CN105367774A - Nitrogen heterocyclic castor oil-based polyester polyol and preparation method and use thereof - Google Patents
Nitrogen heterocyclic castor oil-based polyester polyol and preparation method and use thereof Download PDFInfo
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Abstract
A nitrogen heterocyclic castor oil-based polyester polyol and a preparation method and use thereof are disclosed, the nitrogen heterocyclic castor oil-based polyester polyol is used for flame retardant polyurethane materials in the field of building insulation. The nitrogen heterocyclic castor oil-based polyester polyol is prepared from polyhydric castor oil, a naphthalene aromatic dicarboxylic acid, a dicarboxylic acid and a small molecular alcohol or a small molecular acid by esterification and grafting under the effect of a catalyst, and the nitrogen heterocyclic castor oil-based polyester polyol has high flame retardant properties and excellent mechanical properties. Polyurethane foam prepared from the nitrogen heterocyclic castor oil-based polyester polyol has high flame retardancy, thermal stability and good activity, and also has good compression strength, rate of closed holes, abrasion resistance, aging resistance, heat resistance and other physical properties. The synthesis process is simple, and the polyester polyol is well compatible with other polyester and polyether polyols. The polyurethane foam prepared from the nitrogen heterocyclic castor oil-based polyester polyol has better thermal stability and flame retardancy, and can be used in the field of building insulation.
Description
Technical field
The present invention relates to a kind of modified poly ester polyvalent alcohol that can be used for flame retardant polyurethane material and its production and use, furtherly, the present invention relates to a kind of novel high flame retardant polyester polyol and preparation method thereof, and it can be used as polyester polyol component in polyurethane foam, the application especially in rigid foam.
Background technology
In recent years, Global Oil resource is day by day exhausted, people require more and more higher to the flame retardant properties of material, and the dynamics of national renovating environment problem is also increasing simultaneously, impels the research of macromolecular material towards cleaning chemical, chemical technology and high flame resistance future development.Recyclable organism starting material petroleum replacing chemical raw material is used to be trend of the times.Therefore, develop the novel Viscotrol C polyester polyol of new technical study, polyurethane foam prepared by petroleum replacing industrial chemicals, splits and sends out the raw-material deep processing of bio-based, walks sustainable development path and have important practical significance.
Polyurethane foam light weight, rate of closed hole are high, intensity is high, it is a kind of lagging material efficiently, but because of its vesicular structure, foam easily burns, general its flame retardant properties that improves is mainly based on addition type and response type two kinds, addition type needs to add a large amount of fire retardants, often make the physical mechanical processing characteristics of material significantly reduce, and the time is longer, flame retardant properties can be moved, flame retardant effect reduces greatly, instead there is potential safety hazard.Reactive flame retardant, due to reactive chemical group, forms covalent linkage with urethane, not easily moves, and improves the lasting flame retardant resistance of polyurethane foam.Therefore develop nitrogen heterocyclic ring Viscotrol C flame-proof polyol and there is realistic meaning.
