CN1308373C - Preparation method of fire retardant polymer polyether polyol and method for preparing block fire retardant polyurethane foam mateial therefrom - Google Patents
Preparation method of fire retardant polymer polyether polyol and method for preparing block fire retardant polyurethane foam mateial therefrom Download PDFInfo
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Abstract
一种阻燃聚合物聚醚多元醇制备方法及其用于制备块状阻燃聚氨酯泡沫材料的方法。阻燃聚合物聚醚多元醇由通用聚醚多元醇为连续相、表面接枝部分胺基化二异氰酸酯改性聚醚多元醇(分散剂)的亚纳米超微聚合物粒子为分散相及两相构成的稳定的聚合物胶体分散体系组成。用甲醛-尿素-三聚氰胺-六次甲基四胺在上述分散剂的存在下，于聚醚多元醇中在65℃～98℃下，反应0.5～4小时，干燥制得。产品不含磷、卤素、苯乙烯和丙烯腈等有毒有害物质，工艺简单、成本低。将该产品与通用聚醚多元醇、二异腈酸酯化合物在叔胺、有机金属催化剂、水、物理发泡剂和少量硅油匀泡剂的存在下，经块状发泡工艺制得阻燃聚氨酯泡沫材料。该材料阻燃性和力学性能良好。A method for preparing a flame-retardant polymer polyether polyol and a method for preparing a block-shaped flame-retardant polyurethane foam material. The flame-retardant polymer polyether polyol is composed of general-purpose polyether polyol as the continuous phase, sub-nano ultrafine polymer particles of partially aminated diisocyanate-modified polyether polyol (dispersant) on the surface as the dispersed phase and two Phase composition of stable polymer colloidal dispersion system. It is prepared by reacting formaldehyde-urea-melamine-hexamethylenetetramine in polyether polyol at 65°C-98°C for 0.5-4 hours in the presence of the above-mentioned dispersant and drying. The product does not contain toxic and harmful substances such as phosphorus, halogen, styrene and acrylonitrile, and the process is simple and the cost is low. Combining this product with general-purpose polyether polyols and diisocyanate compounds in the presence of tertiary amines, organic metal catalysts, water, physical foaming agents and a small amount of silicone oil foam stabilizer, the flame-retardant Polyurethane foam. The material has good flame retardancy and mechanical properties.
Description
Technical field
The invention belongs to polyether polyol and preparation Application Areas thereof, be specifically related to a kind of flame-retardant polymer polyether glycol and be used to prepare the method for block resistance combustion polyurethane foam material.
Background technology
Polyurethane foamed material is a kind of superpolymer with special performance and many-sided purposes.It is a basic raw material with polyether glycol and diisocyanate, allocate less water, organic silicon surfactant, whipping agent into, under the acting in conjunction of organotin and tertiary amine catalyst, form, can make hard, semi-rigid and flexible urethane foam with it, be applied to the aspects such as saddle of cushion, back cushion, inside gadget and the motorcycle of vehicle mainly as cushioning material, also can be used for making simultaneously the products for civilian use such as sofa, mattress, finishing material.
Polyether polyol normally, vinyl monomer in the presence of dispersion agent in polyether glycol the diffuse-aggregate product of free radical, the used vinyl monomer of polyether polyol at the beginning of the seventies is a vinyl cyanide, its solid content (polymer content) is 5%～25%, viscosity height, look Huang, easily makes the heartburn variable color of polyurethane foam; The mid-80 prepares polyether polyol with vinyl cyanide and vinylbenzene mix monomer, and its solid content is 20%～30%, and styrene content is more than 50%; At the initial stage nineties, abroad some companies release one after another solid content more than 40%, and viscosity is lower than the polyether polyol of 5500mPas (25 ℃), as European patent Eur.Pat.Ep778,301; PCT.Int.Appl.Wo.97,15,605; PCT.Int.Appl.Wo.97,15,606 disclosed polyether polyols, but these polyether polyols all do not have flame retardant resistance, do not have flame retardant resistance with its prepared polyurethane foam yet.
