CN111548484A - Synthesis method of low isocyanate index full-water rigid foam polyether polyol - Google Patents
Synthesis method of low isocyanate index full-water rigid foam polyether polyol Download PDFInfo
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- CN111548484A CN111548484A CN202010297642.8A CN202010297642A CN111548484A CN 111548484 A CN111548484 A CN 111548484A CN 202010297642 A CN202010297642 A CN 202010297642A CN 111548484 A CN111548484 A CN 111548484A
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- 229920000570 polyether Polymers 0.000 title claims abstract description 79
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 78
- 229920005862 polyol Polymers 0.000 title claims abstract description 70
- 150000003077 polyols Chemical class 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 239000006260 foam Substances 0.000 title claims abstract description 36
- 239000012948 isocyanate Substances 0.000 title claims abstract description 34
- 150000002513 isocyanates Chemical class 0.000 title claims abstract description 34
- 238000001308 synthesis method Methods 0.000 title abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 58
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 41
- 150000007974 melamines Chemical class 0.000 claims abstract description 26
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004640 Melamine resin Substances 0.000 claims abstract description 24
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000007670 refining Methods 0.000 claims abstract description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 22
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- FHCUBHNQRLFINC-UHFFFAOYSA-N dodecamagnesium hexasilicate Chemical group [Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] FHCUBHNQRLFINC-UHFFFAOYSA-N 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 239000008098 formaldehyde solution Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 8
- 238000003786 synthesis reaction Methods 0.000 claims 8
- 239000000203 mixture Substances 0.000 claims 1
- 238000005187 foaming Methods 0.000 abstract description 25
- 239000003999 initiator Substances 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005057 refrigeration Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 229920002994 synthetic fiber Polymers 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
- C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
- C08G65/263—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing heterocyclic amine groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5054—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/5063—Polyethers having heteroatoms other than oxygen having nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
-
- 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 relates to a synthesis method of low isocyanate index full water rigid foam polyether polyol, which takes activated melamine resin and organic amine as composite initiator to have polymerization reaction with propylene oxide and ethylene oxide, and then the low isocyanate index full water rigid foam polyether polyol is prepared by neutralization, refining and filtration. The activated melamine has intersolubility with water, epoxypropane and epoxyethane, so that the melamine is smoothly polymerized; the prepared low isocyanate index full-water rigid foam polyether polyol has low viscosity and good fluidity in the foaming process, and the rigid chain segment is introduced into the polyether chain segment to improve the functionality of the polyether, so that the foam structure is enhanced, the product has high compressive strength and improved dimensional stability, the consumption of isocyanate is reduced, and the foaming cost is reduced.
Description
Technical Field
The invention belongs to the field of polyurethane synthetic materials, and relates to a synthetic method of low isocyanate index full-water rigid foam polyether polyol.
Background
The rigid polyurethane foam plastic has the advantages of low heat conductivity coefficient, excellent mechanical property, good sound insulation effect, aging resistance, chemical resistance, fast curing, convenient molding and the like, is widely applied to many fields of buildings, petrochemical industry, refrigeration, shipbuilding, vehicles, aviation, machinery, instruments, furniture and the like, and is an indispensable high polymer material in production and life.
The majority of conventional rigid polyurethane foams use physical blowing agents, chlorofluorocarbons and hydrochlorofluorocarbons. The destruction of atmospheric ozone layer by chlorofluorocarbons has attracted much attention from governments and related departments, and has been banned for the protection of the environment in which humans rely on living. Hydrochlorofluorocarbons, while relatively less damaging to the atmospheric ozone layer, still have irrecoverable damage to the ozone layer, and thus are being reduced in use and gradually rendered banned worldwide. Water is used as a chemical foaming agent and reacts with isocyanate to generate carbon dioxide, and the harm of the carbon dioxide to the environment is almost zero. Moreover, water is the most common in life, is convenient to obtain, is non-toxic and harmless, and is the most environment-friendly foaming agent. The full water foaming system is also the foaming system with the development prospect, and the development of the full water foaming polyether is very important.
