为DDPO对共混物熔融指数的影响。随着DDPO含量的增加，共混物的熔融指数下降很快，从而证明了扩链反应的发生，所以材料的机械强度得到提高。
表4 共混物抗拉和弯曲强度
含磷无卤阻燃剂DDPO由DOPO和衣康酸成功地合成，该合成方法采用傅立叶变换红外光谱、核磁共振氢谱、磷谱和元素分析对DDPO的结构进行了表征。并用熔融共混的方法制得了的PBT/DDPO共混物，随着DDPO的加入量的逐渐增加，PBT树脂的极限氧指数（LOI）不断增加；当DDPO的含量为15%时，共混物的阻燃性即可达到UL 94V-0级。DOPO的加入，也使PBT树脂的拉伸强度和弯曲强度得到明显改善。当DDPO的加入量为25%时，材料的抗拉强度和弯曲强度分别增加到78 MPa和95 Mpa，对共混物起到了增强的作用。
Claims (3)
1. 一种DOPO基的无卤阻燃PBT树脂制备方法，其特征在于，所述方法包括以下过程：
a. 首先合成DDPO：装有机械搅拌、冷凝器、温度计、氮气导管的四口烧瓶中，加入 DOPO、二甲苯，开启搅拌，在氮气保护情况下，升温到100℃，将衣康酸用二氧六环溶解好后，加入到恒压滴液漏斗中，在1小时内滴加到四口烧瓶中，随后升高温度回流反应，冷却到室温，过滤，用四氢呋喃重结晶，100℃真空干燥8小时，得DDPO白色粉末；
DDPO的合成反应式：
熔点为193.6℃，收率为90.7%；
b. 制备PBT / DDPO共混物：PBT和DDPO在110℃真空干燥8小时，按配比充分混合后加入到同向双螺杆挤出机中熔融共混，拉出造粒即可。
2.根据权利要求1所述的一种DOPO基的无卤阻燃PBT树脂制备方法，其特征在于，所述同向双螺杆挤出机螺杆直径为35mm，长径比为32，螺杆转速为150rpm，加工温度为200～250℃。
3.根据权利要求1所述的一种DOPO基的无卤阻燃PBT树脂制备方法，其特征在于，所述PBT / DDPO共混物在120℃真空干燥6小时，而后加入注射机中注塑成标准试样，注塑温度210～250℃，模具温度30℃。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410117798.8A CN103881333B (zh) | 2014-03-27 | 2014-03-27 | 一种dopo基的无卤阻燃pbt树脂制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410117798.8A CN103881333B (zh) | 2014-03-27 | 2014-03-27 | 一种dopo基的无卤阻燃pbt树脂制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103881333A true CN103881333A (zh) | 2014-06-25 |
| CN103881333B CN103881333B (zh) | 2016-02-03 |
Family
ID=50950481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410117798.8A Expired - Fee Related CN103881333B (zh) | 2014-03-27 | 2014-03-27 | 一种dopo基的无卤阻燃pbt树脂制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103881333B (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037723A (zh) * | 2015-06-26 | 2015-11-11 | 苏州生益科技有限公司 | 一种无卤阻燃预聚物及使用其制作的半固化片及层压板 |
| CN109400650A (zh) * | 2018-11-14 | 2019-03-01 | 湖北省兴发磷化工研究院有限公司 | 一种阻燃剂dopo-ita的合成方法 |
| CN112442088A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种带有羧基的含磷阻燃剂及其制备方法和应用 |
| CN112442072A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种带有羧酸或酸酐基团的反应型阻燃剂及其制备方法和应用 |
| CN113675466A (zh) * | 2021-08-12 | 2021-11-19 | 张火锐 | 一种全固态金属锂电池及其制备方法 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127590A (en) * | 1975-10-14 | 1978-11-28 | Toyo Boseki Kabushiki Kaisha | Phosphorus-containing compounds |
| WO2009079494A1 (en) * | 2007-12-18 | 2009-06-25 | Shell Oil Company | Flame retardant polyester composition and process for producing the same |
| CN101663374A (zh) * | 2007-04-03 | 2010-03-03 | 巴斯夫欧洲公司 | Dopo阻燃剂组合物 |
| CN102746626A (zh) * | 2012-07-02 | 2012-10-24 | 同济大学 | 一种功能化dopo阻燃天然纤维增强聚乳酸复合材料及其制备方法 |
| 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 |
-
2014
- 2014-03-27 CN CN201410117798.8A patent/CN103881333B/zh not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4127590A (en) * | 1975-10-14 | 1978-11-28 | Toyo Boseki Kabushiki Kaisha | Phosphorus-containing compounds |
| CN101663374A (zh) * | 2007-04-03 | 2010-03-03 | 巴斯夫欧洲公司 | Dopo阻燃剂组合物 |
| WO2009079494A1 (en) * | 2007-12-18 | 2009-06-25 | Shell Oil Company | Flame retardant polyester composition and process for producing the same |
| CN102746626A (zh) * | 2012-07-02 | 2012-10-24 | 同济大学 | 一种功能化dopo阻燃天然纤维增强聚乳酸复合材料及其制备方法 |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 黄君仪: "DOPO衍生物阻燃不饱和聚酯树脂的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, 15 March 2011 (2011-03-15) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105037723A (zh) * | 2015-06-26 | 2015-11-11 | 苏州生益科技有限公司 | 一种无卤阻燃预聚物及使用其制作的半固化片及层压板 |
| CN109400650A (zh) * | 2018-11-14 | 2019-03-01 | 湖北省兴发磷化工研究院有限公司 | 一种阻燃剂dopo-ita的合成方法 |
| CN109400650B (zh) * | 2018-11-14 | 2024-03-15 | 湖北省兴发磷化工研究院有限公司 | 一种阻燃剂dopo-ita的合成方法 |