Summary of the invention
The object of the present invention is to provide a kind of nitrogenous heterocyclic castor oil-base flame retardant polyester polyvalent alcohol and its production and use
For achieving the above object, the technical solution used in the present invention is:
A kind of nitrogenous heterocyclic castor oil-base flame retardant polyester polyvalent alcohol, it is characterized in that: by polyol, containing naphthalene system aromatic acid, diprotic acid and small molecular alcohol or acid under the effect of catalyzer, oxidation inhibitor, carry out grafting 2 again after esterification, 4,6-trihydroxy--1, the hydroxymethyl derivative reaction of 3,5-triazine forms; Described polyol, many rings are (5.75-7.75) containing the mass ratio of naphthalene dicarboxylic acid, anhydrides and small molecular alcohol or acid: (1.58-2.75): (1-1.75): (2.83-3.75), (3-3.36); The mass ratio of the hydroxymethyl derivative of described castor oil-base phthalic anhydride polyester and 2,4,6-trihydroxy--1,3,5-triazines is 1:(0.05-0.15).Average functional group is 2.8, acid number < 2.0mgKOH/g, and average hydroxyl value is at 230-260mgKOH/g, and molecular-weight average is 800-1300g/mol, and viscosity is 4000-5000mPas.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that: described polyol is Viscotrol C.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that: described many rings are 2,6-naphthalene dicarboxylic acids containing naphthalene aromatic acid.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that: described anhydrides is Tetra hydro Phthalic anhydride, Succinic anhydried, one or both the mixture in MALEIC ANHYDRIDE, propionic anhydride; Described small molecular alcohol is ethylene glycol, butyleneglycol, isopropylcarbinol, Diethylene Glycol, glycerol, propylene glycol, one or both the mixture in TriMethylolPropane(TMP); Described catalyzer is tetrabutyl titanate, tetrabutyl titanate, triphenylphosphine, tin protochloride, stannous octoate, the one or two or more mixture in Dibutyltin oxide.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that: the structure of the hydroxymethyl derivative of 2,4,6-described trihydroxyies-1,3,5-triazines as shown in the formula:
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that, described polyol, many rings are (5.75-7.75) containing the mass ratio of naphthalene dicarboxylic acid, anhydrides and small molecular alcohol or acid: (1.58-2.75): (1-1.75): (2.83-3.75).
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that, described polyol, many rings are (2.0-2.7) containing total mol ratio of naphthalene dicarboxylic acid, anhydrides and small molecular alcohol or acid: (0.9-1.5): (0.8-1.4): (2.0-2.7).
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that, the mass ratio of the hydroxymethyl derivative of described castor oil-base phthalic anhydride polyester and 2,4,6-trihydroxy--1,3,5-triazines is 1:(0.05-0.15).
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that, described catalyzer is titanium isopropylate, tetrabutyl titanate, triphenylphosphine, tin protochloride, stannous octoate, the mixture of the one or two or more of Dibutyltin oxide.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that, catalyst levels is the 0.006wt%-0.3wt% of total material.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that, 2,4,6-described trihydroxyies-1, the hydroxymethyl derivative of 3,5-triazine is about to 2,4,6-trihydroxy--1,3,5-triazine adds MALEIC ANHYDRIDE after carrying out hydroxylation, carries out Carboxylation at 50-60 DEG C.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that: by following quality proportioning: Viscotrol C, 700kg, 2,6-naphthalene dicarboxylic acids: 220kg, Tetra hydro Phthalic anhydride, 150kg, Diethylene Glycol, 250kg, titanium isopropylate: 0.66kg, take Viscotrol C, 2, 6-naphthalene dicarboxylic acids, Tetra hydro Phthalic anhydride, Diethylene Glycol, titanium isopropylate joins in reactor, and pass into nitrogen protection, then start to heat up, stir, be warmed up to 160 DEG C gradually, carry out synthesis under normal pressure after 2.5 hours, be warming up to 185 DEG C, start have moisture to distillate, when reaching 230 DEG C, be incubated 7 hours, when aquifer yield reaches 85% of aquifer yield, stop passing into nitrogen, be cooled to 190 DEG C, start segmentation to vacuumize, progressively gas clean-up, until pressure reaches-0.1MPa, while vacuumizing, heating makes temperature rise to 230 DEG C, react 1.5 ~ 2 hours under these conditions.After tested, product acid number is down to and is less than 5mgKOH/g, stopped reaction, is cooled to 80 DEG C, adds the hydroxymethyl derivative of 2,4,6-trihydroxy--1,3,5-triazines, 120kg; Be less than 2mgKOH/g, stopped reaction, cooling discharge to reaction acid number, obtain nitrogen heterocyclic ring castor oil-base polyester polyol, product appearance is light yellow viscous liquid, and hydroxyl value is 245mgKOH/g, and viscosity is 4800mPa.s, moisture 0.07%.
