CN115557988A - Oligomeric phosphate polyol and preparation method thereof - Google Patents
Oligomeric phosphate polyol and preparation method thereof Download PDFInfo
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- CN115557988A CN115557988A CN202211385436.8A CN202211385436A CN115557988A CN 115557988 A CN115557988 A CN 115557988A CN 202211385436 A CN202211385436 A CN 202211385436A CN 115557988 A CN115557988 A CN 115557988A
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- phosphate
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- oligomeric phosphate
- polyol
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 50
- 239000010452 phosphate Substances 0.000 title claims abstract description 50
- -1 phosphate polyol Chemical class 0.000 title claims abstract description 47
- 229920005862 polyol Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000004917 polyol method Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910015900 BF3 Inorganic materials 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229920005903 polyol mixture Polymers 0.000 claims description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 2
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 51
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 46
- 239000000463 material Substances 0.000 abstract description 26
- 229920002635 polyurethane Polymers 0.000 abstract description 14
- 239000004814 polyurethane Substances 0.000 abstract description 14
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007259 addition reaction Methods 0.000 abstract description 4
- 125000002947 alkylene group Chemical group 0.000 abstract description 4
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 150000002367 halogens Chemical class 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 230000002045 lasting effect Effects 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 239000002910 solid waste Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 9
- 238000002485 combustion reaction Methods 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000012974 tin catalyst Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/093—Polyol derivatives esterified at least twice by phosphoric acid groups
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
- C08G18/3885—Phosphate compounds
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
-
- 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
- C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
- C08G79/02—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule a linkage containing phosphorus
- C08G79/04—Phosphorus linked to oxygen or to oxygen and carbon
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of phosphorus flame retardants, in particular to an oligomeric phosphate polyol and a preparation method thereof, and the oligomeric phosphate polyol and the preparation method thereof, wherein the oligomeric phosphate polyol contains a hydroxyl-terminated reactive flame retardant, does not contain halogen elements, is environment-friendly and nontoxic, can be combined into a polyurethane material to serve as a novel flame retardant, cannot migrate and separate out, and is favorable for improving the lasting flame retardant property of the material; the method has simple process and easy operation, is beneficial to improving the industrial production efficiency, does not generate solid waste after the preparation reaction, and can reduce the environmental protection pressure; the invention adopts the methods of depolymerization, hydrolysis and addition of the alkyl phosphate to greatly increase the phosphorus content in the product, which is beneficial to improving the flame-retardant effect, and the catalyst can promote the alkylene oxide to participate in the addition reaction, thereby effectively shortening the addition reaction time of the alkylene oxide, phosphoric acid and phosphate ester, being beneficial to reducing the waste of the ethylene oxide and saving the cost.
Description
Technical Field
The invention relates to the technical field of phosphorus flame retardants, in particular to oligomeric phosphate polyol and a preparation method thereof.
Background
Polyurethane, as a part of new-generation artificially synthesized polymer application novel materials, has been incorporated into the aspects of daily life of people, and the polyurethane material is a polymer with strong flammability as other organic polymer materials. In recent years, polyurethane products and raw materials in the domestic polyurethane market are always in short supply, particularly soft ester foam plastics have the advantages of low density, large specific surface area and good heat insulation performance, but the combustion problem is also outstanding, the oxygen index per se is only 14-16, the soft ester foam plastics are extremely easy to ignite and burn, once the soft ester foam plastics are ignited, the combustion speed is violent, the soft ester foam plastics are not easy to extinguish, smoke generated in the combustion process is toxic, and people are extremely easy to suffocate and die, so a flame retardant is required to be added into the raw materials to improve the flame retardant performance of the polyurethane foam plastics.