The urethane foam goods very easily burn, fire-retardant difficulty, and flame resistant method commonly used at present is to add fire retardant in the raw material of producing urethane mostly, used fire retardant mainly contains reaction-type flame-retarding polyether glycol and non-response type small molecules fire retardant; The reaction-type flame-retarding polyether glycol mainly is phosphorous chlorine polyether glycol, and is low with the prepared polyurethane foam cost of this polyether glycol height, bearing capacity; The kind of non-response type small molecules fire retardant mainly contains Sb
2O
3, liquid or solid compounds such as melamine class, phosphorous acid ester and chloride-based, use the non-reacted fire retardant of liquid, volatilize gradually with the use fire retardant of foam materials, flame retardant effect descends, and environment is caused certain harm; Use the non-reactive flame retardant of solid can obviously increase the viscosity of polyether glycol, increase the foam process difficulty, reduce the percentage of open area of foams, and make the density of foams uneven up and down.This based flame retardant uses trouble, and difficulty mixes, large usage quantity, fire-retardant cost height.
United States Patent (USP) 4,214,055,3,953,393 use the fire resistant polymer polylol of two or more mix monomer copolymerization in vinylchlorid, vinylidene chloride, vinylbenzene, the vinyl cyanide, and prepare resistance combustion polyurethane foam with it.But the homopolymer of vinylchlorid, vinylidene chloride and copolymerization are normally heat-labile, emit deleterious HCl gas in foaming process, and foaming machine is had corrodibility; Japanese Patent Jpn.Kokai.Tokyo.JP.0959, the employed fire-retardant thing of 341 disclosed fire resistant polymer polylols is a polyvinyl chloride, equally also is heat-labile; United States Patent (USP) U.S.5,250,581 disclose with tribromo-benzene ethene and vinyl cyanide mix monomer copolymerization polymer polyatomic alcohol, have certain flame retardant resistance with the prepared urethane foam of this polymer polyatomic alcohol, but tribromo-benzene ethene synthesizes difficulty, price is high, is difficult to obtain.
Summary of the invention
One of purpose of the present invention is to provide a kind of preparation method of flame-retardant polymer polyether glycol, it is different from free radical dispersion polymerization traditionally, but condensation polymerization, with the prepared flame-retardant polymer polyether glycol of this method, have hazardous and noxious substances such as dispersed phase polymer particle diameter little (0.1 micron～0.85 micron), not phosphorous, halogen, vinylbenzene and vinyl cyanide, environmental protection, and have that preparation technology is simple, cost is low, be easy to characteristics such as foaming.
Two of purpose of the present invention is to provide a kind of flame retardant polyurethane block foaming method, with the prepared resistance combustion polyurethane foam of this method, have the reinforcement of inferior nano-dispersed gathering compound ultramicron, fire-retardant characteristic, so this polyurethane foamed material have higher flame retardant resistance (the oxygen value number can reach 28%) and higher mechanical property and press and fall into hardness.
Flame-retardant polymer polyether glycol of the present invention is that the polymeric colloid dispersion system that inferior nanometer polymer ultramicron is a disperse phase, two-phase constituted of the aminated vulcabond modified polyether polylol of external phase, surface grafting part (dispersion agent) is formed by general polyether glycol.
Above-mentioned external phase is general polyether glycol, be propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, the functionality of its polyvalent alcohol is between 2～4, hydroxyl value is between 36mgKOH/g～70mgKOH/g, proportion of primary OH groups is between 5%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination.
Above-mentioned inferior nanometer polymer ultramicron disperse phase be median size at 0.1 micron～0.8 micron, " hair " polymer microballoon of the polyether glycol of the aminated vulcabond modification of surface grafting part.
Its ethoxylated polyhydric alcohol is meant propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms in the aminated vulcabond modified polyether polylol of above-mentioned part, its polyvalent alcohol functionality is between 2～4, hydroxyl value is between 19mgKOH/g～40mgHO/g, proportion of primary OH groups is between 5%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination; Its vulcabond is a kind of in tolylene diisocyanate, the '-diphenylmethane diisocyanate or the mixture of the two; It is aminated to be the reaction of diamine and vulcabond.
