CN114853998A - Preparation method of castor oil based reactive flame-retardant polyester polyol - Google Patents
Preparation method of castor oil based reactive flame-retardant polyester polyol Download PDFInfo
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- CN114853998A CN114853998A CN202210485209.6A CN202210485209A CN114853998A CN 114853998 A CN114853998 A CN 114853998A CN 202210485209 A CN202210485209 A CN 202210485209A CN 114853998 A CN114853998 A CN 114853998A
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- castor oil
- polyester polyol
- flame
- retardant
- preparation
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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 64
- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 239000004359 castor oil Substances 0.000 title claims abstract description 56
- 235000019438 castor oil Nutrition 0.000 title claims abstract description 56
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 title claims abstract description 56
- 229920005906 polyester polyol Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- CEDDGDWODCGBFQ-UHFFFAOYSA-N carbamimidoylazanium;hydron;phosphate Chemical compound NC(N)=N.OP(O)(O)=O CEDDGDWODCGBFQ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 8
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 3
- 150000005846 sugar alcohols Polymers 0.000 claims abstract 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000006757 chemical reactions by type Methods 0.000 claims description 8
- 238000005809 transesterification reaction Methods 0.000 claims description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 6
- 239000001361 adipic acid Substances 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 4
- 150000002148 esters Chemical group 0.000 claims description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N guanidine group Chemical group NC(=N)N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- -1 small molecule polyol Chemical class 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 3
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 230000002045 lasting effect Effects 0.000 abstract description 6
- 229920005830 Polyurethane Foam Polymers 0.000 abstract description 5
- 239000011496 polyurethane foam Substances 0.000 abstract description 5
- 125000004185 ester group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000005336 cracking Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000006260 foam Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 230000005587 bubbling Effects 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 5
- 238000009413 insulation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 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 2
- GTRSAMFYSUBAGN-UHFFFAOYSA-N tris(2-chloropropyl) phosphate Chemical compound CC(Cl)COP(=O)(OCC(C)Cl)OCC(C)Cl GTRSAMFYSUBAGN-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000662429 Fenerbahce Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- UTVVREMVDJTZAC-UHFFFAOYSA-N furan-2-amine Chemical compound NC1=CC=CO1 UTVVREMVDJTZAC-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002937 thermal insulation foam Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6928—Polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
-
- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- 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
- C08G2101/00—Manufacture of cellular products
-
- 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
- C08G2110/00—Foam properties
- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a preparation method of castor oil based reactive flame-retardant polyester polyol, which comprises the following steps: a) performing polycondensation reaction on castor oil, micromolecular polyhydric alcohol, micromolecular polybasic acid or anhydride under the action of a catalyst to obtain castor oil-based polyester polyol; b) adding esterified phosphoric acid guanidine into the castor oil-based polyester polyol obtained in the step a), and carrying out ester exchange reaction to obtain the castor oil-based reactive flame-retardant polyester polyol. In the preparation method, the flame-retardant element is introduced into the polyester polyol molecular chain, so that the preparation method has the characteristics of lasting flame-retardant property and excellent flame-retardant effect; in addition, castor oil and esterified phosphoric acid guanidine are introduced into polyester polyol molecules, so that the mechanical property and low-temperature resistance of the polyurethane foam are enhanced.
Description
Technical Field
The invention belongs to the field of bio-based flame-retardant materials, and particularly relates to a preparation method of castor oil-based reactive flame-retardant polyester polyol.
Background
Polyester polyol is generally reacted with isocyanate to prepare polyurethane foam for a heat insulation plate, a flame retardant is generally introduced to the polyurethane heat insulation plate in order to avoid fire caused by high-temperature combustion when the polyurethane heat insulation plate is used, a common flame retardant in the prior art is generally added into the preparation process of a polyurethane material in an adding mode, however, the additive flame retardant is migrated when the polyurethane material is used for a long time, and the flame retardant effect of the additive flame retardant is lost.