CN 108383990A discloses a preparation method of rigid polyether polyol for full water foaming, which is a process for preparing rigid foam by using low-polymerization-degree phenolic resin and activated melamine as composite initiators and ethylene oxide and epoxy propylene as polymerization monomers. The method improves the problems of viscosity, fluidity and hard bubble size of the foaming system. The disadvantages are as follows: (1) the isocyanate has more consumption and high cost; (2) the foaming activity is applied to the spraying field with high requirement on fluidity and high requirement on foaming speed, and the using effect is not ideal.
Disclosure of Invention
The invention aims to provide a method for synthesizing the full-water rigid foam polyether polyol with low isocyanate index, low isocyanate consumption, low raw material cost, high foaming activity and good fluidity in the foaming process, and the obtained full-water rigid foam polyether polyol rigid foam has good dimensional stability.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the invention provides a full water hard foam polyether polyol with low isocyanate index, which is prepared by taking activated melamine resin and organic amine as composite initiators, carrying out polymerization reaction with propylene oxide and ethylene oxide, and then carrying out neutralization, refining and filtering. The method comprises the following specific steps:
a synthetic method of low isocyanate index full water rigid foam polyether polyol is characterized by comprising the following steps: the method comprises the following steps:
first step, preparation of activated Melamine resin
Adding melamine, a formaldehyde solution with the mass concentration of 37% and organic amine into a reaction kettle according to a certain proportion, stirring, heating and polymerizing, wherein the organic amine is one of monoethanolamine, diethanolamine, triethanolamine, urea and diethylenetriamine; wherein the molar ratio of the melamine to the formaldehyde to the organic amine is 1:1:1, 1:2:1 or 1:3:3, the polymerization temperature is 40-100 ℃, and the polymerization time is 2-7 hours; after the polymerization is finished, continuously heating to 100-110 ℃ for dehydration, and analyzing that the water content is less than 0.05 percent to prepare activated melamine resin; the method is used for improving the intersolubility of melamine with water, Propylene Oxide (PO) and Ethylene Oxide (EO) so as to lead the melamine to be polymerized smoothly;
second step, preparation of crude polyether polyol
Adding activated melamine resin and organic amine into a reaction kettle according to a certain proportion, stirring and heating to a polymerization temperature, adding an epoxy compound for polymerization reaction, wherein the organic amine is one of monoethanolamine, diethanolamine, triethanolamine, urea and diethylenetriamine;
the epoxy compound is added in a segmented mode or a mixed polymerization mode, and the epoxy compound is Propylene Oxide (PO) and Ethylene Oxide (EO);
when the epoxy compound is added in a segmented mode, the epoxy compound is sprayed at a high foaming speed, the polymerization temperature is 80-130 ℃, the epoxy compound is added in a segmented mode, the first stage is PO, the second stage is EO, the adding mode is continuous adding, the polymerization temperature of the first stage and the second stage is the same, the mass ratio of PO to EO is 1: 0-1: 1 and does not include 1:0, and the adding amount is 60-70% of the mass of a finished product;
when the mixed polymerization is added, the polymerization temperature is 100 ℃ to 130 ℃ in the aspect of molding foaming with relatively low activity and good fluidity requirement, wherein the ratio of the epoxy compound: the mass ratio of PO to EO is 1: 0-1: 1 and does not include 1:0, the adding mode is continuous adding, and the adding amount is 60-70% of the finished product mass;
until the pressure in the kettle is unchanged, finishing polymerization and degassing to prepare crude polyether polyol;
third step, polyether polyol refining
Adding deionized water into the prepared crude polyether polyol for emulsification, wherein the adding amount of the deionized water accounts for 5% of the mass of the crude polyether polyol, heating to the neutralization temperature of 80-120 ℃, adding inorganic acid for neutralization, stirring for neutralization for 2 hours, analyzing the pH value to be 6-8, adding a refining agent, wherein the adding amount of the refining agent accounts for 0.3% of the mass of the crude polyether polyol, stirring for 0.5 hour, dehydrating, analyzing the water content to be less than 0.05%, cooling and filtering to obtain the low isocyanate index all-water rigid foam polyether polyol.