Above-mentioned polymer microballoon is formaldehyde and urea, trimeric cyanamide, hexamethylenetetramine polycondensate.
Fire-retardant ammonia ester foam of the present invention be with flame-retardant polymer polyether glycol of the present invention and diisocyanate cpd in the presence of tertiary amine, organo-metallic catalyst, water, pneumatogen and a small amount of silicone oil foam stabilizer, make through block foam process.
Above-mentioned diisocyanate cpd is a kind of in tolylene diisocyanate (T80/20), the '-diphenylmethane diisocyanate (PAPI) or the mixture of the two, the blending ratio of the two was at 65: 35～100: 0, tolylene diisocyanate (T80/20) preferably, and reduce the flame retardant resistance that makes resistance combustion polyurethane foam with diisocyanate index and improve.
That above-mentioned block foam process is meant is box, vertical, level and continuous foamed technology.
The manufacture method of flame-retardant polymer polyether glycol of the present invention is as follows:
Respectively with external phase-general polyether glycol, the aminated vulcabond modified polyether polylol of dispersion agent-part, nitrogen containing monomer-urea, trimeric cyanamide, contain aldehyde monomer-formaldehyde, reach condensation reaction promotor and join in the closed reactor that has agitator, temperature regulator meter, make temperature rise to setting-up point, behind this temperature isothermal reaction certain hour, vacuum-drying removes volatile components, obtains the flame-retardant polymer polyether glycol.
Above-mentioned general polyether glycol is propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, the functionality of its polyvalent alcohol is between 2～4, hydroxyl value is between 36mgKOH/g～70mgKOH/g, proportion of primary OH groups is between 5%～98%, its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, its consumption is nitrogen containing monomer consumption-urea, 100%～9000% of trimeric cyanamide quality sum is preferably 150%～2000%.
Above-mentioned formaldehyde is concentration at 25%～45% formaldehyde, and preferably concentration is at 37% formaldehyde, and its consumption (in 37% concentration of formaldehyde) is 40%～400% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum, is preferably 60%～150%.
Above-mentioned nitrogen containing monomer is urea, trimeric cyanamide, and the ratio of the quality of its urea, trimeric cyanamide was preferably 100: 50 between 0: 100～100: 0; Nitrogen containing monomer consumption-urea, trimeric cyanamide quality sum are 2%～60% of whole reaction system quality, are preferably 10%～48%.
Above-mentioned condensation reaction promotor is hexamethylenetetramine, tosic acid, ammoniacal liquor, formic acid etc., is preferably hexamethylenetetramine, and its hexamethylenetetramine consumption is 0.07%～20% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum
Above-mentioned temperature of reaction is a setting-up point, generally at 50 ℃～100 ℃, is preferably 65 ℃～95 ℃, preferably 75 ℃～85 ℃
The above-mentioned reaction times is at 0.5～6 hour, is preferably at 1～4 hour preferably 2～4 hours.
Above-mentioned vacuum-drying is meant at a certain temperature, generally at 35 ℃～100 ℃, is preferably 40 ℃～95 ℃; The vacuum-drying certain hour generally at 1～12 hour, is preferably at 2～10 hours.
The polyether glycol of the aminated vulcabond modification of above-mentioned dispersion agent-part plays the effect of dispersion agent in synthetic flame-retardant polymer polyether glycol, its consumption is 0.5%～150% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum, is preferably 10%～80%.
The preparation method of the polyether glycol of the aminated vulcabond modification of above-mentioned part is as follows:
Under 35 ℃～45 ℃, respectively polyether glycol, vulcabond encapsulant, vulcabond and tertiary amine are joined in the closed reactor that has agitator, thermometer, make temperature rise to 75 ℃～85 ℃, in this temperature isothermal reaction after 4～6 hours, add diamine, be warming up to 110 ℃～125 ℃ again, reacted 0.5～3 hour.Obtain the aminated vulcabond modified polyether polylol of part.