The patent CN113150522A discloses a modified flame-retardant polyester material containing a full-bio-based flame retardant and a preparation method thereof, wherein the flame-retardant polyester material is prepared by a melt blending mode of a self-made phytic furan amine flame retardant and polyester, and the flame retardant and the polyester are physically mixed, so that the problems of easy migration of the flame retardant, non-lasting flame-retardant effect and the like exist. Patent CN103232703A discloses a preparation method of flame-retardant polyester polyol, which uses a method of physically mixing castor oil and tricresyl phosphite to prepare a flame-retardant polyester product, and the process has the defects that the compatibility of the castor oil and a flame retardant is poor, so that the flame-retardant effect is not durable.
In addition, the castor oil-based polyol has better environmental protection property and is more and more widely applied, but the polyester polyol prepared by directly adopting castor oil and polybasic acid has the defect of poor mechanical properties such as hardness, tearing strength and the like. How to create a polyester polyol with good flame-retardant effect and strong durability, and the prepared polyurethane product has excellent mechanical property has very positive significance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide the preparation method of the castor oil-based reactive flame-retardant polyester polyol, and the process adopts castor oil as a raw material and has the advantages of being renewable and degradable; secondly, flame-retardant elements are introduced into the molecular chain of the polyester polyol in a chemical reaction mode, so that the polyester polyol has the characteristics of lasting flame-retardant property and excellent flame-retardant effect; in addition, castor oil and esterified phosphoric acid guanidine are introduced into polyester polyol molecules, so that the mechanical property and low-temperature resistance of the polyurethane foam are enhanced.
In order to realize the purpose of the invention, the invention adopts the following technical scheme:
a preparation method of castor oil based reactive flame-retardant polyester polyol comprises the following steps:
step a), performing polycondensation reaction on castor oil, micromolecular polyol, micromolecular polybasic acid or anhydride under the action of a catalyst to obtain castor oil-based polyester polyol;
and b) adding esterified guanidine phosphate into the castor oil-based polyester polyol obtained in the step a) to perform ester exchange reaction to obtain castor oil-based reactive flame-retardant polyester polyol.
Preferably, in the step a), the mass ratio of the castor oil, the small molecular polyol and the small molecular polyacid is 20-40: 10-30: 40 to 47 percent, and the adding amount of the catalyst is 0.05 to 0.5 percent of the total mass of the raw materials.
Preferably, in the step a), the small molecule polyol is C 2 -C 8 Including but not limited to one or more of ethylene glycol, diethylene glycol, propylene glycol, glycerol, dipropylene glycol, butylene glycol, and the like; the small molecular polybasic acid or anhydride is C 4- C 10 The polybasic acid or anhydride of (a) includes, but is not limited to, one or more of adipic acid, phthalic anhydride, and the like; the catalyst includes, but is not limited to, one or more of isopropyl titanate, isobutyl titanate, tin tetrachloride, diethylamine, and the like.
Preferably, in the step a), the temperature of the polycondensation reaction is 150-230 ℃, and the reaction time is 4-12 h.
Preferably, the temperature of the transesterification reaction in step b) is 150-200 ℃; the reaction time is 4-8 h.
Preferably, in the step b), the mass ratio of the amount of the esterified phosphoric acid monoguanidine to the amount of the castor oil is 1: 10-100.
Preferably, in the step b), the preparation method of the esterified phosphoric acid monoguanidine comprises the following steps: carrying out esterification modification on the guanidine phosphate and the small molecular alcohol under the catalysis of concentrated sulfuric acid to synthesize esterified guanidine phosphate, and after the reaction is finished, removing the unreacted small molecular alcohol in vacuum.
Preferably, in the step b), the small molecule alcohol is C in the preparation method of the esterified phosphoric acid monoguanidine 1 -C 14 The monofunctional alcohol of (a) includes one or more of methanol, ethanol, propanol, etc.;
preferably, the mole ratio of the small molecule alcohol to the guanidine phosphate is 2-3: 1; the dosage of the concentrated sulfuric acid is 0.1 to 0.5 percent of the mass of the phosphoric acid monoguanidine;
preferably, the reaction temperature is 120-200 ℃; the reaction time is 2-8 h.
