WO2023060560A1 - P-n-b flame-retardant pbs plastic and preparation method therefor - Google Patents
P-n-b flame-retardant pbs plastic and preparation method therefor Download PDFInfo
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- WO2023060560A1 WO2023060560A1 PCT/CN2021/124113 CN2021124113W WO2023060560A1 WO 2023060560 A1 WO2023060560 A1 WO 2023060560A1 CN 2021124113 W CN2021124113 W CN 2021124113W WO 2023060560 A1 WO2023060560 A1 WO 2023060560A1
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000003063 flame retardant Substances 0.000 title claims abstract description 94
- 239000004033 plastic Substances 0.000 title claims abstract description 35
- 229920003023 plastic Polymers 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004631 polybutylene succinate Substances 0.000 claims abstract description 57
- 229920002961 polybutylene succinate Polymers 0.000 claims abstract description 57
- -1 polybutylene succinate Polymers 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000013638 trimer Substances 0.000 claims description 22
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 claims description 13
- 238000001125 extrusion Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000779 smoke Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- BLZVCIGGICSWIG-UHFFFAOYSA-N 2-aminoethoxydiphenylborane Chemical compound C=1C=CC=CC=1B(OCCN)C1=CC=CC=C1 BLZVCIGGICSWIG-UHFFFAOYSA-N 0.000 abstract 2
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000002390 rotary evaporation Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 230000000670 limiting effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004786 cone calorimetry Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- C08K5/55—Boron-containing compounds
-
- 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
- C07F9/6581—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 nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
Definitions
- the invention belongs to the technical field of flame-retardant plastics, and in particular relates to a P-N-B flame-retardant PBS plastic and a preparation method thereof.
- Polybutylene succinate is a polymer with good biodegradability. Compared with biodegradable plastics such as polylactic acid, polyhydroxyalkanoate, and polycaprolactone, the price of PBS is relatively low. Excellent mechanical properties, wide range of uses. However, a large number of saturated hydrocarbon structures in PBS have serious flammability hazards, and the molten droplets are obvious during the combustion process, which increases the difficulty of fire search and rescue and reduces the probability of escape.
- Patent CN109627452A discloses a polybutylene succinate-based flame retardant material, the flame retardant can achieve a higher limiting oxygen index (36%) under the condition of more than 20wt% of the content of the flame retardant, and the flame retardant efficiency is relatively high.
- patent CN101781445A discloses an intumescent flame-retardant polybutylene succinate, in which a variety of additives are required, and various additives are compatible with the matrix Inconsistencies in the performance of flame-retardant plastics will have a certain impact on the performance of flame-retardant plastics during long-term use. At the same time, it is necessary to obtain high flame-retardant properties under the condition of a dosage of up to 20wt%, and the flame-retardant efficiency is low. And the preparation process involved More complex, not conducive to promotion.
- the main purpose of the present invention is to provide a kind of P-N-B composite PBS flame-retardant plastics for the deficiencies in the prior art, and utilize the product obtained by reacting phosphonochloride trimer and 2-aminoethyl biphenyl borate
- the modification of butanediol ester can effectively improve the flame retardancy, smoke suppression and anti-dripping properties of polybutylene succinate and maintain its mechanical properties, and the preparation method involved is relatively simple and has broad application prospects.
- a PNB composite PBS flame-retardant plastic which is made of PNB flame retardant and polybutylene succinate as raw materials, which are mixed and extruded in sequence; wherein the PNB flame retardant is made of phosphonyl chloride trimer and 2 -Aminoethyl biphenyl borate is the main raw material to react (-P-Cl in the phosphonyl chloride trimer reacts with -NH in 2 -aminoethyl biphenyl borate to generate -P-NH -)get.
- the mass ratio of the P-N-B flame retardant to polybutylene succinate (PBS) is (1-25):(75-99).
- the mass ratio of the P-N-B flame retardant to PBS is (2-8):(92-98); for the unit dosage of PBS, excellent flame retardancy can be achieved under the condition of low flame retardant dosage performance.
- the mass ratio of the P-N-B flame retardant to PBS is (2-4):(96-98).
- the mass ratio of the P-N-B flame retardant to PBS is (15 ⁇ 25):(75 ⁇ 85); the flame retardant properties of the resulting PBS products can be significantly improved (limiting oxygen index can reach 39%); and it is in In the cone calorimetry test, it showed strong smoke suppression (the smoke production decreased by 47%), which can greatly improve the safety of people's lives in the fire, and can also be used for the preparation of high-performance PBS flame-retardant environmental protection materials and their performance. Further optimization provides a certain research basis.
- the preparation method of the P-N-B flame retardant includes the following steps: dissolving the phosphonochloride trimer and 2-aminoethyl biphenyl borate in an organic solvent, mixing them uniformly, and using a condensation reflux device to Under an anhydrous and protective atmosphere, the resulting mixed solution is stirred and reacted, and then filtered, washed and dried to obtain the P-N-B flame retardant.
- the molar ratio of the phosphonochloride trimer to 2-aminoethyl biphenyl borate is 1:(4-6).
- the molar ratio of the phosphonochloride trimer to 2-aminoethyl biphenyl borate is 1:(5-6).
- the stirring reaction temperature is 0-120° C., and the time is 6-24 hours.
- the reaction is first performed at 0-30° C. for 2-4 hours, and then heated to 60-120° C. for 4-20 hours.