At present, two methods are mainly used for flame retardance of polyurethane materials: additive method and reactive flame retardant method. The additive method adds additive flame retardant containing flame retardant elements such as phosphorus, chlorine, bromine, antimony, aluminum, boron, nitrogen and the like into the formula of the polyurethane product, so that the prepared product has flame retardant performance, but the required addition amount is large, so that the mechanical performance of the polyurethane foam material is reduced on one hand, and the flame retardant can be gradually migrated and separated out from the material along with the passage of time, so that the flame retardant performance and the physical and mechanical properties of the material are further reduced in the using process, and secondary pollution is caused to the environment; the currently marketed flame retardants for polyurethane materials are mainly halogen-containing phosphate ester additive type flame retardants, which are prone to generate hydrogen halide corrosive gases during combustion. The reactive flame retardant method adds the reactive flame retardant such as polyhydroxy compound containing phosphorus, chlorine, bromine, boron and nitrogen flame retardant elements in the formula for producing the polyurethane, and can effectively overcome the defects of the additive flame retardant because the flame retardant is connected to a polyurethane macromolecular structure in a covalent bond mode.
The existing Chinese patent 201010227072.1 discloses a preparation method of oligomeric phosphate polyol, although a reactive flame retardant is prepared by the method, a large amount of hydrogen chloride gas is generated in the reaction process, and the generated triethylamine hydrochloride has certain solubility in the oligomeric phosphate polyol serving as a target product, so that the using effect of the flame retardant at an application end is seriously influenced, the production efficiency is reduced due to the complexity of a post-treatment process, and the production cost is increased; chinese patent 201510567252.7 discloses a preparation method of oligomeric phosphate polyol, which is a reaction type flame retardant, but the reaction of phosphorus pentoxide and water is a violent exothermic reaction, the reaction is extremely difficult to control, the industrial production is not facilitated, the requirement on reaction equipment is extremely high, the phosphorus content in the product is low, and the flame retardant effect is poor. In order to solve the above technical problems, it is necessary to provide a novel preparation method which is easy to control the reaction, so as to improve the flame retardant property of the material and reduce the production cost. In view of this, we propose an oligomeric phosphate polyol and a method for preparing the same.
Disclosure of Invention
In order to make up for the above disadvantages, the invention provides an oligomeric phosphate polyol and a preparation method thereof.
The technical scheme of the invention is as follows:
an oligomeric phosphate polyol having the formula:
wherein: p represents the degree of polymerization of the group and is a natural number between 1 and 4; n represents the polymerization degree of the polymer and is a natural number between 0 and 10; r is C1-C4 halogen-free alkyl; r 1 Is a hydrogen atom or R; r is 2 Is the following group:
preferably, the oligomeric phosphate polyol is purified starting material by: the catalyst comprises alkyl phosphate, phosphorus pentoxide, a catalyst, ethylene oxide and water, wherein the raw materials comprise the following components in parts by mass: alkyl phosphate ester: 100-110, phosphorus pentoxide: 45-78, ethylene oxide: 55-80, catalyst: 0.5-2, water: 2.5-15.5.
Preferably, the oligomeric phosphate ester polyol has an acid value of less than 2mgK0H/g, a hydroxyl value of 120-220mgK0H/g, a viscosity of 500-6000mPa.s and a phosphorus content of 15-18%.
Preferably, the specific preparation method comprises the following steps: firstly, 100-110 parts by mass of alkyl phosphate is added into a reaction kettle, the reaction kettle is started to stir, 45-78 parts by mass of phosphorus pentoxide is added, and the reaction kettle is heated to 60-100 ℃ for full reaction for 4-8 hours.
Preferably, after the reaction kettle is cooled to 50-80 ℃, continuously dropwise adding 2.5-15.5 parts by mass of water into the reaction kettle, controlling the reaction temperature to be 60-80 ℃, and reacting for 1-1.5 hours.
Preferably, 0.5-2 parts by mass of catalyst is continuously added into the reaction kettle, then 55-80 parts by mass of ethylene oxide is introduced for further reaction, and the reaction temperature is controlled to be maintained between 100-150 ℃ by controlling the flow rate of the ethylene oxide.
Preferably, the heating is stopped and the cooling is carried out after the reaction is continued for 1 to 1.5 hours until continuous ethylene oxide reflux in the condenser occurs. Preferably, the oligomeric phosphate polyol mixture is then prepared by removing volatile materials from the mixture by vacuum stripping or nitrogen flow.
Preferably, the alkyl phosphate adopts any one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate.