Preferably, in step b), the esterified phosphoric acid monoguanidine has a structural formula:
wherein Gu is guanidine and has the structure of
R 1 Is C 1 -C 14 Alkane chain, R 2 Is C 1 -C 14 An alkane chain.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the castor oil based reactive flame-retardant polyester polyol prepared by the invention, the esterified phosphoric acid guanidine containing N, P is introduced into the molecular chain of the castor oil based polyester polyol, so that the castor oil based reactive flame-retardant polyester polyol has the advantages of lasting flame-retardant effect and excellent flame-retardant effect;
2) after esterified guanidine phosphate and castor oil molecules are introduced into the structure of the castor oil-based reactive flame-retardant polyester polyol prepared by the invention, the cross-linking reaction with isocyanate is favorably enhanced, and the mechanical properties such as tearing, stretching and the like of the prepared polyurethane foam are enhanced;
3) according to the castor oil based reactive flame-retardant polyester polyol prepared by the invention, a castor oil structure is introduced into a molecular chain segment, and the castor oil structure contains a carbon-carbon single bond (-C-) and a carbon-carbon double bond (-C ═ C-); introducing an esterified phosphoric acid monoguanidine structure containing N and P; is beneficial to improving the flexibility of the polymer chain segment and reducing intermolecular (internal) interaction force, thereby reducing the content of the polyurethaneGlass transition temperature (T) of ester foam g ) The low-temperature resistance of the material is enhanced, and the material can be applied for a long time in the fields of external wall heat-insulation polyurethane boards, cold chain transportation heat-insulation foams and the like, and the foam performance is lasting and stable.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative only and not to limit the scope of the invention.
The raw material sources are as follows:
the concentrated sulfuric acid is 98% concentrated sulfuric acid by mass, and the brand is Adamas;
the purity of the phosphoric acid mono-guanidine is 99.98 percent, and the supplier is Condisi chemical company Limited;
the purity of the tris (2-chloropropyl) phosphate is 99 percent, and the supplier is Jiangsu Chang Yu chemical industry Co., Ltd;
diphenylmethane diisocyanate, available from Vanhua chemical Co., Ltd;
n, N dimethyl cyclohexylamine, supplier air chemical, usa;
stannous octoate, a supplier of air chemical in the united states;
AK8001, a supplier of south kyo de mei seiko;
b8681, the supplier is shanghai degussa;
HCFC-141B, a supplier of environmental protection technologies, Inc. of Shanghai Rui.
Example 1:
the preparation method of the esterified phosphoric acid monoguanidine comprises the following steps: adding 157g of phosphoric acid monoguanidine and 64g of methanol into a 1000mL reaction kettle, dropwise adding 0.16g of concentrated sulfuric acid, stirring, heating to 200 ℃, keeping the temperature for reaction for 4 hours, removing unreacted small molecular alcohol under vacuum of-90 kPa for 1 hour, and cooling to 30 ℃ to obtain esterified phosphoric acid monoguanidine A.
Example 2:
the preparation method of the esterified phosphoric acid monoguanidine comprises the following steps: 157g of phosphoric acid monoguanidine and 138g of ethanol are added into a 1000mL reaction kettle, 0.78g of concentrated sulfuric acid is added dropwise, the mixture is stirred, the temperature is raised to 120 ℃, the temperature is kept for reaction for 2 hours, the vacuum pressure is minus 90kPa, unreacted small molecular alcohol is removed for 1 hour, and the temperature is lowered to 30 ℃ to obtain the esterified phosphoric acid monoguanidine B.