- the organic solvent can be selected from N,N-dimethylformamide, dimethyl sulfoxide, toluene or xylene and the like.
- the concentration of the phosphonochloride trimer in the obtained mixed solution is 0.01-1 mol/L.
- the protective atmosphere includes nitrogen or argon.
- the preparation method of the above-mentioned P-N-B composite PBS flame-retardant plastic specifically includes the following steps: P-N-B flame retardant and PBS are placed in a twin-screw extruder through premixing, and the materials are mixed in the twin-screw extruder, extruded Obtain the PBS flame-retardant plastic.
- the extrusion temperature is 80-110° C.
- the extrusion pressure is 10-20 MPa.
- the present invention uses phosphonochloride trimer and 2-aminoethyl biphenyl borate as main raw materials and optimizes its reaction conditions.
- the obtained P-N-B flame retardant has multi-element functionality and can effectively improve the carbon layer. Compactness and stability, inhibiting the heat and oxygen exchange of the matrix, significantly improving the flame retardant performance and reducing its burning drop; it is applied to the preparation of PBS plastic products, especially under the condition of low dosage, it can effectively take into account good mechanical properties and Excellent flame retardant properties;
- the P-N-B flame retardant obtained in the present invention can greatly reduce the smoke production of the material while fully exerting its excellent flame retardant performance, and effectively improve the fire escape rate;
- the present invention can further increase the amount of filler, and significantly improve its flame retardant performance, which can provide a certain amount for the preparation of high-performance PBS flame-retardant environmental protection materials and the further optimization of their performance.
- the PBS raw material used is from Thailand PTT Company. It is worth noting that the raw materials used in the following examples are all calculated in parts by mass.
- a kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
- a kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
- a kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
- a kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
- a kind of PBS flame-retardant plastics comprises the steps:
- a kind of PBS flame-retardant plastics comprises the steps:
- a PBS flame-retardant plastic the preparation method of which comprises the following steps: 4 parts of 2-aminoethyl biphenyl borate and 96 parts of PBS are premixed and then put into a twin-screw extruder, and the barrel temperature is controlled at 110°C , the extrusion pressure is 15 MPa, extruded and shredded to obtain PBS flame-retardant plastic 7.
- Example 1 18.7 30.2 V-1, no burning drops 14.2
- Example 2 18.4 32.6 V-0, no burning drops 13.6
- Example 3 15.2 37.8 V-0, no burning drops 10.2
- Example 4 11.4 39.2 V-0, no burning drops 8.5 Comparative example 1 17.8 35.4 V-2, with burning drops 15.4 Comparative example 2 13.3 28.9 V-2, with burning drops 18.9 Comparative example 3 16.4 25.4 NR, with burning drops 17.6
- the obtained P-N-B flame retardant of the present invention can significantly improve the flame retardancy of PBS plastic products, especially when the mol ratio of phosphonochloride trimer and 2-aminoethyl biphenyl borate is 1:6.
- the prepared P-N-B flame retardant can exhibit excellent flame retardant performance under the condition of low dosage of about 4wt%, on the basis of ensuring the good mechanical properties of the obtained PBS product; in addition, the flame retardant has obvious inhibition Smoke and anti-dripping effects have an important impact on improving the fire survival rate.
- the content of flame retardant fillers can be further effectively increased, thereby significantly improving the resistance of the obtained PBS products. flammability.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
A P-N-B and PBS composite flame-retardant plastic, which is formed by sequentially mixing and extruding a P-N-B flame retardant and polybutylene succinate as raw materials, wherein the P-N-B flame retardant is obtained by reacting a phosphonitrilic chloride trimer and 2-aminoethyl diphenylborinate as main raw materials. The P-N-B flame retardant is prepared by the reaction of the phosphonitrilic chloride trimer and 2-aminoethyl diphenylborinate, and is applied to the preparation of a PBS plastic product, thus both good mechanical properties and excellent flame retardant properties can be effectively achieved, the problems, such as smoke production and burning droplets, of the material can be greatly reduced, effectively improving the fire escape rate, and the P-N-B and PBS composite flame-retardant plastic is suitable for popularization for application.
Description
本发明属于阻燃塑料技术领域，具体涉及一种P-N-B阻燃PBS塑料及其制备方法。The invention belongs to the technical field of flame-retardant plastics, and in particular relates to a P-N-B flame-retardant PBS plastic and a preparation method thereof.
聚丁二酸丁二醇酯(PBS)是具有良好可生物降解性能的聚合物，与聚乳酸、聚羟基烷酸酯、聚己内酯等可生物降解塑料相比，PBS价格相对较低，力学性能优异，用途广泛。然而PBS中大量的饱和烃类结构存在着严重的易燃隐患，且燃烧过程中熔滴明显，扩大火灾搜救难度及降低了逃生几率。Polybutylene succinate (PBS) is a polymer with good biodegradability. Compared with biodegradable plastics such as polylactic acid, polyhydroxyalkanoate, and polycaprolactone, the price of PBS is relatively low. Excellent mechanical properties, wide range of uses. However, a large number of saturated hydrocarbon structures in PBS have serious flammability hazards, and the molten droplets are obvious during the combustion process, which increases the difficulty of fire search and rescue and reduces the probability of escape.