Preferably, the catalyst adopts any one or more of aluminum trichloride, boron trifluoride, zinc chloride or organic tin.
Compared with the prior art, the invention has the beneficial effects that:
the oligomeric phosphate polyol synthesized by the invention contains a hydroxyl-terminated reactive flame retardant, does not contain halogen elements, is environment-friendly and nontoxic, can be combined into a polyurethane material to serve as a novel flame retardant, cannot migrate and separate out when heated, is favorable for improving the lasting flame retardant property of the material, and has remarkable performance advantage compared with the current phosphate ester additive flame retardant on the market; the preparation method adopts a one-pot reaction, has simple process and easy operation, is beneficial to improving the industrial production efficiency, does not generate solid waste after the preparation reaction, and can reduce the environmental protection pressure; in addition, the main raw material alkyl phosphate is a common additive flame retardant, the phosphorus content in the product is greatly increased by adopting methods of depolymerization, hydrolysis and addition of the alkyl phosphate, the flame retardant effect is favorably improved, the catalyst adopted by the invention can promote alkylene oxide to participate in addition reaction, the addition reaction time of the alkylene oxide, phosphoric acid and phosphate can be effectively shortened, the waste of ethylene oxide is favorably reduced, and the cost is saved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The invention details the above technical solution by the following embodiments:
an oligomeric phosphate polyol having the following structural formula:
in this embodiment: p represents the degree of polymerization of the group, specifically 4; n represents the degree of polymerization of the polymer, specifically 9; r is C4 halogen-free alkyl; r 1 Is a hydrogen atom; r is 2 Is the following group:
the specific preparation method of the oligomeric phosphate polyol of the embodiment is as follows: weighing raw materials by workers: alkyl phosphate ester: 100g, phosphorus pentoxide: 63.5g, ethylene oxide: 65g, catalyst: 0.5g, water: 5.2 g.
100g of triethyl phosphate are initially introduced into a reactor equipped with stirrer, thermometer, gas inlet and reflux condenser, 63.5g of phosphorus pentoxide are subsequently added, the mixture is heated at 70 ℃ for 5 hours after vigorous stirring; then, 5.2g of water is slowly added into the cooled light yellow reaction mixture, ice is used for external cooling, the temperature can influence the reaction rate, the violent reaction at the position can raise the temperature of the reaction kettle by heat release, if the violent reaction is not controlled, the instantaneous temperature rise can be caused, so that the solvent in the reaction kettle is easy to boil, and the potential safety hazard also exists, therefore, the reaction temperature of the reaction kettle is controlled to be 70 ℃, the reaction is stirred and reacted for 1 hour at 70 ℃, and the temperature control is also beneficial to judging whether the reaction is sufficient according to the reaction time in the actual production.
Then adding an organic tin catalyst: 0.5g of stannous octoate, 65g of ethylene oxide is introduced for further reaction, and the reaction temperature is controlled to be maintained between 120 and 140 ℃ by controlling the flow rate of the ethylene oxide. The reaction was continued for 1 hour until a vigorous and noticeable reflux was observed in the reaction condenser;
finally, removing the unreacted residual excess ethylene oxide from the reaction mixture through strong nitrogen flow, and preventing a small amount of ethylene oxide in the product from playing a combustion promoting role in a later-stage flame retardant to influence the flame retardant effect; about 210g of a yellowish viscous transparent liquid was finally obtained. And the detection shows that the low-polymer polyesterpolyol has the viscosity of 1570mPa.s at 25 ℃, the acid value of 0.7mgKOH/g, the hydroxyl value of 145mgKOH/g and the phosphorus content of 15.7 percent.
Example 2
This example differs from example 1 only in that: in this example 2, 66.6g of ethylene oxide was consumed by using 100g of triethyl phosphate, 70g of phosphorus pentoxide, 12.7g of water, and 0.5g of stannous octoate as an organic tin catalyst, to obtain 217g of a pale yellow viscous transparent liquid; the detection proves that the viscosity of the product at 25 ℃ is 500mPa.s, the acid value is 0.4mgKOH/g, the hydroxyl value is 215mgKOH/g, and the phosphorus content is 13.7 percent
Example 3
This example only differs from example 1 in that: example 3 Using 100g of trimethyl phosphate, 77g of phosphorus pentoxide, 3.5g of water, 0.5g of stannous octoate as a catalyst, and 70g of ethylene oxide consumed, 240g of a pale yellow viscous transparent liquid was obtained. The detection shows that the viscosity of the product at 25 ℃ is 5600mPa.s, the acid value is 0.8mgKOH/g, the hydroxyl value is 125mgKOH/g, and the phosphorus content is 18.5%.