Above-mentioned polyether glycol is meant propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, its polyvalent alcohol functionality is between 2～4, hydroxyl value is between 19mgKOH/g～56mgHO/g, proportion of primary OH groups is between 28%～98%, and its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination.
Above-mentioned vulcabond encapsulant can be phenolic compound, beta-dicarbonyl compound, oxime compounds, is preferably oxime compounds, as methyl ethyl ketoxime.
Above-mentioned diisocyanate compound is a kind of in tolylene diisocyanate, the '-diphenylmethane diisocyanate or the mixture of the two, is preferably tolylene diisocyanate.
Above-mentioned tertiary amine is a kind of in triethylamine, tripropyl amine, the Tributylamine or the two and the two above mixture, is preferably triethylamine.
Above-mentioned diamine is a kind of in quadrol, propylene diamine, the butanediamine or the two and the two above mixture, is preferably quadrol.
The mol ratio of above-mentioned polyether glycol, tolylene diisocyanate, quadrol, triethylamine was at 3: 1: 1: 0.001～1: 1:: 1: 0.08.
With flame-retardant polymer polyether glycol of the present invention is that the method for feedstock production resistance combustion polyurethane foam material is as follows:
In mixing tank respectively with flame-retardant polymer polyether glycol, polyether glycol, tertiary amine catalyst, organo-metallic catalyst, water, pneumatogen and a small amount of silicone oil foam stabilizer, mix the back and add diisocyanate cpd, high-speed mixing adopts box, vertical, the continuous foamed resistance combustion polyurethane foam that makes of level.
Above-mentioned a small amount of silicone oil foam stabilizer is the silicone foam stabilizer, and its consumption (w/w) is 0.08%～1.8% of a polyether glycol, is preferably 0.13%～0.8%, and reduces with silicone oil foam stabilizer consumption, and the hardness and the rebound resilience that make resistance combustion polyurethane foam increase.
Above-mentioned organotin catalysts mainly contains organotin catalysts commonly used such as dibutyl tin laurate, two 2 ethyl hexanoic acid dibutyl tins, dibutyltin diacetate, stannous octoate, stannous oleate.
Above-mentioned tertiary amine catalyst mainly contains triethylene diamine, triethylamine, N, N, N ', N '-tetramethyl--1,3, the tertiary amine catalyst that-butanediamine, N-Ethylmorphine quinoline, two (beta-dimethyl-amine ethyl) ether etc. are commonly used.
Above-mentioned pneumatogen mainly contains methylene dichloride, F
11, F
12, F
113Deng pneumatogen.
Above-mentioned diisocyanate cpd is a kind of in tolylene diisocyanate (T80/20), the '-diphenylmethane diisocyanate (PAPI) or the mixture of the two, the blending ratio of the two was at 65: 35～100: 0, tolylene diisocyanate (T80/20) preferably, and reduce the flame retardant resistance that makes resistance combustion polyurethane foam with diisocyanate index and improve.
Basic recipe is as follows:
The A component:
Common polyether glycol: 30～70 parts
Water: 1～3 part
Stannous octoate: 0.05～0.9 part
Sanya ethylene diamine: 0.05～0.9 part
Silicone oil: 0.1～1.6 part
Flame-retardant polymer polyether glycol of the present invention: all the other flame-retardant polymer polyether glycol parts of the present invention
Add up to 100 parts
The B component:
Diisocyanate index: 95%～123%
The present invention has the following advantages compared with prior art:
1. this flame-retardant polymer polyether glycol, hazardous and noxious substances such as not phosphorous, halogen, vinylbenzene and vinyl cyanide, and have that preparation technology is simple, cost is low, be easy to characteristics such as foaming.
2. Zhi Bei resistance combustion polyurethane foam has the reinforcement of inferior nano-dispersed gathering compound ultramicron, fire-retardant characteristic, so this polyurethane foamed material has higher flame retardant resistance (the oxygen value number can reach 28%) and higher mechanical property and presses and fall into hardness.