目前大部分阻燃塑料的环境问题亟待解决或同时存在阻燃效率低、对机械性能影响较大等问题。如：专利CN109627452A公开了一种聚丁二酸丁二醇酯基阻燃材料，阻燃剂在20wt％以上的掺量条件下才能实现较高的极限氧指数(36％)，阻燃效率较低，且较高的阻燃剂添加量容易进一步影响力学性能等；专利CN101781445A公开了一种膨胀阻燃聚丁二酸丁二醇酯，其中需要使用多种添加剂，各种添加剂与基体相容性不一致，在长期使用过程中会对阻燃塑料的使用性能产生一定影响，同时需要在高达20wt％的掺量条件下得到较高的阻燃性能，阻燃效率较低，且涉及的制备工艺较为复杂，不利于推广。At present, most of the environmental problems of flame-retardant plastics need to be solved urgently, or there are problems such as low flame-retardant efficiency and great influence on mechanical properties. Such as: Patent CN109627452A discloses a polybutylene succinate-based flame retardant material, the flame retardant can achieve a higher limiting oxygen index (36%) under the condition of more than 20wt% of the content of the flame retardant, and the flame retardant efficiency is relatively high. Low, and higher flame retardant additions are likely to further affect mechanical properties; patent CN101781445A discloses an intumescent flame-retardant polybutylene succinate, in which a variety of additives are required, and various additives are compatible with the matrix Inconsistencies in the performance of flame-retardant plastics will have a certain impact on the performance of flame-retardant plastics during long-term use. At the same time, it is necessary to obtain high flame-retardant properties under the condition of a dosage of up to 20wt%, and the flame-retardant efficiency is low. And the preparation process involved More complex, not conducive to promotion.
因此，进一步探索和优化阻燃型PBS塑料，提高其阻燃性能并增强其抗滴落能力，具有重要的研究和应用意义。Therefore, it is of great research and application significance to further explore and optimize flame-retardant PBS plastics, improve their flame-retardant properties and enhance their anti-dripping ability.
发明内容Contents of the invention
本发明的主要目的在于针对现有技术存在的不足，提供一种P-N-B复合PBS阻燃塑料，利用膦酰氯三聚体和2-氨基乙基联苯基硼酸酯反应所得产物对聚丁二酸丁二醇酯进行改性，可有效提高聚丁二酸丁二醇酯的阻燃、抑烟、抗滴落性能并保持其力学性能，且涉及的制备方法较简单，具有广阔的应用前景。The main purpose of the present invention is to provide a kind of P-N-B composite PBS flame-retardant plastics for the deficiencies in the prior art, and utilize the product obtained by reacting phosphonochloride trimer and 2-aminoethyl biphenyl borate The modification of butanediol ester can effectively improve the flame retardancy, smoke suppression and anti-dripping properties of polybutylene succinate and maintain its mechanical properties, and the preparation method involved is relatively simple and has broad application prospects.
为实现上述目的，本发明采用的技术方案为：To achieve the above object, the technical solution adopted in the present invention is:
一种P-N-B复合PBS阻燃塑料，它以P-N-B阻燃剂和聚丁二酸丁二醇酯为原料，依次进行混料和挤出而成；其中P-N-B阻燃剂以膦酰氯三聚体和2-氨基乙基联苯基硼酸酯为主要原料进行反应(膦酰氯三聚体中的-P-Cl与2-氨基乙基联苯基硼酸酯中的-NH
2反应生成-P-NH-)得到。
A PNB composite PBS flame-retardant plastic, which is made of PNB flame retardant and polybutylene succinate as raw materials, which are mixed and extruded in sequence; wherein the PNB flame retardant is made of phosphonyl chloride trimer and 2 -Aminoethyl biphenyl borate is the main raw material to react (-P-Cl in the phosphonyl chloride trimer reacts with -NH in 2 -aminoethyl biphenyl borate to generate -P-NH -)get.
上述方案中，所述P-N-B阻燃剂与聚丁二酸丁二醇酯(PBS)的质量比为(1～25):(75～99)。In the above scheme, the mass ratio of the P-N-B flame retardant to polybutylene succinate (PBS) is (1-25):(75-99).
优选的，所述P-N-B阻燃剂和PBS的质量比为(2～8):(92～98)；针对单位用量的PBS，在低阻燃剂掺量的条件下即可实现优异的阻燃性能。Preferably, the mass ratio of the P-N-B flame retardant to PBS is (2-8):(92-98); for the unit dosage of PBS, excellent flame retardancy can be achieved under the condition of low flame retardant dosage performance.
更优选的，所述P-N-B阻燃剂和PBS的质量比为(2～4):(96～98)。More preferably, the mass ratio of the P-N-B flame retardant to PBS is (2-4):(96-98).
优选的，所述P-N-B阻燃剂和PBS的质量比为(15～25):(75～85)；可显著提升所得PBS制品的阻燃性能(极限氧指数可达39％)；并且其在锥形量热测试中表现出较强的抑烟性(产烟量下降47％)，能大大提高火灾中人民的生命安全，同时也可为高性能PBS阻燃环保材料的制备及其性能的进一步优化提供一定研究基础。Preferably, the mass ratio of the P-N-B flame retardant to PBS is (15～25):(75～85); the flame retardant properties of the resulting PBS products can be significantly improved (limiting oxygen index can reach 39%); and it is in In the cone calorimetry test, it showed strong smoke suppression (the smoke production decreased by 47%), which can greatly improve the safety of people's lives in the fire, and can also be used for the preparation of high-performance PBS flame-retardant environmental protection materials and their performance. Further optimization provides a certain research basis.