Example 3:
the preparation method of the esterified phosphoric acid monoguanidine comprises the following steps: adding 157g of phosphoric acid monoguanidine and 120g of propanol into a 1000mL reaction kettle, dropwise adding 0.42g of concentrated sulfuric acid, stirring, heating to 150 ℃, keeping the temperature for reaction for 3h, removing unreacted small molecular alcohol under vacuum of-90 kPa for 1h, and cooling to 30 ℃ to obtain esterified phosphoric acid monoguanidine C.
Example 4:
a preparation method of castor oil based reactive flame-retardant polyester polyol comprises the following steps: adding 400g of castor oil, 300g of diethylene glycol and 470g of phthalic anhydride into a reaction kettle, then reacting for 8h at 200 ℃, bubbling nitrogen to extract water generated by the reaction, adding 5.85g of isobutyl titanate under the pressure of 1.0-2.0kPa, dehydrating for 4h under the vacuum of-90 kPa, adding 40g of esterified phosphoric acid-guanidine A, controlling the temperature at 200 ℃, and carrying out transesterification for 5h to obtain the castor oil-based reactive flame-retardant polyester polyol.
Example 5:
a preparation method of castor oil based reactive flame-retardant polyester polyol comprises the following steps: adding 4000g of castor oil, 1000g of glycerol and 4000g of terephthalic acid into a reaction kettle, reacting for 5h at 230 ℃, bubbling produced water by adopting nitrogen with the pressure of 1.0-2.0kPa, adding 4.5g of diethylamine, dehydrating for 3h under vacuum-99 kPa, adding 40g of esterified phosphoric acid guanidine B, controlling the temperature at 150 ℃, and carrying out transesterification reaction for 8h to obtain the castor oil-based reactive flame-retardant polyester polyol.
Example 6:
a preparation method of castor oil based reactive flame-retardant polyester polyol comprises the following steps: adding 2500g of castor oil, 600g of ethylene glycol, 1500g of propylene glycol, 4400g of adipic acid into a reaction kettle, reacting for 2h at 150 ℃, bubbling produced water with nitrogen under the pressure of 1.0-2.0kPa, adding 9.2g of stannic chloride, dehydrating for 2h under the vacuum of-95 kPa, adding 100g of esterified phosphoric acid-guanidine C, controlling the temperature at 200 ℃, and carrying out transesterification for 4h to obtain the castor oil-based reactive flame-retardant polyester polyol.
Comparative example 1:
a preparation method of castor oil-based polyester polyol comprises the following steps: adding 2500g of castor oil, 600g of ethylene glycol, 1500g of propylene glycol and 4400g of adipic acid into a reaction kettle, reacting at 150 ℃, adding 9.2g of stannic chloride into produced water for 2h under the nitrogen bubbling pressure of 1.0-2.0kPa, and dehydrating under the vacuum of-95 kPa for 2h to obtain the castor oil-based polyester polyol.
Comparative example 2:
a preparation method of reactive flame-retardant polyester polyol comprises the following steps: adding 2500g of glycerol, 600g of ethylene glycol, 1500g of propylene glycol and 4400g of adipic acid into a reaction kettle, reacting at 150 ℃, controlling the nitrogen bubbling pressure to be 1.0-2.0kPa, extracting water for 2h, adding 9.2g of stannic chloride, dehydrating at vacuum-95 kPa for 2h, adding 100g of esterified phosphoric acid-guanidine C, controlling the temperature to be 200 ℃, and carrying out transesterification for 4h to obtain the reactive flame-retardant polyester polyol.
Comparative example 3:
a preparation method of phosphate reaction type flame-retardant polyester polyol comprises the following steps: adding 2500g of glycerol, 600g of ethylene glycol, 1500g of propylene glycol and 4400g of adipic acid into a reaction kettle, reacting at 150 ℃, controlling the nitrogen bubbling pressure to be 1.0-2.0kPa, extracting water for 2h, adding 9.2g of stannic chloride, dehydrating at vacuum-95 kPa for 2h, adding 100g of tris (2-chloropropyl) phosphate, controlling the temperature to be 200 ℃, and carrying out transesterification for 4h to obtain the phosphate ester reaction type flame-retardant polyester polyol.