In the technical scheme, the refining agent is magnesium hexasilicate.
In the technical scheme, the molar ratio of the activated melamine resin to the organic amine in the second step is 1: 1-1: 4.
In the technical scheme, when the mixed polymerization is added or added in a segmented mode, the mass ratio of the propylene oxide to the ethylene oxide is 2:1, and the adding amount of the epoxy compound is 60% of the mass of a finished product.
In the technical scheme, when the materials are added in a segmented mode, the polymerization temperature is 115 ℃, the first-segment polymerization time is 1.5 hours, and the second-segment polymerization time is 3 hours.
In the technical scheme, when the mixed polymerization is added, the polymerization temperature is 125 ℃.
In the above technical scheme, the mass ratio of the activated melamine resin to the organic amine in the second step is 1: (0.36-0.61).
In the technical scheme, the molar ratio of the melamine to the formaldehyde to the organic amine is 1:1:1, the polymerization temperature is 80 ℃, and the polymerization time is 3 hours.
In the above technical scheme, the inorganic acid is phosphoric acid. The phosphoric acid is a phosphoric acid solution, the mass concentration of the phosphoric acid solution is 75%, and the adding amount of the phosphoric acid solution accounts for 1% of the mass of the crude polyether polyol.
The working principle of the invention is as follows:
melamine activation equation (diethanolamine for example):
preparation of polyether polyol by ring-opening polymerization of epoxy compound (taking propylene oxide as an example):
the invention has the following characteristics and positive effects:
the melamine is activated by formaldehyde and organic amine to improve the intersolubility of the melamine with water, propylene oxide and ethylene oxide, so that the melamine is polymerized smoothly; the prepared low isocyanate index full water rigid foam polyether polyol has low viscosity, high foaming activity and good fluidity in the foaming process, and the rigid chain segment is introduced into the polyether chain segment to improve the polyether functionality, so that the foam structure is enhanced, the product compressive strength is high, the dimensional stability is improved, the consumption of isocyanate is reduced, and the foaming cost is reduced.
Detailed Description
Example 1 (for Molding)
First step, preparation of activated Melamine resin
Adding 126g of melamine, 81g of formaldehyde solution with the mass concentration of 37% and 105g of diethanolamine into a reaction kettle, stirring and heating to the polymerization temperature of 80 ℃, carrying out polymerization reaction for 3 hours, continuously heating to 100 ℃ for dehydration, and analyzing the water content to be less than 0.05% to obtain the activated melamine resin.
Second step, preparation of crude polyether polyol
Adding 243g of activated melamine resin and 149g of triethanolamine into a reaction kettle, stirring and heating to the polymerization temperature of 125 ℃, mixing and polymerizing, adding 600g of epoxy compound (the mass ratio of PO to EO is 2:1), curing until the pressure in the kettle is unchanged, and degassing to obtain the crude polyether polyol.
Third step, polyether polyol refining
Adding deionized water into the prepared crude polyether polyol for emulsification, wherein the adding amount of the deionized water accounts for 5% of the mass of the crude polyether polyol, heating to the neutralization temperature of 80-120 ℃, adding a phosphoric acid solution with the mass concentration of 75%, the adding amount of the phosphoric acid solution accounts for 1% of the mass of the crude polyether polyol, stirring for 2 hours, analyzing the pH value within the range of 6-8, and if the pH value is qualified, adding a refining agent of magnesium hexasilicate, wherein the adding amount of the magnesium hexasilicate accounts for 0.3% of the mass of the crude polyether polyol, stirring for 0.5 hour, dehydrating, analyzing the water content to be less than 0.05%, cooling and filtering to obtain the low isocyanate index all-water rigid.