According to described nitrogen heterocyclic ring castor oil-base polyester polyol, it is characterized in that: by following quality proportioning: Viscotrol C, 690kg, 2,6-naphthalene dicarboxylic acids: 220kg, Tetra hydro Phthalic anhydride, 155kg, Diethylene Glycol, 280kg, titanium isopropylate: 0.66kg, take Viscotrol C, 2, 6-naphthalene dicarboxylic acids, Tetra hydro Phthalic anhydride, Diethylene Glycol, titanium isopropylate joins in reactor, and pass into nitrogen protection, then start to heat up, stir, be warmed up to 160 DEG C gradually, carry out synthesis under normal pressure after 2.5 hours, be warming up to 185 DEG C, start have moisture to distillate, when reaching 230 DEG C, be incubated 6 hours, when aquifer yield reaches 82% of aquifer yield, stop passing into nitrogen, be cooled to 190 DEG C, start segmentation to vacuumize, progressively gas clean-up, until pressure reaches-0.1MPa, while vacuumizing, heating makes temperature rise to 230 DEG C, react 2 hours under these conditions.After tested, product acid number is down to and is less than 5mgKOH/g, stopped reaction, is cooled to 80 DEG C, adds the hydroxymethyl derivative of 2,4,6-trihydroxy--1,3,5-triazines, 100kg; Be less than 2mgKOH/g, stopped reaction, cooling discharge to reaction acid number, obtain nitrogen heterocyclic ring castor oil-base polyester polyol, product appearance is light yellow viscous liquid, and hydroxyl value is 255mgKOH/g, and viscosity is 4200mPa.s, moisture 0.05%.
The application of nitrogen heterocyclic ring castor oil-base polyester polyol in flame retardant polyurethane hard foam described in a kind of basis.
Beneficial effect of the present invention:
Polyester polyol of the present invention has high flame resistance and excellent mechanical property, by polyurethane foam prepared by this kind of polyester polyol, there is thermostability, good activity and high flame retardant resistance, and there is good compressive strength, rate of closed hole, wear resistance, ageing resistance, the physicalies such as thermotolerance.
The invention provides above-mentioned nitrogen heterocyclic ring castor oil-base polyester polyol as the application of flame-proof polyol in flame retardant polyurethane material, be applied in polyurethane material, introduce the method for modifying of bio-based starting material and employing response type, the nitrogen heterocyclic ring structure of many rings of rigid structure naphthalene structure and Heat stability is good is incorporated on polyol backbone, enhance the flame retardant effect of polyester polyol, improve the high flame resistance of foam itself, and there is the low character of viscosity, be conducive to the degree of uniformity of foam, the polyurethane foam obtained is finer and smoother, and abscess is less.
3rd object of the present invention is that above-mentioned nitrogen heterocyclic ring castor oil-base polyester polyol adds Viscotrol C, many rings naphthalene structure, nitrogen heterocyclic ring in flame retardant polyurethane material, more environmental protection, more economical, tradition fire retardant material many introducings ignition-proof element phosphorus and halogen, environmental pollution is comparatively serious, and this kind of novel azaheterocyclic castor oil-base fire retardant material can replace traditional fire retardant material completely.
Embodiment
Be below specific embodiments of the invention, technical scheme of the present invention is further described, but the present invention is not limited to following embodiment.
Preparation method of the present invention mainly comprises the following steps:
The first step: synthesize hydroxyl telechelic polyester under the condition that alcohols is excessive.Raw material monomer, catalyzer etc. are added in reactor, be progressively warming up to 220 ~ 240 DEG C, react 5 ~ 8 hours.Reaction is carried out under nitrogen protection at normal pressure early stage, reaches the acid number to setting, under reduced pressure, 190 ~ 230 DEG C, reacts 1.5 ~ 2 hours, reach required index; Second step: at 80 DEG C, adds 2,4, the 6-trihydroxyies-1,3,5-triazines of modification until reach required index can react complete.