3. the polyether glycol of the aminated vulcabond modification of part plays the effect of dispersion agent in synthetic flame-retardant polymer polyether glycol, plays the effect of foam stabilizer in the synthetic resistance combustion polyurethane foam material.
Description of drawings
Fig. 1 is synthetic, the foaming formulation and the resistance combustion polyurethane foam performance synopsis of flame-retardant polymer polyether glycol.
Annotate among the figure: dispersion agent I, pastern divide aminated vulcabond modified polyether polylol I.
Dispersion agent II, pastern divide aminated vulcabond modified polyether polylol II.
Performance A is the performance of flame-retardant polymer polyether glycol; Stability/the moon is that nature is deposited non-setting time, the moon.
Performance B is a polyurathamc foamy performance.
Foaming basic recipe (quality):
The A component:
Common polyether glycol: 39 parts
Water: 2.2 parts
Stannous octoate: 0.16 part
Sanya ethylene diamine: 0.16 part
Silicone oil: 0.2 part
Flame-retardant polymer polyether glycol of the present invention: all the other flame-retardant polymer polyether glycols of the present invention
Add up to 100 parts
The B component:
Toluene diisocyanate index: 110%
Specific embodiments
The raw material of the embodiment of the invention is as follows:
Polyether glycol N330: glycerine or TriMethylolPropane(TMP) are initiator, propylene oxide ring-opening polymerization, the 16% ethylene oxide-capped polyether glycol that forms, its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, hydroxyl value 34mgKOH/g～38mgKOH/g, proportion of primary OH groups is between 60%～85%.
Polyether glycol 6000: glycerine or TriMethylolPropane(TMP) are initiator, propylene oxide ring-opening polymerization, the 16% ethylene oxide-capped polyether glycol that forms, its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, hydroxyl value 26mgKOH/g～30mgKOH/g, proportion of primary OH groups is between 60%～85%.
Polyether glycol 551C: glycerine or TriMethylolPropane(TMP) are initiator, propylene oxide ring-opening polymerization, the 16% ethylene oxide-capped polyether glycol that forms, its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, hydroxyl value 54mgKOH/g～58mgKOH/g, proportion of primary OH groups is between 50%～85%.
Polyether glycol 3030: glycerine or TriMethylolPropane(TMP) are initiator, propylene oxide polyether glycol that ring-opening polymerization forms, its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, hydroxyl value 54mgKOH/g～58mgKOH/g, proportion of primary OH groups is between 10%～60%.
Polyether glycol 3031K: glycerine or TriMethylolPropane(TMP) are initiator, propylene oxide, oxyethane polyether glycol that ring-opening copolymerization forms, its polymerization process can adopt traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, hydroxyl value 54mgKOH/g～58mgKOH/g, proportion of primary OH groups is between 15%～80%.
Formaldehyde: the formalin of concentration 37%
Embodiment 1: under 40 ℃ respectively with polyether glycol N330,960 kilograms, 17.4 kilograms of methyl ethyl ketoximes, 34.8 kilograms of tolylene diisocyanates and triethylamine, 0.12 kilogram joins in the closed reactor that has agitator, thermometer, make temperature rise to 80 ℃, after 5 hours, add quadrol, 12 kilograms in this temperature isothermal reaction, be warming up to 118 ℃ again, reacted 1 hour.Obtain the aminated vulcabond modified polyether polylol of part I.
Embodiment 2: under 40 ℃ respectively with polyether glycol 6000,600 kilograms, 8.7 kilograms of methyl ethyl ketoximes, 17.4 kilograms of tolylene diisocyanates and triethylamine, 0.06 kilogram joins in the closed reactor that has agitator, thermometer, make temperature rise to 80 ℃, after 5 hours, add quadrol, 6 kilograms in this temperature isothermal reaction, be warming up to 118 ℃ again, reacted 1 hour.Obtain the aminated vulcabond modified polyether polylol of part II.