上述方案中，所述P-N-B阻燃剂的制备方法包括如下步骤：将膦酰氯三聚体和2-氨基乙基联苯基硼酸酯溶于有机溶剂中，混合均匀，在有冷凝回流装置作用下将所得混合溶液在无水及保护气氛下，进行搅拌反应，再经过滤、清洗、烘干，得所述P-N-B阻燃剂。In the above scheme, the preparation method of the P-N-B flame retardant includes the following steps: dissolving the phosphonochloride trimer and 2-aminoethyl biphenyl borate in an organic solvent, mixing them uniformly, and using a condensation reflux device to Under an anhydrous and protective atmosphere, the resulting mixed solution is stirred and reacted, and then filtered, washed and dried to obtain the P-N-B flame retardant.
上述方案中，所述膦酰氯三聚体与2-氨基乙基联苯基硼酸酯的摩尔比为1:(4～6)。In the above scheme, the molar ratio of the phosphonochloride trimer to 2-aminoethyl biphenyl borate is 1:(4-6).
优选的，所述膦酰氯三聚体与2-氨基乙基联苯基硼酸酯的摩尔比为1:(5～6)。Preferably, the molar ratio of the phosphonochloride trimer to 2-aminoethyl biphenyl borate is 1:(5-6).
上述方案中，所述搅拌反应温度为0～120℃，时间为6～24h。In the above scheme, the stirring reaction temperature is 0-120° C., and the time is 6-24 hours.
优选的，所述搅拌反应步骤中，首先在0～30℃反应2～4h，然后升温至60～120℃反应4～20h。Preferably, in the stirring reaction step, the reaction is first performed at 0-30° C. for 2-4 hours, and then heated to 60-120° C. for 4-20 hours.
上述方案中，所述有机溶剂可选用N,N-二甲基甲酰胺、二甲亚砜、甲苯或二甲苯等。In the above scheme, the organic solvent can be selected from N,N-dimethylformamide, dimethyl sulfoxide, toluene or xylene and the like.
上述方案中，所得混合液中膦酰氯三聚体的浓度为0.01～1mol/L。In the above scheme, the concentration of the phosphonochloride trimer in the obtained mixed solution is 0.01-1 mol/L.
上述方案中，所述保护气氛包括氮气或氩气等。In the above solution, the protective atmosphere includes nitrogen or argon.
上述一种P-N-B复合PBS阻燃塑料的制备方法，具体包括如下步骤：将P-N-B阻燃剂和PBS经过预混置于双螺杆挤出机中，在双螺杆挤出机中进行混料，挤出得所述PBS阻燃塑料。The preparation method of the above-mentioned P-N-B composite PBS flame-retardant plastic specifically includes the following steps: P-N-B flame retardant and PBS are placed in a twin-screw extruder through premixing, and the materials are mixed in the twin-screw extruder, extruded Obtain the PBS flame-retardant plastic.
上述方案中，所述挤出温度为80～110℃，挤出压力为10～20Mpa。In the above solution, the extrusion temperature is 80-110° C., and the extrusion pressure is 10-20 MPa.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
1)本发明以膦酰氯三聚体和2-氨基乙基联苯基硼酸酯为主要原料并优化其反应条件，所得P-N-B阻燃剂兼具多元素的功能性，可有效提高炭层的致密性及稳定性，抑制基体的热氧交换，显著提高阻燃性能并降低其燃滴性；将其应用于制备PBS塑料制品，尤其在低掺量条件下即可有效兼顾良好的力学性能和优异的阻燃性能；1) The present invention uses phosphonochloride trimer and 2-aminoethyl biphenyl borate as main raw materials and optimizes its reaction conditions. The obtained P-N-B flame retardant has multi-element functionality and can effectively improve the carbon layer. Compactness and stability, inhibiting the heat and oxygen exchange of the matrix, significantly improving the flame retardant performance and reducing its burning drop; it is applied to the preparation of PBS plastic products, especially under the condition of low dosage, it can effectively take into account good mechanical properties and Excellent flame retardant properties;
2)本发明所得P-N-B阻燃剂在充分发挥优异的阻燃性能的同时，能够大大降低材料的产烟量，有效提高火灾逃生率；2) The P-N-B flame retardant obtained in the present invention can greatly reduce the smoke production of the material while fully exerting its excellent flame retardant performance, and effectively improve the fire escape rate;
3)在保证所得PBS制品基本使用性能的基础上，本发明可进一步增大填料量，并显著提升其阻燃性能，可为高性能PBS阻燃环保材料的制备及其性能的进一步优化提供一定研究基础。3) On the basis of ensuring the basic performance of the obtained PBS products, the present invention can further increase the amount of filler, and significantly improve its flame retardant performance, which can provide a certain amount for the preparation of high-performance PBS flame-retardant environmental protection materials and the further optimization of their performance. research Foundation.
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.
以下实施例中，采用的PBS原料源自泰国PTT公司。值得说明的是，以下实施例中所使用的原料均按质量份计算。In the following examples, the PBS raw material used is from Thailand PTT Company. It is worth noting that the raw materials used in the following examples are all calculated in parts by mass.