Preparation of polyurethane foam:
the foaming formula comprises the following raw materials in parts by weight:
TABLE 1
| Polyester polyols | 100 |
| Diphenylmethane diisocyanate | 125 |
| N, N dimethyl cyclohexylamine | 2.5 |
| Stannous octoate | 0.3 |
| AK8001 | 0.5 |
| B8681 | 1.5 |
| HCFC-141B | 25 |
| Deionized water | 2 |
Note-1: the polyester polyols were derived from examples 4-6 and comparative examples 1-3, respectively. Note-2: comparative example 1 foam preparation, an additional 4 parts by weight of esterified monoguanidine phosphate C were added.
The polyester polyols in the examples and comparative examples were subjected to foaming evaluation and performance tests, and the test results were as follows:
and (3) testing the flame retardant property:
the test method comprises the following steps: the oxygen index is tested with reference to the ASTM D2863 standard. The sample size was (120 ± 0.5) × (10 ± 0.5) × (4 ± 0.2) mm of the sample, and at least 5 specimens per group were averaged.
TABLE 2 foam oxygen index Performance test
| Sources of polyester polyols | Example 4 | Example 5 | Example 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Oxygen index | 28.6 | 28.9 | 30.1 | 18.6 | 27.8 | 25.3 |
Note: the higher the oxygen index, the better the flame retardant performance. As in example 4, the oxygen index is 28.6, indicating that the atmosphere with an oxygen content of about 28.6% can be ignited.
And (3) flame retardant test results: the castor oil reaction type flame-retardant polyester polyol has the oxygen index of over 28 generally, and is obviously superior to polyester polyol without a flame retardant (comparative example 1), flame-retardant polyester polyol without a castor oil component (comparative example 2) and phosphate ester flame-retardant polyester polyol (comparative example 3). The castor oil reaction type flame-retardant polyester polyol prepared by the invention has excellent flame-retardant effect.
And (4) testing the storage stability:
TABLE 3
| Change in oxygen index | 3 months old | 6 months old | 12 months old | 24 months |
| Example 4 | 28.6 | 28.6 | 28.6 | 28.5 |
| Example 5 | 28.9 | 28.8 | 28.9 | 28.9 |
| Example 6 | 30.1 | 30.1 | 30.1 | 30.1 |
| Comparative example 2 | 27.8 | 27.6 | 27.7 | 27.6 |
| Comparative example 3 | 25.3 | 25.0 | 24.9 | 24.3 |
The stability test results are: the castor oil reaction type flame-retardant polyester polyol prepared by the invention has no reduction of flame-retardant effect after being placed for 2 years, which shows that the flame-retardant effect is lasting and stable.
Testing the mechanical property of the foam:
the test method comprises the following steps: tear strength and elongation at break were tested using standard DIN 53504; the hardness was measured using the standard DIN 53505.
TABLE 4
| Sample (I) | Tear Strength kN/m | Elongation at break% | Hardness Shore D |
| Example 4 | 132.3 | 82 | 72 |
| Example 5 | 131.5 | 85 | 73 |
| Example 6 | 129.6 | 83 | 73 |
| Comparative example 1 | 120.0 | 78 | 68 |
| Comparative example 2 | 123.8 | 80 | 65 |
| Comparative example 3 | 118.2 | 75 | 70 |
The mechanical property test result is as follows: the foam sample prepared from the castor oil reaction type flame-retardant polyester polyol prepared by the invention has better tear strength, elongation at break and hardness than the polyester polyol foam sample in the comparative example.