Embodiment 3: respectively with general polyether glycol 3030,500 kilograms, the aminated vulcabond modified polyether polylol of part I, 69 kilograms, 221 kilograms in formaldehyde, 138 kilograms in urea, 69 kilograms of trimeric cyanamides, hexamethylenetetramine joins for 8.3 kilograms and has agitator, in airtight 2000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, obtain the flame-retardant polymer polyether glycol, see the synthetic of flame-retardant polymer polyether glycol, foaming formulation and resistance combustion polyurethane foam performance synopsis embodiment 3.
Embodiment 4: respectively with general polyether glycol 551C, 500 kilograms, the aminated vulcabond modified polyether polylol of part I, 69 kilograms, 221 kilograms in formaldehyde, 138 kilograms in urea, 69 kilograms of trimeric cyanamides, hexamethylenetetramine joins for 8.3 kilograms and has agitator, in airtight 2000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, obtain the flame-retardant polymer polyether glycol, see the synthetic of flame-retardant polymer polyether glycol, foaming formulation and resistance combustion polyurethane foam performance synopsis embodiment 4.
Embodiment 5: respectively with general polyether glycol 3031K, 500 kilograms, the aminated vulcabond modified polyether polylol of part I, 69 kilograms, 221 kilograms in formaldehyde, 138 kilograms in urea, 69 kilograms of trimeric cyanamides, hexamethylenetetramine joins for 8.3 kilograms and has agitator, in airtight 2000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, obtain the flame-retardant polymer polyether glycol, see the synthetic of flame-retardant polymer polyether glycol, foaming formulation and resistance combustion polyurethane foam performance synopsis embodiment 5.
Embodiment 6: respectively with general polyether glycol 3030,500 kilograms, the aminated vulcabond modified polyether polylol of part II, 69 kilograms, 221 kilograms in formaldehyde, 138 kilograms in urea, 69 kilograms of trimeric cyanamides, hexamethylenetetramine joins for 8.3 kilograms and has agitator, in airtight 2000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, obtain the flame-retardant polymer polyether glycol, see the synthetic of flame-retardant polymer polyether glycol, foaming formulation and resistance combustion polyurethane foam performance synopsis embodiment 6.
Embodiment 7: respectively with general polyether glycol 551C, 500 kilograms, the aminated vulcabond modified polyether polylol of part II, 69 kilograms, 221 kilograms in formaldehyde, 138 kilograms in urea, 69 kilograms of trimeric cyanamides, hexamethylenetetramine joins for 8.3 kilograms and has agitator, in airtight 2000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, obtain the flame-retardant polymer polyether glycol, see the synthetic of flame-retardant polymer polyether glycol, foaming formulation and resistance combustion polyurethane foam performance synopsis embodiment 7.
Embodiment 8: respectively with general polyether glycol 3031K, 500 kilograms, the aminated vulcabond modified polyether polylol of part II, 69 kilograms, 221 kilograms in formaldehyde, 138 kilograms in urea, 69 kilograms of trimeric cyanamides, hexamethylenetetramine joins for 8.3 kilograms and has agitator, in airtight 2000 liters of reactors of thermometer, make temperature rise to 80 ℃, this temperature isothermal reaction 4 hours, removed volatile components in 4 hours 92 ℃ of vacuum-dryings, obtain the flame-retardant polymer polyether glycol, see the synthetic of flame-retardant polymer polyether glycol, foaming formulation and resistance combustion polyurethane foam performance synopsis embodiment 8.
Comparison example 9: feed way is with example 1, feeding quantity is 0 kilogram except that the add-on of the aminated vulcabond modified polyether polylol of part I, other add-ons are with example 1, the polyether polyol that obtains, stability is bad, naturally deposit five days precipitations, see synthetic, the foaming formulation and the resistance combustion polyurethane foam performance synopsis embodiment 9 of flame-retardant polymer polyether glycol.