A kind of nitrogen heterocyclic ring castor oil-base of the present invention polyester polyol, by polyol, containing naphthalene system aromatic acid, diprotic acid and small molecular alcohol or acid under the effect of catalyzer, carry out esterification to obtain, average functional group is 2.8, acid number < 2.0mgKOH/g, and average hydroxyl value is at 230-260mgKOH/g, molecular-weight average is 800-1300g/mol, and viscosity is 4000-5000mPas(25 DEG C).
Novel azaheterocyclic castor oil-base polyester polyol is 2 by containing naphthalene system aromatic acid, the triazines of 6-naphthalene dicarboxylic acids and modification, because of its naphthalene structure containing many rings and heterocycle structure, rigid-skeleton makes the polyvalent alcohol goods participated in by its synthesis have high-intensity performance, having more commercialization in fire-retardant to be worth, is the indispensable important monomer of urethane resin.
Described polyester polyol, is characterized in that: described polyol is Viscotrol C, and described many rings are 2,6-naphthalene dicarboxylic acids containing naphthalene aromatic acid.
Described anhydrides is Tetra hydro Phthalic anhydride, Succinic anhydried, one or both the mixture in MALEIC ANHYDRIDE, propionic anhydride, one or both mixtures of preferred Tetra hydro Phthalic anhydride and Succinic anhydried; Described small molecular alcohol is ethylene glycol, butyleneglycol, isopropylcarbinol, Diethylene Glycol, glycerol, propylene glycol, one or both the mixture in TriMethylolPropane(TMP), one or both mixtures of preferred ethylene glycol and Diethylene Glycol; Described catalyzer is tetrabutyl titanate, tetrabutyl titanate, triphenylphosphine, tin protochloride, stannous octoate, the one or two or more mixture in Dibutyltin oxide, the one in preferred tetrabutyl titanate, tetrabutyl titanate, triphenylphosphine and two kinds.
The structure of the hydroxymethyl derivative of 2,4,6-described trihydroxyies-1,3,5-triazines as shown in the formula:
Described polyol, many rings be (5.75-7.75) containing the mass ratio of naphthalene dicarboxylic acid, anhydrides and small molecular alcohol or acid: (1.58-2.75): (1-1.75): (2.83-3.75), preferred (5.85-6.38): (2-2.3): (1-1.25): (3-3.36).
Described polyol, many rings be (2.0-2.7) containing total mol ratio of naphthalene dicarboxylic acid, anhydrides and small molecular alcohol or acid: (0.9-1.5): (0.8-1.4): (2.0-2.7), preferred (2.2-2.4): (1.2-1.4): (0.9-1.1): (2.3-2.6).
The mass ratio of the hydroxymethyl derivative of described castor oil-base phthalic anhydride polyester and 2,4,6-trihydroxy--1,3,5-triazines is 1:(0.05-0.15), preferred 1:(0.06-0.12).
Described catalyzer is titanium isopropylate, tetrabutyl titanate, triphenylphosphine, tin protochloride, stannous octoate, the mixture of the one or two or more of Dibutyltin oxide, preferred titanium isopropylate, tetrabutyl titanate, one or both mixtures of triphenylphosphine.
Catalyst levels is the 0.006wt%-0.3wt% of total material, preferred 0.01wt%-0.08wt%.
Described esterification is divided into synthesis under normal pressure and Depressor response, and synthesis under normal pressure is 120-250 DEG C, preferred 150-240 DEG C, and the reaction times is 5-13 hour, preferred 8-10 hour; Depressor response temperature is 170-250 DEG C, preferred 190-230 DEG C, and the reaction times is 1-4 hour.Preferred 1-2 hour, reaction pressure is 0.01-0.1MPa.