Example 2
First step, preparation of activated Melamine resin
Adding 126g of melamine, 162g of formaldehyde solution with the mass concentration of 37% and 103g of diethylenetriamine into a reaction kettle, stirring and heating to the polymerization temperature of 85 ℃, carrying out polymerization reaction for 3 hours, continuously heating to 100 ℃ for dehydration, and analyzing the water content to be less than 0.05% to obtain the activated melamine resin.
Second step, preparation of crude polyether polyol
Adding activated melamine resin (292g) and triethanolamine (105g) into a reaction kettle, stirring and heating to the polymerization temperature of 115 ℃, adding epoxy compounds (one-section PO 400g and two-section EO 200g) in sections, polymerizing for 1.5 hours at the first-section polymerization temperature of 115 ℃, polymerizing for 3 hours at the second-section 115 ℃, continuously adding, cutting into the second section immediately after adding the first section, curing until the pressure in the kettle is unchanged, and degassing to obtain the crude polyether polyol.
Third step, polyether polyol refining
Adding deionized water into the prepared crude polyether polyol for emulsification, wherein the adding amount of the deionized water accounts for 5% of the mass of the crude polyether polyol, heating to the neutralization temperature of 80-120 ℃, adding a phosphoric acid solution with the mass concentration of 75%, the adding amount of the phosphoric acid solution accounts for 1% of the mass of the crude polyether polyol, stirring for 2 hours, analyzing the pH value within the range of 6-8, and if the pH value is qualified, adding a refining agent of magnesium hexasilicate, wherein the adding amount of the magnesium hexasilicate accounts for 0.3% of the mass of the crude polyether polyol, stirring for 0.5 hour, dehydrating, analyzing the water content to be less than 0.05%, cooling and filtering to obtain the low isocyanate index all-water rigid.
Example 3 (for spray coating)
First step, preparation of activated Melamine resin
Adding 126g of melamine, 162g of formaldehyde solution with the mass concentration of 37% and 103g of diethylenetriamine into a reaction kettle, stirring and heating to the polymerization temperature of 40 ℃, carrying out polymerization reaction for 7 hours, continuously heating to 105 ℃ for dehydration, and analyzing the water content to be less than 0.05% to obtain the activated melamine resin.
Second step, preparation of crude polyether polyol
Adding activated melamine resin (292g) and triethanolamine (105g) into a reaction kettle, stirring and heating to the polymerization temperature of 80 ℃, adding epoxy compounds (one-section PO 400g and two-section EO 200g) in sections, polymerizing for 4 hours at the first-section polymerization temperature of 80 ℃, polymerizing for 3 hours at the second-section polymerization temperature of 80 ℃, continuously adding, cutting into the second section immediately after adding the first section, curing until the pressure in the kettle is unchanged, and degassing to obtain the crude polyether polyol.
Third step, polyether polyol refining
Adding deionized water into the prepared crude polyether polyol for emulsification, wherein the adding amount of the deionized water accounts for 5% of the mass of the crude polyether polyol, heating to the neutralization temperature of 80-120 ℃, adding a phosphoric acid solution with the mass concentration of 75%, the adding amount of the phosphoric acid solution accounts for 1% of the mass of the crude polyether polyol, stirring for 2 hours, analyzing the pH value within the range of 6-8, and if the pH value is qualified, adding a refining agent of magnesium hexasilicate, wherein the adding amount of the magnesium hexasilicate accounts for 0.3% of the mass of the crude polyether polyol, stirring for 0.5 hour, dehydrating, analyzing the water content to be less than 0.05%, cooling and filtering to obtain the low isocyanate index all-water rigid foam.