Comparison example 10: feed way is with example 4, feeding quantity is 0 kilogram except that the add-on of the aminated vulcabond modified polyether polylol of part II, other add-ons are with example 4, the polyether polyol that obtains, stability is bad, naturally deposit three days precipitations, see synthetic, the foaming formulation and the resistance combustion polyurethane foam performance synopsis embodiment 10 of flame-retardant polymer polyether glycol.
Claims (15)
1. flame-retardant polymer polyether glycol preparation method is characterized in that it is made up of following technology:
Respectively with external phase-general polyether glycol, the aminated vulcabond modified polyether polylol of dispersion agent-part, nitrogen containing monomer-urea, trimeric cyanamide, contain aldehyde monomer-formaldehyde, reach condensation reaction promotor and join in the closed reactor that has agitator, temperature regulator meter, make temperature rise to setting-up point, after this temperature isothermal reaction, vacuum-drying removes volatile components, obtains the flame-retardant polymer polyether glycol; General polyether glycol is propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization, the ethylene oxide-capped polyether glycol that forms, the functionality of its polyvalent alcohol is between 2～4, hydroxyl value is between 36mgKOH/g～70mgKOH/g, proportion of primary OH groups is between 5%～98%, its polymerization process adopts traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination, and its consumption is 100%～9000% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum; Formaldehyde is concentration at 25%～45% formaldehyde, and its consumption is 40%～400% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum in 37% concentration of formaldehyde; Nitrogen containing monomer is urea, trimeric cyanamide, and the ratio of the quality of its urea, trimeric cyanamide is between 0: 100～100: 0, and nitrogen containing monomer consumption-urea, trimeric cyanamide quality sum are 2%～60% of whole reaction system quality; Condensation reaction promotor is hexamethylenetetramine, tosic acid, ammoniacal liquor, formic acid, and its hexamethylenetetramine consumption is 0.07%～20% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum.
2. according to the described flame-retardant polymer polyether glycol of claim 1 preparation method, it is characterized in that temperature of reaction is that setting-up point is at 50 ℃～100 ℃.
3. according to the described flame-retardant polymer polyether glycol of claim 1 preparation method, it is characterized in that the reaction times is at 0.5～6 hour.
4. according to the described flame-retardant polymer polyether glycol of claim 1 preparation method, it is characterized in that vacuum-drying is meant under 35 ℃～100 ℃ temperature vacuum-drying 1～12 hour.
5. according to the described flame-retardant polymer polyether glycol of claim 1 preparation method, it is characterized in that the polyether glycol of the aminated vulcabond modification of dispersion agent-part plays the effect of dispersion agent in synthetic flame-retardant polymer polyether glycol, its consumption is 0.5%～150% of nitrogen containing monomer consumption-urea, a trimeric cyanamide quality sum.
6. according to the described flame-retardant polymer polyether glycol of claim 1 preparation method, the preparation method of polyether glycol of the aminated vulcabond modification of raw material midbody-part who it is characterized in that being used to preparing the flame-retardant polymer polyether glycol is as follows:
Under 35 ℃～45 ℃, respectively polyether glycol, vulcabond encapsulant, vulcabond and tertiary amine are joined in the closed reactor that has agitator, thermometer, make temperature rise to 75 ℃～85 ℃, in this temperature isothermal reaction after 4～6 hours, add diamine, be warming up to 110 ℃～125 ℃ again, reacted 0.5～3 hour, and obtained the aminated vulcabond modified polyether polylol of part.
7. according to the described flame-retardant polymer polyether glycol of claim 6 preparation method, it is characterized in that polyether glycol is meant propylene oxide ring-opening polymerization or propylene oxide and oxyethane ring-opening copolymerization or propylene oxide ring-opening polymerization among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part, the ethylene oxide-capped polyether glycol that forms, its polyvalent alcohol functionality is between 2～4, hydroxyl value is between 36mgKOH/g～70mgKOH/g, proportion of primary OH groups is between 28%～98%, and its polymerization process adopts traditional anionic ring-opening polymerization technology and DMC catalysts polymerization technique or the two combination.