Described esterification is divided into synthesis under normal pressure and Depressor response, and synthesis under normal pressure is 120-250 DEG C, preferred 150-240 DEG C, and the reaction times is 5-13 hour, preferred 8-10 hour; Depressor response temperature is 170-250 DEG C, preferred 190-230 DEG C, and the reaction times is 1-4 hour.Preferred 1-2 hour, reaction pressure is-0.01-(-0.1) MPa;
The fire-retardant intermediate temperature of described graft modification triazines is 80 degree.
Embodiment 1
The preparation of polyester polyol: by following quality proportioning: Viscotrol C, 700kg, 2,6-naphthalene dicarboxylic acids: 220kg, Tetra hydro Phthalic anhydride, 150kg, Diethylene Glycol, 250kg, titanium isopropylate: 0.66kg, take Viscotrol C, 2, 6-naphthalene dicarboxylic acids, Tetra hydro Phthalic anhydride, Diethylene Glycol, titanium isopropylate joins in reactor, and pass into nitrogen protection, then start to heat up, stir, be warmed up to 160 DEG C gradually, carry out synthesis under normal pressure after 2.5 hours, be warming up to 185 DEG C, start have moisture to distillate, when reaching 230 DEG C, be incubated 7 hours, when aquifer yield reaches 85% of aquifer yield, stop passing into nitrogen, be cooled to 190 DEG C, start segmentation to vacuumize, progressively gas clean-up, until pressure reaches-0.1MPa, while vacuumizing, heating makes temperature rise to 230 DEG C, react 1.5 ~ 2 hours under these conditions.After tested, product acid number is down to and is less than 5mgKOH/g, stopped reaction, is cooled to 80 DEG C, adds the hydroxymethyl derivative of 2,4,6-trihydroxy--1,3,5-triazines, 120kg; Be less than 2mgKOH/g, stopped reaction, cooling discharge to reaction acid number, obtain the castor oil-base polyester polyol of novel azaheterocyclic, product appearance is light yellow viscous liquid, and hydroxyl value is 245mgKOH/g, and viscosity is 4800mPa.s, moisture 0.07%.
Embodiment 2
The preparation of polyester polyol: by following quality proportioning: by following quality proportioning: Viscotrol C, 690kg, 2,6-naphthalene dicarboxylic acids: 220kg, Tetra hydro Phthalic anhydride, 155kg, Diethylene Glycol, 280kg, titanium isopropylate: 0.66kg, take Viscotrol C, 2, 6-naphthalene dicarboxylic acids, Tetra hydro Phthalic anhydride, Diethylene Glycol, titanium isopropylate joins in reactor, and pass into nitrogen protection, then start to heat up, stir, be warmed up to 160 DEG C gradually, carry out synthesis under normal pressure after 2.5 hours, be warming up to 185 DEG C, start have moisture to distillate, when reaching 230 DEG C, be incubated 6 hours, when aquifer yield reaches 82% of aquifer yield, stop passing into nitrogen, be cooled to 190 DEG C, start segmentation to vacuumize, progressively gas clean-up, until pressure reaches-0.1MPa, while vacuumizing, heating makes temperature rise to 230 DEG C, react 2 hours under these conditions.After tested, product acid number is down to and is less than 5mgKOH/g, stopped reaction, is cooled to 80 DEG C, adds the hydroxymethyl derivative of 2,4,6-trihydroxy--1,3,5-triazines, 100kg; Be less than 2mgKOH/g, stopped reaction, cooling discharge to reaction acid number, obtain nitrogen heterocyclic ring castor oil-base polyester polyol, product appearance is light yellow viscous liquid, and hydroxyl value is 255mgKOH/g, and viscosity is 4200mPa.s, moisture 0.05%.
Polyvalent alcohol based on the invention process 1 and the fire-retardant benzoic anhydride polyester polyol of the novel azaheterocyclic implementing 2 preparations are composite with conventional polyether glycol 4110, according to the recipe configuration combined polyether (in vain expect) of table 1, then with the black material of many subunits polyphenyl polyisocyanate PM-200() mix high-speed stirring and carry out foaming experiment; And flame retardant properties and Mechanics Performance Testing are carried out to the hard polyurethane foam of preparation; And with conventional polyester polyol 4110 as a comparison.