Example 4
This example only differs from example 1 in that: example 4 the remaining excess ethylene oxide was removed from the reaction mixture by an intense stream of nitrogen using 100g of triethyl phosphate, 63.5g of phosphorus pentoxide, 0.5g of catalyst stannous octoate, 80g of propylene oxide. 230g of a pale yellow, viscous, transparent liquid are obtained. The viscosity of the product at 25 ℃ is 1770mPa.s, the acid value is 0.5mgKOH/g, the hydroxyl value is 148mgKOH/g, and the phosphorus content is 15.8 percent.
It should be explained that the Limiting Oxygen Index (LOI) is determined by using JF-3 oxygen index tester according to the GB/T2406-1993 standard, and the Limiting Oxygen Index (LOI) is the minimum oxygen concentration required for the material to be tested to burn in the mixed flow of oxygen and nitrogen, so as to judge the difficulty of burning the material in the air, if the oxygen index of the material to be tested is higher, it means that the material is less easy to burn, generally, LOI less than 22% is flammable, LOI between 22-27% is flammable, and LOI greater than 27% is flammable; for a vertical burning test (UL-94) which refers to a test method of applying flame to a vertically arranged test sample according to GB/T2408-2008 standard and then grading according to burning phenomenon, the UL-94 flame retardant grade can be generally divided into three grades of V-0, V-1 and V-2, wherein the flame retardant grade of V-0 is the highest; the mechanical property of the material is tested according to a GB/T9641-1988 standard universal tensile testing machine.
Oligomeric phosphate polyols prepared according to examples 1 to 4, respectively, were added as flame retardants to polyurethane materials and tested for the effect of different addition levels on Limiting Oxygen Index (LOI), vertical burning test (UL-94) and mechanical properties of the materials, with specific data as given in the following table:
table 1 (example 1):
| the additive content | 0％ | 10％ | 20％ | 30％ | 40％ | 50％ |
| LOI | 17％ | 23％ | 26％ | 31％ | 32％ | 33％ |
| UL-94 | V-2 | V-2 | V-1 | V-0 | V-0 | V-0 |
| Tensile Strength (kpa) | 148.6 | 139.8 | 141.2 | 141.8 | 142.3 | 143.5 |
Table 2 (example 2):
| the additive content | 0％ | 10％ | 20％ | 30％ | 40％ | 50％ |
| LOI | 17％ | 22％ | 25％ | 29％ | 31％ | 32％ |
| UL-94 | V-2 | V-2 | V-1 | V-0 | V-0 | V-0 |
| Tensile Strength (kpa) | 148.6 | 137.8 | 140.6 | 140.9 | 141.8 | 142.4 |
Table 3 (example 3):
| the additive content | 0％ | 10％ | 20％ | 30％ | 40％ | 50％ |
| LOI | 17％ | 24％ | 27％ | 31％ | 33％ | 35％ |
| UL-94 | V-2 | V-2 | V-0 | V-0 | V-0 | V-0 |
| Tensile Strength (kpa) | 148.6 | 141.3 | 141.8 | 142.5 | 143.2 | 143.6 |
Table 4 (example 4):
| content of addition | 0％ | 10％ | 20％ | 30％ | 40％ | 50％ |
| LOI | 17％ | 23％ | 26％ | 31％ | 32％ | 33％ |
| UL-94 | V-2 | V-2 | V-1 | V-0 | V-0 | V-0 |
| Tensile Strength (kpa) | 148.6 | 140.2 | 140.8 | 141.3 | 142.1 | 142.7 |
As shown in tables 1-4, it is found that the mechanical properties of the polyurethane material with the flame retardant are maintained at a higher level and still can meet the use requirements of the material compared with the polyurethane material without the flame retardant; and with the increase of the addition amount of the flame retardant, the phosphorus content in the system is gradually increased, and the limiting oxygen index of the material is also gradually increased; the flame retardant prepared in the mass part of the invention has excellent flame retardant performance, and the phosphorus content is highest in example 3, so the flame retardant has a V-0 grade combustion grade after being added with 20% of flame retardant, the other examples also have a V-0 grade combustion grade after being added with 30% of flame retardant, and all examples have a limiting oxygen index which is more than 27% when being added with 30% of flame retardant, which indicates that the flame retardant has flame retardant performance when being added with 30% of flame retardant, the combustion grade is V-0 grade, and the mechanical property of the material is higher at the moment, and the influence on the mechanical property of the material is smaller, so the flame retardant prepared in the mass part of the invention has excellent flame retardant performance, and the preferable addition content is 30%.