8. according to the described flame-retardant polymer polyether glycol of claim 6 preparation method, it is characterized in that the vulcabond encapsulant is phenolic compound, beta-dicarbonyl compound, oxime compounds among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part.
9. according to the described flame-retardant polymer polyether glycol of claim 6 preparation method, it is characterized in that isocyanide ester compound among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part is a kind of in tolylene diisocyanate, the '-diphenylmethane diisocyanate or the mixture of the two.
10. according to the described flame-retardant polymer polyether glycol of claim 6 preparation method, it is characterized in that tertiary amine is triethylamine, tripropyl amine, Tributylamine among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part.
11., it is characterized in that diamine among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part is a kind of in quadrol, propylene diamine, the butanediamine or the two and the two above mixture according to the described flame-retardant polymer polyether glycol of claim 6 preparation method.
12., it is characterized in that the mol ratio 3: 1: 1 of polyether glycol, tolylene diisocyanate, quadrol, triethylamine among the preparation method of polyether glycol of the aminated vulcabond modification of above-mentioned part: 0.001～1: 1 according to the described flame-retardant polymer polyether glycol of claim 6 preparation method:: 1: 0.08.
13. one kind is used to prepare the method for block resistance combustion polyurethane foam material according to claim 1, it is characterized in that it comprises following technology:
In mixing tank, respectively flame-retardant polymer polyether glycol, polyether glycol, tertiary amine catalyst, organo-metallic catalyst, water, pneumatogen and a small amount of silicone oil foam stabilizer are mixed the back and add diisocyanate cpd, high-speed mixing adopts box, vertical, the continuous foamed resistance combustion polyurethane foam that makes of level.
14. method according to the block resistance combustion polyurethane foam material of the described preparation of claim 13, it is characterized in that above-mentioned a small amount of silicone oil foam stabilizer is the silicone foam stabilizer, its consumption w/w is 0.08%～1.8% of a polyether glycol, and reduce with silicone oil foam stabilizer consumption, the hardness and the rebound resilience that make resistance combustion polyurethane foam increase.
15. method according to the block resistance combustion polyurethane foam material of the described preparation of claim 13, it is characterized in that above-mentioned diisocyanate cpd is a kind of among tolylene diisocyanate T80/20, the '-diphenylmethane diisocyanate PAPI or the mixture of the two, the blending ratio of the two was at 65: 35～100: 0, and reduce with diisocyanate index, the flame retardant resistance that makes resistance combustion polyurethane foam improves.
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| CNB2004100359006A CN1308373C (en) | 2004-09-30 | 2004-09-30 | Preparation method of fire retardant polymer polyether polyol and method for preparing block fire retardant polyurethane foam mateial therefrom |
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| CNB2004100359006A CN1308373C (en) | 2004-09-30 | 2004-09-30 | Preparation method of fire retardant polymer polyether polyol and method for preparing block fire retardant polyurethane foam mateial therefrom |
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| CN102070764B (en) * | 2010-12-24 | 2012-07-18 | 东莞市源聚德实业有限公司 | Carrier sponge for medical framework accessory and preparation method thereof |
| CN102585272B (en) * | 2012-01-15 | 2015-04-08 | 齐鲁工业大学 | Production method of ultralow density high-tenacity high-elasticity melamine foams |
| CN107540811B (en) * | 2017-08-08 | 2020-06-09 | 海泉风雷新能源发电股份有限公司 | Melamine graft modified polyurethane plastic and preparation method thereof |
| CN110078885B (en) * | 2019-05-27 | 2021-06-18 | 江苏钟山化工有限公司 | A combined polyether polyol with flame retardant and autocatalytic properties and its application |
| CN110467710A (en) * | 2019-08-20 | 2019-11-19 | 浙江坤月新材料有限公司 | A kind of melamine polyol combination material for manufacturing well antiseep sleeve |
| CN111499828B (en) * | 2020-04-15 | 2022-04-12 | 黎明化工研究设计院有限责任公司 | Resin composition for low-density high-flame-retardant polyurethane material and application thereof |
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