Contrast and experiment shows, and when raw materials used kind and ratio change, prepared polyester polyol product over-all properties can rise and fall to some extent.But conventional polyester polyvalent alcohol goods oxygen index (OI) are starkly lower than the goods oxygen index (OI) of nitrogenous heterocyclic castor oil-base polyester polyol in embodiment.Adopt the hard polyurethane foam prepared based on the castor oil-base polyester polyol of novel azaheterocyclic of the present invention, under identical formula system and foam density, substantially increase the oxygen index of foam to more than 31%, also obviously change foam size stability.Under simultaneously equal catalyst levels, the expansion rate adding the foam of this new polyester polyvalent alcohol, also faster than the formula system being raw material with conventional polyester polyvalent alcohol, can reduce the consumption of catalyzer with this, reduces cost.Other components in the castor oil-base polyester polyol of last novel azaheterocyclic and premixed systems have excellent consistency, and its premixed systems of joining is transparent and homogeneous, has excellent storage stability.
Claims (10)
1. a nitrogenous heterocyclic castor oil-base polyester polyol, it is characterized in that: contain naphthalene dicarboxylic acid, anhydrides and small molecular alcohol under the effect of catalyzer by polyol, many rings, carry out the polyester polyol that esterification obtains, and grafting one 2,4, the hydroxymethyl derivative of 6-trihydroxy--1,3,5-triazines; Average functional group is 2.8, acid number < 2.0mgKOH/g, and average hydroxyl value is at 230-260mgKOH/g, and molecular-weight average is 800-1300g/mol, and viscosity is 4000-5000mPas.
2. the nitrogenous heterocyclic castor oil-base polyester polyol of one according to claim 1, is characterized in that:
Described polyol is Viscotrol C;
Described many rings are 2,6-naphthalene dicarboxylic acids containing naphthalene aromatic acid;
Described anhydrides is Tetra hydro Phthalic anhydride, Succinic anhydried, one or both or two or more mixtures in MALEIC ANHYDRIDE, propionic anhydride, one or both mixtures in preferred Tetra hydro Phthalic anhydride and Succinic anhydried;
Described small molecular alcohol is ethylene glycol, butyleneglycol, isopropylcarbinol, Diethylene Glycol, glycerol, propylene glycol, one or both or two or more mixtures in TriMethylolPropane(TMP), one or both mixtures in preferred ethylene glycol and Diethylene Glycol;
Described catalyzer is tetrabutyl titanate, tetrabutyl titanate, triphenylphosphine, tin protochloride, stannous octoate, one or both or two or more mixtures in Dibutyltin oxide, one or both or two or more mixtures in preferred tetrabutyl titanate, tetrabutyl titanate, triphenylphosphine.
3. the nitrogenous heterocyclic castor oil-base polyester polyol of one according to claim 1, is characterized in that: the structure of the hydroxymethyl derivative of 2,4,6-described trihydroxyies-1,3,5-triazines as shown in the formula:
4. the nitrogenous heterocyclic castor oil-base polyester polyol of one according to claims 1 to 2, is characterized in that,
Described polyol, many rings be (5.75-7.75) containing the mass ratio of naphthalene dicarboxylic acid, anhydrides and small molecular alcohol or acid: (1.58-2.75): (1-1.75): (2.83-3.75), preferred (5.85-6.38): (2-2.3): (1-1.25): (3-3.36);
Described polyol, many rings be (2.0-2.7) containing total mol ratio of naphthalene dicarboxylic acid, anhydrides and small molecular alcohol or acid: (0.9-1.5): (0.8-1.4): (2.0-2.7), preferred (2.2-2.4): (1.2-1.4): (0.9-1.1): (2.3-2.6);
The mass ratio of the hydroxymethyl derivative of described polyester polyol and 2,4,6-trihydroxy--1,3,5-triazines is 1:(0.05-0.15), preferred 1:(0.06-0.12);
Described catalyst levels is the 0.006wt%-0.3wt% of total material, preferred 0.01wt%-0.08wt%.