The foregoing shows and describes the general principles, principal features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and are not intended to limit the present invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. An oligomeric phosphate polyol, characterized in that: the oligomeric phosphate polyol has the following structural formula:
wherein: p represents the degree of polymerization of the group and is a natural number between 1 and 4; n represents the polymerization degree of the polymer and is a natural number between 0 and 10; r is C1-C4 halogen-free alkyl; r 1 Is a hydrogen atom or R; r is 2 Is the following group:
2. the oligomeric phosphate polyol of claim 1, wherein: the oligomeric phosphate polyol was analytically pure in raw materials by: the catalyst comprises alkyl phosphate, phosphorus pentoxide, a catalyst, ethylene oxide and water, wherein the chemical reaction of the raw materials comprises the following components in parts by weight: alkyl phosphate ester: 100-110, phosphorus pentoxide: 45-78, ethylene oxide: 55-80, catalyst: 0.5-2, water: 2.5-15.5.
3. The oligomeric phosphate polyol according to claim 2, wherein: the oligomeric phosphate ester polyol has an acid value of less than 2mgK0H/g, a hydroxyl value of 120-220mgK0H/g, a viscosity of 500-6000mPa.s and a phosphorus content of 15-18%.
4. A preparation method of oligomeric phosphate polyol is characterized by comprising the following steps: for the preparation of an oligomeric phosphate polyol according to any of claims 1 to 3: firstly, 100-110 parts by mass of alkyl phosphate is added into a reaction kettle, the reaction kettle is started to stir, 45-78 parts by mass of phosphorus pentoxide is added, and the reaction kettle is heated to 60-100 ℃ for full reaction for 4-8 hours.
5. The method of preparing an oligomeric phosphate polyol according to claim 4, wherein: after the reaction kettle is cooled to 50-80 ℃, continuously dripping 2.5-15.5 parts by weight of water into the reaction kettle, controlling the reaction temperature to be 60-80 ℃ and reacting for 1-1.5 hours.
6. The method of preparing an oligomeric phosphate polyol according to claim 5, wherein: continuously adding 0.5-2 parts by mass of catalyst into the reaction kettle, then introducing 55-80 parts by mass of ethylene oxide for further reaction, and controlling the reaction temperature to be maintained between 100-150 ℃ by controlling the flow rate of the ethylene oxide.
7. The method of preparing an oligomeric phosphate polyol according to claim 6, wherein: and when the reaction is carried out until continuous ethylene oxide reflux appears in the condenser, the reaction is continued for 1 to 1.5 hours, and then the heating is stopped and the reaction is cooled.
8. The method of preparing an oligomeric phosphate polyol according to claim 7, wherein: then introducing vacuum stripping or nitrogen flow to remove volatile substances in the mixture, thus obtaining the oligomeric phosphate polyol mixture.
9. The method of preparing an oligomeric phosphate polyol according to claim 2, wherein: the alkyl phosphate adopts any one or more of trimethyl phosphate, triethyl phosphate, tripropyl phosphate or tributyl phosphate.
10. The method of preparing an oligomeric phosphate polyol according to claim 6, wherein: the catalyst adopts any one or more of aluminum trichloride, boron trifluoride, zinc chloride or organic tin.
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