实施例1Example 1
一种P-N-B复合PBS阻燃塑料，其制备方法包括如下步骤：A kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
1)将0.41份膦酰氯三聚体(PCT)和1.59份2-氨基乙基联苯基硼酸酯(膦酰氯三聚体和2-氨基乙基联苯基硼酸酯的摩尔比为1:6)溶于N,N-二甲基甲酰胺(调节c(PCT)＝0.01mol/L)中，将所得混合溶液置于无水及氮气保护气氛的磁力搅拌条件下，首先在0℃反应2h，然后在60℃反应6h，旋蒸除去溶剂后得P-N-B阻燃剂；1) Mix 0.41 parts of phosphonyl chloride trimer (PCT) and 1.59 parts of 2-aminoethyl biphenyl borate (the molar ratio of phosphonyl chloride trimer and 2-aminoethyl biphenyl borate is 1 :6) Dissolved in N,N-dimethylformamide (adjusting c(PCT)=0.01mol/L), the resulting mixed solution was placed under magnetic stirring conditions of anhydrous and nitrogen protection atmosphere, first at 0°C React for 2 hours, then react at 60°C for 6 hours, and get P-N-B flame retardant after removing the solvent by rotary evaporation;
2)将2份所得P-N-B阻燃剂和98份PBS预混后投入双螺杆挤出机中，料筒温度控制在110℃，挤出压力为15MPa，进行挤出、剪碎，得到P-N-B复合PBS阻燃塑料1。2) Put 2 parts of the obtained P-N-B flame retardant and 98 parts of PBS into a twin-screw extruder after premixing. The temperature of the barrel is controlled at 110 ° C, and the extrusion pressure is 15 MPa. Extrude and shred to obtain P-N-B composite PBS Flame retardant plastic1.
实施例2Example 2
一种P-N-B复合PBS阻燃塑料，其制备方法包括如下步骤：A kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
1)将0.41份膦酰氯三聚体(PCT)和1.59份2-氨基乙基联苯基硼酸酯溶于N,N-二甲基甲酰胺(调节c(PCT)＝0.01mol/L)中，将所得混合溶液置于无水及氮气保护气氛的磁力搅拌条件下，首先在0℃反应2h，然后在60℃反应6h，旋蒸除去溶剂后得P-N-B阻燃剂；1) Dissolve 0.41 parts of phosphonochloride trimer (PCT) and 1.59 parts of 2-aminoethyl biphenyl borate in N,N-dimethylformamide (adjust c(PCT)=0.01mol/L) , the resulting mixed solution was placed under the condition of magnetic stirring under anhydrous and nitrogen protection atmosphere, firstly reacted at 0°C for 2h, then reacted at 60°C for 6h, and obtained P-N-B flame retardant after rotary evaporation to remove the solvent;
2)将4份所得P-N-B阻燃剂和96份PBS预混后投入双螺杆挤出机中，料筒温度控制在110℃，挤出压力为15MPa，进行挤出、剪碎，得到P-N-B复合PBS阻燃塑料2。2) Premix 4 parts of the obtained P-N-B flame retardant and 96 parts of PBS and put them into a twin-screw extruder. The barrel temperature is controlled at 110°C, and the extrusion pressure is 15MPa. Extrude and shred to obtain P-N-B composite PBS Flame retardant plastic 2.
实施例3Example 3
一种P-N-B复合PBS阻燃塑料，其制备方法包括如下步骤：A kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
1)将0.41份膦酰氯三聚体(PCT)和1.59份2-氨基乙基联苯基硼酸酯溶于N,N-二甲基甲酰胺(调节c(PCT)＝0.01mol/L)中，将所得混合溶液置于无水及氮气保护气氛的磁力搅拌条件下，首先在0℃反应2h，然后在60℃反应6h，旋蒸除去溶剂后得P-N-B阻燃剂；1) Dissolve 0.41 parts of phosphonochloride trimer (PCT) and 1.59 parts of 2-aminoethyl biphenyl borate in N,N-dimethylformamide (adjust c(PCT)=0.01mol/L) , the resulting mixed solution was placed under the condition of magnetic stirring under anhydrous and nitrogen protection atmosphere, firstly reacted at 0°C for 2h, then reacted at 60°C for 6h, and obtained P-N-B flame retardant after rotary evaporation to remove the solvent;
2)将8份所得P-N-B阻燃剂和92份PBS预混后投入双螺杆挤出机中，料筒温度控制在110℃，挤出压力为15MPa，进行挤出、剪碎，得到P-N-B复合PBS阻燃塑料3。2) Put 8 parts of the obtained P-N-B flame retardant and 92 parts of PBS into a twin-screw extruder after premixing. The barrel temperature is controlled at 110°C, and the extrusion pressure is 15MPa. Extrude and shred to obtain P-N-B composite PBS Flame retardant plastic3.