5. the nitrogenous heterocyclic castor oil-base polyester polyol of one according to claim 1, it is characterized in that, described esterification is divided into synthesis under normal pressure and Depressor response, synthesis under normal pressure is 120-250 DEG C, preferred 150-240 DEG C, the reaction times is 5-13 hour, preferred 8-10 hour; Depressor response temperature is 170-250 DEG C, preferred 190-230 DEG C, and the reaction times is 1-4 hour, preferred 1-2 hour, and reaction pressure is-0.01-(-0.1) MPa.
6. the nitrogenous heterocyclic castor oil-base polyester polyol of one according to claim 1, is characterized in that, described 2,4, the hydroxymethyl derivative of 6-trihydroxy--1,3,5-triazines is about to 2,4, after 6-trihydroxy--1,3,5-triazines carries out hydroxylation, add MALEIC ANHYDRIDE, carry out Carboxylation at 50-60 DEG C.
7. the nitrogenous heterocyclic castor oil-base polyester polyol of one according to claim 1, is characterized in that: by following quality proportioning: Viscotrol C, 700kg, 2,6-naphthalene dicarboxylic acids: 220kg, Tetra hydro Phthalic anhydride, 150kg, Diethylene Glycol, 250kg, titanium isopropylate: 0.66kg, take Viscotrol C, 2, 6-naphthalene dicarboxylic acids, Tetra hydro Phthalic anhydride, Diethylene Glycol, titanium isopropylate joins in reactor, and pass into nitrogen protection, then start to heat up, stir, be warmed up to 160 DEG C gradually, carry out synthesis under normal pressure after 2.5 hours, be warming up to 185 DEG C, start have moisture to distillate, when reaching 230 DEG C, be incubated 7 hours, when aquifer yield reaches 85% of aquifer yield, stop passing into nitrogen, be cooled to 190 DEG C, start segmentation to vacuumize, progressively gas clean-up, until pressure reaches-0.1MPa, while vacuumizing, heating makes temperature rise to 230 DEG C, react 1.5 ~ 2 hours under these conditions, after tested, product acid number is down to and is less than 5mgKOH/g, stopped reaction, is cooled to 80 DEG C, adds the hydroxymethyl derivative of 2,4,6-trihydroxy--1,3,5-triazines, 120kg, be less than 2mgKOH/g, stopped reaction, cooling discharge to reaction acid number, obtain nitrogenous heterocyclic castor oil-base polyester polyol, product appearance is light yellow viscous liquid, and hydroxyl value is 245mgKOH/g, and viscosity is 4800mPa.s, moisture 0.07%.
8. the nitrogenous heterocyclic castor oil-base polyester polyol of one according to claim 1, is characterized in that: by following quality proportioning: Viscotrol C, 690kg, 2,6-naphthalene dicarboxylic acids: 220kg, Tetra hydro Phthalic anhydride, 155kg, Diethylene Glycol, 280kg, titanium isopropylate: 0.66kg, take Viscotrol C, 2, 6-naphthalene dicarboxylic acids, Tetra hydro Phthalic anhydride, Diethylene Glycol, titanium isopropylate joins in reactor, and pass into nitrogen protection, then start to heat up, stir, be warmed up to 160 DEG C gradually, carry out synthesis under normal pressure after 2.5 hours, be warming up to 185 DEG C, start have moisture to distillate, when reaching 230 DEG C, be incubated 6 hours, when aquifer yield reaches 82% of aquifer yield, stop passing into nitrogen, be cooled to 190 DEG C, start segmentation to vacuumize, progressively gas clean-up, until pressure reaches-0.1MPa, while vacuumizing, heating makes temperature rise to 230 DEG C, react 2 hours under these conditions, after tested, product acid number is down to and is less than 5mgKOH/g, stopped reaction, is cooled to 80 DEG C, adds the hydroxymethyl derivative of 2,4,6-trihydroxy--1,3,5-triazines, 100kg, be less than 2mgKOH/g, stopped reaction, cooling discharge to reaction acid number, obtain nitrogenous heterocyclic castor oil-base polyester polyol polyvalent alcohol, product appearance is light yellow viscous liquid, and hydroxyl value is 255mgKOH/g, and viscosity is 4200mPa.s, moisture 0.05%.