Example 4 (for spray coating)
First step, preparation of activated Melamine resin
Adding 126g of melamine, 162g of formaldehyde solution with the mass concentration of 37% and 103g of diethylenetriamine into a reaction kettle, stirring and heating to the polymerization temperature of 100 ℃, carrying out polymerization reaction for 2 hours, continuously heating to 110 ℃ for dehydration, and analyzing the water content to be less than 0.05% to obtain the activated melamine resin.
Second step, preparation of crude polyether polyol
Adding activated melamine resin (292g) and triethanolamine (105g) into a reaction kettle, stirring and heating to the polymerization temperature of 130 ℃, adding epoxy compounds (one-section PO 400g and two-section EO 200g) in sections, polymerizing for 1.5 hours at the first-section polymerization temperature of 130 ℃, polymerizing for 3 hours at the second-section polymerization temperature of 130 ℃, continuously adding, cutting into the second section immediately after adding the first section, curing until the pressure in the kettle is unchanged, and degassing to obtain the crude polyether polyol.
Third step, polyether polyol refining
Adding deionized water into the prepared crude polyether polyol for emulsification, wherein the adding amount of the deionized water accounts for 5% of the mass of the crude polyether polyol, heating to the neutralization temperature of 80-120 ℃, adding a phosphoric acid solution with the mass concentration of 75%, the adding amount of the phosphoric acid solution accounts for 1% of the mass of the crude polyether polyol, stirring for 2 hours, analyzing the pH value within the range of 6-8, and if the pH value is qualified, adding a refining agent of magnesium hexasilicate, wherein the adding amount of the magnesium hexasilicate accounts for 0.3% of the mass of the crude polyether polyol, stirring for 0.5 hour, dehydrating, analyzing the water content to be less than 0.05%, cooling and filtering to obtain the low isocyanate index all-water rigid.
Table one: the embodiment of the invention provides a quality index table of full-water hard bubbles
According to the first table: compared with JH-350W (traditional polyether prepared by taking cane sugar and glycerol as initiators), the hard foam polyether disclosed by the embodiment of the invention has low viscosity and high functionality, so that the viscosity of a later-stage foaming system is reduced, and the flowability is good. The quality index of the all-water hard bubbles in the examples 3 and 4 of the invention is basically consistent with that in the example 2.
Table two: foaming data comparison table of foam prepared from all-water-hardening polyether in embodiment of the invention
According to table two: the foaming data of the foam prepared from the full water hard foam of the invention and the traditional full water hard foam (JH-350W) are compared:
under the condition that the product has the same compressive strength, high and low temperature dimensional stability, water absorption and thermal conductivity, the isocyanate dosage index in the full water rigid foam system is 1, and the isocyanate dosage index in the traditional full water rigid foam (350W) system is 1.5. The addition of isocyanate is saved, and the foaming cost is reduced. The foaming data for the foams made from the fully water-rigid polyethers according to the invention from examples 3 and 4 correspond substantially to example 2.
As can be seen from the cream time, the drawing time and the tack-free time of the product, when the crude polyether polyol is prepared in the embodiments 2-4 of the invention, PO is added firstly and then EO is added in sections, the activity is high during foaming, and the product is suitable for spraying with high foaming speed requirement. The crude polyether polyol prepared in example 1 of the present invention is mixed and polymerized, so that the foaming activity is low, and the polyether polyol can be used for molding foaming requiring relatively low activity and good fluidity.