实施例4Example 4
一种P-N-B复合PBS阻燃塑料，其制备方法包括如下步骤：A kind of P-N-B composite PBS flame-retardant plastics, its preparation method comprises the steps:
1)将0.41份膦酰氯三聚体(PCT)和1.59份2-氨基乙基联苯基硼酸酯溶于N,N-二甲基甲酰胺(调节c(PCT)＝0.01mol/L)中，将所得混合溶液置于无水及氮气保护气氛的磁力搅拌条件下，首先在0℃反应2h，然后在60℃反应6h，旋蒸除去溶剂后得P-N-B阻燃剂；1) Dissolve 0.41 parts of phosphonochloride trimer (PCT) and 1.59 parts of 2-aminoethyl biphenyl borate in N,N-dimethylformamide (adjust c(PCT)=0.01mol/L) , the resulting mixed solution was placed under the condition of magnetic stirring under anhydrous and nitrogen protection atmosphere, firstly reacted at 0°C for 2h, then reacted at 60°C for 6h, and obtained P-N-B flame retardant after rotary evaporation to remove the solvent;
2)将16份所得P-N-B阻燃剂和84份PBS预混后投入双螺杆挤出机中，料筒温度控制在110℃，挤出压力为15MPa，进行挤出、剪碎，得到P-N-B复合PBS阻燃塑料4。2) Put 16 parts of the obtained P-N-B flame retardant and 84 parts of PBS into a twin-screw extruder after premixing. The temperature of the barrel is controlled at 110 ° C, and the extrusion pressure is 15 MPa. Extrude and shred to obtain P-N-B composite PBS Flame retardant plastic4.
对比例1Comparative example 1
一种PBS阻燃塑料，其制备方法包括如下步骤：A kind of PBS flame-retardant plastics, its preparation method comprises the steps:
1)将1.36份膦酰氯三聚体(PCT)和2.64份2-氨基乙基联苯基硼酸酯(膦酰氯三聚体和2-氨基乙基联苯基硼酸酯的摩尔比为1:3)溶于相应量的N,N-二甲基甲酰胺(调节c(PCT)＝0.01mol/L)中，置于无水及氮气保护气氛的磁力搅拌条件下，首先在0℃反应2h，然后在60℃反应6h，旋蒸除去溶剂后得P-N-B阻燃剂；1) Mix 1.36 parts of phosphonyl chloride trimer (PCT) and 2.64 parts of 2-aminoethyl biphenyl borate (the molar ratio of phosphonyl chloride trimer and 2-aminoethyl biphenyl borate is 1 :3) Dissolve in a corresponding amount of N,N-dimethylformamide (adjust c(PCT)=0.01mol/L), place under magnetic stirring conditions of anhydrous and nitrogen protection atmosphere, and first react at 0°C 2h, then reacted at 60°C for 6h, and obtained P-N-B flame retardant after removing the solvent by rotary evaporation;
2)将4份所得P-N-B阻燃剂和96份PBS预混后投入双螺杆挤出机中，料筒温度控制在110℃，挤出压力为15MPa，进行挤出、剪碎，得到PBS阻燃塑料5。2) Premix 4 parts of the obtained P-N-B flame retardant with 96 parts of PBS and put it into a twin-screw extruder. The barrel temperature is controlled at 110°C, and the extrusion pressure is 15MPa. Extrude and shred to obtain PBS flame retardant plastic5.
对比例2Comparative example 2
一种PBS阻燃塑料，其制备方法包括如下步骤：A kind of PBS flame-retardant plastics, its preparation method comprises the steps:
1)将2.43份膦酰氯三聚体(PCT)和1.57份2-氨基乙基联苯基硼酸酯(膦酰氯三聚体和2-氨基乙基联苯基硼酸酯的摩尔比为1:1)溶于相应量的N,N-二甲基甲酰胺(c(PCT)＝0.01mol/L)中，置于无水及氮气保护气氛的磁力搅拌条件下，首先在0℃反应2h，然后在60℃反应6h，旋蒸除去溶剂后得P-N-B阻燃剂；1) Mix 2.43 parts of phosphonyl chloride trimer (PCT) and 1.57 parts of 2-aminoethyl biphenyl borate (the molar ratio of phosphonyl chloride trimer and 2-aminoethyl biphenyl borate is 1 :1) Dissolve in the corresponding amount of N,N-dimethylformamide (c(PCT)=0.01mol/L), place under the condition of magnetic stirring under anhydrous and nitrogen protection atmosphere, and first react at 0°C for 2h , then reacted at 60°C for 6h, and obtained P-N-B flame retardant after rotary evaporation to remove the solvent;
2)将4份所得P-N-B阻燃剂和96份PBS预混后投入双螺杆挤出机中，料筒温度控制在110℃，挤出压力为15MPa，进行挤出、剪碎，得到PBS阻燃塑料6。2) Premix 4 parts of the obtained P-N-B flame retardant with 96 parts of PBS and put it into a twin-screw extruder. The barrel temperature is controlled at 110°C, and the extrusion pressure is 15MPa. Extrude and shred to obtain PBS flame retardant Plastic6.
对比例3Comparative example 3
一种PBS阻燃塑料，其制备方法包括如下步骤：将4份2-氨基乙基联苯基硼酸酯和96份PBS预混后投入双螺杆挤出机中，料筒温度控制在110℃，挤出压力为15MPa，进行挤出、剪碎，得到PBS阻燃塑料7。A PBS flame-retardant plastic, the preparation method of which comprises the following steps: 4 parts of 2-aminoethyl biphenyl borate and 96 parts of PBS are premixed and then put into a twin-screw extruder, and the barrel temperature is controlled at 110°C , the extrusion pressure is 15 MPa, extruded and shredded to obtain PBS flame-retardant plastic 7.