9. prepare the method for the castor oil-base polyester polyol of novel azaheterocyclic described in claim 1 ~ 8 for one kind, it is characterized in that: under the condition that alcohols is excessive, synthesize hydroxyl telechelic polyester, raw material monomer, catalyzer etc. are added in reactor, be progressively warming up to 220 ~ 240 DEG C, react 5 ~ 8 hours; Reaction is in earlier stage at normal pressure, and carry out under nitrogen protection, reach the acid number of setting, hydroxyl value and range of viscosities, synthesis under normal pressure temperature is 120 ~ 250 DEG C, and the reaction times is 5 ~ 10 hours; Under reduced pressure, 190 ~ 230 DEG C, react 1.5 ~ 2 hours, reaction pressure is-0.08 ~ (-0.1) Mpa, reaches required index, can add 2,4, the 6-trihydroxyies-1,3,5-triazines of modification until reach required index can react complete.
10. the application of nitrogenous heterocyclic castor oil-base flame retardant polyester polyvalent alcohol in flame retardant polyurethane hard foam according to any one of claim 1 ~ 8.
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| CN107383368A (en) * | 2017-08-18 | 2017-11-24 | 浙江心源科技有限公司 | A kind of application containing amide groups PEPA and on polyurethane is prepared |
| CN107602831A (en) * | 2017-10-31 | 2018-01-19 | 山东诺威聚氨酯股份有限公司 | The production method of hard bubble PEPA |
| CN110372851A (en) * | 2019-07-18 | 2019-10-25 | 重庆韩拓科技有限公司 | A kind of synthetic method of the carpenter's glue flame-proof polyol of three-functionality-degree high cohesion energy |
| CN111978524A (en) * | 2020-09-08 | 2020-11-24 | 江苏德励达新材料有限公司 | Method for preparing nitrogenous heterocyclic polyester polyol with good pentane compatibility |
| CN114853998A (en) * | 2022-05-06 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method of castor oil based reactive flame-retardant polyester polyol |
| CN118271584A (en) * | 2024-04-30 | 2024-07-02 | 湖南聚仁新材料股份公司 | Low-viscosity flame-retardant polyester polyol and preparation method and application thereof |
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| CN107383368A (en) * | 2017-08-18 | 2017-11-24 | 浙江心源科技有限公司 | A kind of application containing amide groups PEPA and on polyurethane is prepared |
| CN107602831A (en) * | 2017-10-31 | 2018-01-19 | 山东诺威聚氨酯股份有限公司 | The production method of hard bubble PEPA |
| CN110372851A (en) * | 2019-07-18 | 2019-10-25 | 重庆韩拓科技有限公司 | A kind of synthetic method of the carpenter's glue flame-proof polyol of three-functionality-degree high cohesion energy |
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| CN114853998A (en) * | 2022-05-06 | 2022-08-05 | 万华化学集团股份有限公司 | Preparation method of castor oil based reactive flame-retardant polyester polyol |
| CN118271584A (en) * | 2024-04-30 | 2024-07-02 | 湖南聚仁新材料股份公司 | Low-viscosity flame-retardant polyester polyol and preparation method and application thereof |
| CN118271584B (en) * | 2024-04-30 | 2024-09-20 | 湖南聚仁新材料股份公司 | Low-viscosity flame-retardant polyester polyol and preparation method and application thereof |
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