Claims (10)
1. A synthetic method of low isocyanate index full water rigid foam polyether polyol is characterized by comprising the following steps: the method comprises the following steps:
first step, preparation of activated Melamine resin
Adding melamine, a formaldehyde solution with the mass concentration of 37% and organic amine into a reaction kettle according to a certain proportion, stirring, heating and polymerizing, wherein the organic amine is one of monoethanolamine, diethanolamine, triethanolamine, urea and diethylenetriamine; wherein the molar ratio of the melamine to the formaldehyde to the organic amine is 1:1:1, 1:2:1 or 1:3:3, the polymerization temperature is 40-100 ℃, and the polymerization time is 2-7 hours; after the polymerization is finished, continuously heating to 100-110 ℃ for dehydration, and analyzing that the water content is less than 0.05 percent to prepare activated melamine resin;
second step, preparation of crude polyether polyol
Adding activated melamine resin and organic amine into a reaction kettle according to a certain proportion, stirring and heating to a polymerization temperature, adding an epoxy compound for polymerization reaction, wherein the organic amine is one of monoethanolamine, diethanolamine, triethanolamine, urea and diethylenetriamine;
the epoxy compound is added in a segmented mode or a mixed polymerization mode, and the epoxy compound is Propylene Oxide (PO) and Ethylene Oxide (EO);
when the epoxy compound is added in a segmented mode, the polymerization temperature is 80-130 ℃, the first stage of adding the epoxy compound in a segmented mode is PO, the second stage of adding the epoxy compound is EO, the adding mode is continuous adding, the polymerization temperature of the first stage and the polymerization temperature of the second stage are the same, the mass ratio of PO to EO is 1: 0-1: 1 and does not include 1:0, and the adding amount is 60-70% of the mass of a finished product;
when mixed polymerization is added, the polymerization temperature is 100-130 ℃, wherein the ratio of epoxy compound: the mass ratio of PO to EO is 1: 0-1: 1 and does not include 1:0, the adding mode is continuous adding, and the adding amount is 60-70% of the finished product mass;
until the pressure in the kettle is unchanged, finishing polymerization and degassing to prepare crude polyether polyol;
third step, polyether polyol refining
Adding deionized water into the prepared crude polyether polyol for emulsification, wherein the adding amount of the deionized water accounts for 5% of the mass of the crude polyether polyol, heating to the neutralization temperature of 80-120 ℃, adding inorganic acid for neutralization, stirring for neutralization for 2 hours, analyzing the pH value to be 6-8, adding a refining agent, wherein the adding amount of the refining agent accounts for 0.3% of the mass of the crude polyether polyol, stirring for 0.5 hour, dehydrating, analyzing the water content to be less than 0.05%, cooling and filtering to obtain the low isocyanate index all-water rigid foam polyether polyol.
2. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: the refining agent is magnesium hexasilicate.
3. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: the mol ratio of the activated melamine resin to the organic amine in the second step is 1: 1-1: 4.
4. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: when the mixed polymerization is added or added in a segmented mode, the mass ratio of the propylene oxide to the ethylene oxide is 2:1, and the adding amount of the epoxy compound is 60% of the mass of a finished product.
5. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: when the materials are added in a segmented mode, the polymerization temperature is 115 ℃, the first-stage polymerization time is 1.5 hours, and the second-stage polymerization time is 3 hours.
6. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: when the mixture was added, the polymerization temperature was 125 ℃.
7. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: the mass ratio of the activated melamine resin to the organic amine in the second step is 1: (0.36-0.61).
8. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: the molar ratio of the melamine to the formaldehyde to the organic amine is 1:1:1, the polymerization temperature is 80 ℃, and the polymerization time is 3 hours.
9. The process for the synthesis of the low isocyanate index all-water rigid foam polyether polyol according to claim 1, wherein: the inorganic acid is phosphoric acid.
10. The process of synthesizing a low isocyanate index all-water rigid foam polyether polyol as claimed in claim 9, wherein: the phosphoric acid is a phosphoric acid solution, the mass concentration of the phosphoric acid solution is 75%, and the adding amount of the phosphoric acid solution accounts for 1% of the mass of the crude polyether polyol.
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| CN101775131A (en) * | 2010-02-03 | 2010-07-14 | 山东蓝星东大化工有限责任公司 | Method for synthesis of novel flame-retardant rigid-foam polyether polyol |
| CN105585707A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Synthetic method of flame-retardation hard foam polyether polyol |
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