将实施例1～4和对比例1～3所得PBS制品分别进行力学性能和阻燃性能等测试，结果见表1。The PBS products obtained in Examples 1-4 and Comparative Examples 1-3 were tested for mechanical properties and flame-retardant properties, respectively, and the results are shown in Table 1.
表1 实施例1～4和对比例1～3所得PBS阻燃塑料的性能测试结果Table 1 The performance test results of the PBS flame-retardant plastics obtained in Examples 1-4 and Comparative Examples 1-3
| 编号serial number | 拉伸强度(MPa)Tensile strength (MPa) | 极限氧指数(％)Limiting Oxygen Index (%) | 垂直燃烧评级Vertical Burn Rating | 总烟释放量(m 2) Total smoke release (m 2 ) |
| 实施例1Example 1 | 18.718.7 | 30.230.2 | V-1，无燃滴V-1, no burning drops | 14.214.2 |
| 实施例2Example 2 | 18.418.4 | 32.632.6 | V-0，无燃滴V-0, no burning drops | 13.613.6 |
| 实施例3Example 3 | 15.215.2 | 37.837.8 | V-0，无燃滴V-0, no burning drops | 10.210.2 |
| 实施例4Example 4 | 11.411.4 | 39.239.2 | V-0，无燃滴V-0, no burning drops | 8.58.5 |
| 对比例1Comparative example 1 | 17.817.8 | 35.435.4 | V-2，有燃滴V-2, with burning drops | 15.415.4 |
| 对比例2Comparative example 2 | 13.313.3 | 28.928.9 | V-2，有燃滴V-2, with burning drops | 18.918.9 |
| 对比例3Comparative example 3 | 16.416.4 | 25.425.4 | NR，有燃滴NR, with burning drops | 17.617.6 |
上述结果表明，本发明所得P-N-B阻燃剂可显著提升PBS塑料制品的阻燃性能，尤其在膦 酰氯三聚体和2-氨基乙基联苯基硼酸酯的摩尔比为1:6时所制备的P-N-B阻燃剂，在4wt％左右的低掺量条件下，在保证所得PBS产品良好力学性能的基础上，即可表现出优异的阻燃性能；此外，该阻燃剂有明显的抑烟和抗滴落效果，对提高火灾生存率有重要影响，在保证PBS产品使用性能(力学性能)的基础上，可进一步有效提升阻燃剂填料的掺量，进而显著提升所得PBS产品的阻燃性能。The above results show that the obtained P-N-B flame retardant of the present invention can significantly improve the flame retardancy of PBS plastic products, especially when the mol ratio of phosphonochloride trimer and 2-aminoethyl biphenyl borate is 1:6. The prepared P-N-B flame retardant can exhibit excellent flame retardant performance under the condition of low dosage of about 4wt%, on the basis of ensuring the good mechanical properties of the obtained PBS product; in addition, the flame retardant has obvious inhibition Smoke and anti-dripping effects have an important impact on improving the fire survival rate. On the basis of ensuring the performance (mechanical properties) of PBS products, the content of flame retardant fillers can be further effectively increased, thereby significantly improving the resistance of the obtained PBS products. flammability.
上述实施例仅是为了清楚地说明所做的实例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或者变动，这里无需也无法对所有的实施方式予以穷举，因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。The above-mentioned embodiments are only examples made for the purpose of clearly illustrating, and are not intended to limit the implementation. For those of ordinary skill in the art, on the basis of the above description, other different forms of changes or changes can also be made, and it is not necessary and impossible to exhaustively list all the implementation modes here, so the obvious changes or changes extended Still within the scope of protection of the present invention.
Claims (9)
- 一种P-N-B复合PBS阻燃塑料，其特征在于，它以P-N-B阻燃剂和聚丁二酸丁二醇酯为原料，依次进行混料和挤出成型而成；其中P-N-B阻燃剂以膦酰氯三聚体和2-氨基乙基联苯基硼酸酯为主要原料进行反应得到。A P-N-B composite PBS flame-retardant plastic is characterized in that it uses P-N-B flame retardant and polybutylene succinate as raw materials, which are sequentially mixed and extruded; wherein the P-N-B flame retardant is made of phosphonyl chloride The trimer and 2-aminoethyl biphenyl borate are obtained by reacting the main raw materials.
- 根据权利要求1所述的P-N-B复合PBS阻燃塑料，其特征在于，所述P-N-B阻燃剂与聚丁二酸丁二醇酯的质量比为(1～25):(75～99)。The P-N-B composite PBS flame-retardant plastic according to claim 1, wherein the mass ratio of the P-N-B flame retardant to polybutylene succinate is (1-25):(75-99).
- 根据权利要求1所述的P-N-B复合PBS阻燃塑料，其特征在于，所述P-N-B阻燃剂的制备方法包括如下步骤：将膦酰氯三聚体和2-氨基乙基联苯基硼酸酯溶于有机溶剂中，混合均匀，将所得混合溶液在无水及保护气氛下，进行搅拌反应，再经过滤、清洗、烘干，得所述P-N-B阻燃剂。P-N-B composite PBS flame retardant plastics according to claim 1, is characterized in that, the preparation method of described P-N-B flame retardant comprises the following steps: dissolving phosphonochloride trimer and 2-aminoethyl biphenyl borate Mix evenly in an organic solvent, stir the obtained mixed solution in an anhydrous and protective atmosphere, and then filter, wash and dry to obtain the P-N-B flame retardant.