And (3) low temperature resistance test:
the test method comprises the following steps: taking the samples in the examples and the comparative examples, adjusting the state of the samples for not less than 4 hours according to the standard environment regulation of GB 291823/25, putting the samples into a low-temperature box with the temperature fluctuation of not more than +/-2 ℃ in the environment of the test, starting timing after the temperature is adjusted to minus 30 to minus 50 ℃ and kept constant for 0.5 hour, taking out the instrument panel mask after 4 hours, standing for 0.5 hour, and checking whether the surfaces of the samples have abnormal conditions such as cracking, deformation, discoloration and the like. The results are shown in Table 5:
TABLE 5
| Sample (I) | -30℃ | -40℃ | -50℃ |
| Example 4 | Intact | Intact | Intact |
| Example 5 | Intact | Intact | Intact |
| Example 6 | Intact | Intact | Is intact |
| Comparative example 1 | Slight cracking | Cracking, deformation | Cracking, deformation |
| Comparative example 2 | Intact | Cracking of | Cracking, deformation |
| Comparative example 3 | Slight cracking | Cracking of | Cracking, deformation |
Test results of low temperature resistance: the foam sample prepared from the castor oil reaction type flame-retardant polyester polyol can be normally used at the temperature of 50 ℃ below zero, and has excellent low-temperature resistance.
Claims (9)
1. A preparation method of castor oil based reaction type flame-retardant polyester polyol is characterized by comprising the following steps:
step a): performing polycondensation reaction on castor oil, micromolecular polyhydric alcohol, micromolecular polybasic acid or anhydride under the action of a catalyst to obtain castor oil-based polyester polyol;
step b): adding esterified phosphoric acid guanidine into the castor oil-based polyester polyol obtained in the step a), and carrying out ester exchange reaction to obtain the castor oil-based reactive flame-retardant polyester polyol.
2. The preparation method according to claim 1, wherein in the step a), castor oil, small molecule polyol, small molecule polyacid or anhydride is added in a mass ratio of 20-40: 10-30: 40 to 47 percent, and the adding amount of the catalyst is 0.05 to 0.5 percent of the total mass of the raw materials.
3. The method according to claim 1 or 2, wherein in step a), the small-molecule polyol is C 2 -C 8 The polyhydric alcohol of (1) comprises one or more of ethylene glycol, diethylene glycol, propylene glycol, glycerol, dipropylene glycol and butanediol;
the small molecular polybasic acid or anhydride is C 4- C 10 The polybasic acid or anhydride of (2) comprises one or more of adipic acid, phthalic anhydride;
the catalyst comprises one or more of isopropyl titanate, isobutyl titanate, stannic chloride and diethylamine.
4. The process according to any one of claims 1 to 3, wherein in step a), the temperature of the polycondensation reaction is 150 ℃ to 230 ℃ and the reaction time is 4 to 12 hours.
5. The method as claimed in any one of claims 1 to 4, wherein the temperature of the transesterification reaction in step b) is 150-200 ℃; the reaction time is 4-8 h.
6. The method according to any one of claims 1 to 5, wherein in step b), the mass ratio of the amount of the esterified monoguanidine phosphate to the amount of the castor oil is 1: 10-100.
7. The method of any one of claims 1-6, wherein in step b), the esterified monoguanidine phosphate has the formula:
wherein Gu is guanidine and has the structure of
R 1 Is C 1 -C 14 Alkane chain, R 2 Is C 1 -C 14 An alkane chain.
8. The method of any one of claims 1-7, wherein in step b), the esterified monohydroguanadine phosphate is prepared by: carrying out esterification modification on guanidine phosphate and small molecular alcohol under the catalysis of concentrated sulfuric acid to synthesize esterified guanidine phosphate;
preferably, in the preparation method of the esterified phosphoric acid monoguanidine, the small molecular alcohol is C 1 -C 14 The monofunctional alcohol of (a) includes one or more of methanol, ethanol, propanol, etc.;
preferably, the mole ratio of the small molecule alcohol to the guanidine phosphate is 2-3: 1; the dosage of the concentrated sulfuric acid is 0.1-0.5 percent of the mass of the phosphoric acid monoguanidine.
9. The method according to any one of claims 1 to 8, wherein the reaction temperature in the method for preparing esterified phosphoric acid-guanidine is 120-200 ℃; the reaction time is 2-8 h.
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