| CN112442088A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种带有羧基的含磷阻燃剂及其制备方法和应用 |
| CN112442072A (zh) * | 2019-08-28 | 2021-03-05 | 广东广山新材料股份有限公司 | 一种带有羧酸或酸酐基团的反应型阻燃剂及其制备方法和应用 |
| CN113675466A (zh) * | 2021-08-12 | 2021-11-19 | 张火锐 | 一种全固态金属锂电池及其制备方法 |
| CN113675466B (zh) * | 2021-08-12 | 2023-02-24 | 张火锐 | 一种全固态金属锂电池及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103881333B (zh) | 2016-02-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cheng et al. | Benzimidazolyl-substituted cyclotriphosphazene derivative as latent flame-retardant curing agent for one-component epoxy resin system with excellent comprehensive performance | |
| Rao et al. | High strength, low flammability, and smoke suppression for epoxy thermoset enabled by a low-loading phosphorus-nitrogen-silicon compound | |
| Huo et al. | Synthesis of a novel phosphorus-nitrogen type flame retardant composed of maleimide, triazine-trione, and phosphaphenanthrene and its flame retardant effect on epoxy resin | |
| Wen et al. | A novel oligomer containing DOPO and ferrocene groups: Synthesis, characterization, and its application in fire retardant epoxy resin | |
| Yang et al. | Preparation and flame retardancy of an intumescent flame-retardant epoxy resin system constructed by multiple flame-retardant compositions containing phosphorus and nitrogen heterocycle | |
| Liang et al. | Synthesis of novel intumescent flame retardant containing phosphorus, nitrogen and boron and its application in polyethylene | |
| Liu et al. | Synthesis of a novel linear polyphosphazene-based epoxy resin and its application in halogen-free flame-resistant thermosetting systems | |
| CN103881333B (zh) | 一种dopo基的无卤阻燃pbt树脂制备方法 | |
| Liu et al. | A novel nitrogen-rich phosphinic amide towards flame-retardant, smoke suppression and mechanically strengthened epoxy resins | |
| Fang et al. | An effective flame retardant for poly (ethylene terephthalate) synthesized by phosphaphenanthrene and cyclotriphosphazene | |
| You et al. | The synthesis and characterization of a novel phosphorus–nitrogen containing flame retardant and its application in epoxy resins | |
| CN104311877B (zh) | 一种反应型尼龙阻燃剂及制备方法 | |
| CN105669760B (zh) | 一种有机磷杂菲衍生物及其制备方法与应用 | |
| Lin et al. | Synthesis of a novel highly effective flame retardant containing multivalent phosphorus and its application in unsaturated polyester resins | |
| EP2581379B1 (de) | Halogenfreies, phosphorhaltiges flammschutzmittel | |
| Wang et al. | A phosphorus-and nitrogen-containing DOPO derivative as flame retardant for polylactic acid (PLA) | |
| CN109957114B (zh) | 一种木质素膨胀型阻燃剂及其制备方法 | |
| Zhang et al. | Synthesis of a novel branched cyclophosphazene-PEPA flame retardant and its application on polypropylene | |
| You et al. | Synthesis and performance of a novel nitrogen‐containing cyclic phosphate for intumescent flame retardant and its application in epoxy resin | |
| Luo et al. | Synergistic flame-retardant behavior and mechanism of tris (3-nitrophenyl) phosphine and DOPO in epoxy resins | |
| CN113861241B (zh) | 一种桥联dopo磷氮阻燃剂及其制备方法和应用 | |
| CN113372695A (zh) | 一种环境友好的阻燃聚酯复合材料及其制备方法 | |
| CN110105395B (zh) | 一种吡啶阻燃剂及其制备方法和应用 | |
| Bao et al. | Synthesis of a novel flame retardant with phosphaphenanthrene and phosphazene double functional groups and flame retardancy of poly (lactic acid) composites | |
| CN109503884B (zh) | 一种色胺类阻燃剂及其合成和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160203 |