- 根据权利要求1或3所述的P-N-B复合PBS阻燃塑料，其特征在于，所述膦酰氯三聚体与2-氨基乙基联苯基硼酸酯的摩尔比为1:(4～6)。P-N-B composite PBS flame-retardant plastics according to claim 1 or 3, is characterized in that, the mol ratio of described phosphonochloride trimer and 2-aminoethyl biphenyl borate is 1:(4～6) .
- 根据权利要求3所述的P-N-B复合PBS阻燃塑料，其特征在于，所述搅拌反应温度为0～120℃，时间为6～24h。The P-N-B composite PBS flame-retardant plastic according to claim 3, characterized in that, the stirring reaction temperature is 0-120° C., and the time is 6-24 hours.
- 根据权利要求3所述的P-N-B复合PBS阻燃塑料，其特征在于，所得混合溶液中膦酰氯三聚体的浓度为0.01～1mol/L。The P-N-B composite PBS flame-retardant plastic according to claim 3, characterized in that the concentration of the phosphonochloride trimer in the obtained mixed solution is 0.01-1 mol/L.
- 根据权利要求3所述的P-N-B复合PBS阻燃塑料，其特征在于，所述有机溶剂为N,N-二甲基甲酰胺、二甲亚砜、甲苯或二甲苯。The P-N-B composite PBS flame-retardant plastic according to claim 3, wherein the organic solvent is N,N-dimethylformamide, dimethyl sulfoxide, toluene or xylene.
- 权利要求1～7任一项所述P-N-B复合PBS阻燃塑料的制备方法，其特征在于，具体包括如下步骤：将P-N-B阻燃剂和PBS初混后置于双螺杆挤出机中，在双螺杆挤出机的作用下挤出后剪碎得所述PBS阻燃塑料。The preparation method of the P-N-B composite PBS flame-retardant plastic described in any one of claims 1 to 7 is characterized in that it specifically comprises the following steps: placing the P-N-B flame retardant and PBS in a twin-screw extruder after initial mixing, The PBS flame-retardant plastic is obtained by extruding and shredding under the action of a screw extruder.
- 根据权利要求8所述的制备方法，其特征在于，所述挤出温度为80～110℃，挤出压力为10～20Mpa。The preparation method according to claim 8, characterized in that, the extrusion temperature is 80-110° C., and the extrusion pressure is 10-20 MPa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111199568.7 | 2021-10-14 | ||
| CN202111199568.7A CN113861633B (en) | 2021-10-14 | 2021-10-14 | P-N-B flame-retardant PBS plastic and preparation method thereof |
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| WO2023060560A1 true WO2023060560A1 (en) | 2023-04-20 |
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| PCT/CN2021/124113 WO2023060560A1 (en) | 2021-10-14 | 2021-10-15 | P-n-b flame-retardant pbs plastic and preparation method therefor |
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| WO (1) | WO2023060560A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116925560B (en) * | 2023-07-15 | 2024-02-09 | 广东安拓普聚合物科技股份有限公司 | Building decorative plate and preparation method thereof |
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| CN110527206A (en) * | 2019-08-15 | 2019-12-03 | 安徽壹石通材料科技股份有限公司 | A kind of preparation and its application of nitrogen-phosphorus-boron expansion type flame retardant |
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| JP5754663B2 (en) * | 2010-07-14 | 2015-07-29 | 株式会社伏見製薬所 | Cyclic phosphazene compound having oligolactic acid segment and method for producing the same |
| AU2014244053B2 (en) * | 2013-03-13 | 2018-08-30 | University Of Cincinnati | Treatment of a diastolic cardiac dysfunction with a TRPV2 receptor agonist |
| CN105237968A (en) * | 2015-11-10 | 2016-01-13 | 安徽工业大学 | Flame-retardant polybutylene succinate composite and preparation method thereof |
| CN109679138B (en) * | 2018-12-18 | 2021-01-08 | 江苏利思德新材料有限公司 | Halogen-free flame retardant melamine polyphosphate borate salt and preparation method and application thereof |
| CN113234228B (en) * | 2021-05-31 | 2022-05-27 | 浙大宁波理工学院 | Boron-containing polyphosphazene amide flame retardant with efficient flame retardance and smoke suppression as well as preparation method and application thereof |
| CN113372550B (en) * | 2021-06-03 | 2022-11-22 | 江南大学 | Flame-retardant plasticizer and flame-retardant polymer-based composite material |
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| WO2006071772A2 (en) * | 2004-12-23 | 2006-07-06 | Dow Corning Corporation | Crosslinkable saccharide-siloxane compositions, and networks, coatings and articles formed therefrom |
| CN102898842A (en) * | 2012-09-28 | 2013-01-30 | 沈阳化工大学 | Polymer type boron-containing flame retardant and preparation method thereof |
| CN106009383A (en) * | 2016-06-22 | 2016-10-12 | 安徽电信器材贸易工业有限责任公司 | Nylon plastic flame-retardant optical cable material and preparation method thereof |
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| CN116925560B (en) * | 2023-07-15 | 2024-02-09 | 广东安拓普聚合物科技股份有限公司 | Building decorative plate and preparation method thereof |
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| CN113861633B (en) | 2022-12-20 |
| CN113861633A (en) | 2021-12-31 |
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