CN110041553B - Foam stabilizer for full-water foaming system - Google Patents
Foam stabilizer for full-water foaming system Download PDFInfo
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- CN110041553B CN110041553B CN201910400650.8A CN201910400650A CN110041553B CN 110041553 B CN110041553 B CN 110041553B CN 201910400650 A CN201910400650 A CN 201910400650A CN 110041553 B CN110041553 B CN 110041553B
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- 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
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
The invention relates to a polyurethane foam stabilizing technology, in particular to a foam stabilizer for a full-water foaming system. The foam stabilizer is a modified polyether grafted organic silicon surfactant; the main raw materials for preparing the modified polyether grafted silicone surfactant comprise low-hydrogen silicone oil and unsaturated polyether, and the weight ratio of the low-hydrogen silicone oil to the unsaturated polyether is 1: (1-10).
Description
Technical Field
The invention relates to a polyurethane foam stabilizing technology, in particular to a foam stabilizer for a full-water foaming system.
Background
Polyurethane foam is one of the main varieties of polyurethane synthetic materials, and has the advantages of porosity, small relative density, high specific strength and the like. Can be made into soft, semi-hard and hard polyurethane foam plastics by adjusting the used raw materials and formula. The polyurethane foam plastic has a wide application range, almost permeates all departments of national economy, is generally applied to the industries of furniture, bedding, transportation, refrigeration, construction, heat insulation and the like, and becomes one of indispensable materials.
The foam stabilizer is one of key components in the production formula of polyurethane foam plastics, and the functions of the foam stabilizer in the production process of the polyurethane foam plastics, such as emulsification, nucleation, foam stabilization, material flowability and the like, are mutually restricted. For example, emulsification and flowability of the material increases when the foam stabilizer reduces the surface tension of the polyurethane foam system a lot, but this has a negative effect on nucleation and foam stabilization. Therefore, how to design the molecular structure of the foam stabilizer to ensure that various properties of the foam stabilizer are comprehensively balanced is the key for ensuring the quality of the foam stabilizer. Meanwhile, when the performance of the foam stabilizer is sought to be improved, how to optimize the production process of the foam stabilizer to reduce the discharge of pollutants harmful to the environment and reduce the product cost is also a great challenge for foam stabilizer practitioners. At present, the traditional foaming agent F-11 is completely forbidden, 141B is limited in use, and an all-water foaming system is one of the most promising applications. The development of novel foam stabilizers for all-aqueous systems is very urgent.
Disclosure of Invention
In order to solve the technical problems, the first aspect of the invention provides a foam stabilizer for an all-water foaming system, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the main raw materials for preparing the modified polyether grafted silicone surfactant comprise low-hydrogen silicone oil and unsaturated polyether, and the weight ratio of the low-hydrogen silicone oil to the unsaturated polyether is 1: (1-10).
As a preferable technical scheme, the hydrogen content of the low-hydrogen silicone oil is 0.05-0.8 wt%.
As a preferable technical scheme, the raw materials for preparing the low hydrogen-containing silicone oil comprise octamethylcyclotetrasiloxane, hexamethyldisiloxane and high hydrogen-containing silicone oil.
As a preferable technical scheme, the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding low-hydrogen silicone oil, unsaturated polyether, a dispersing agent and a complex metal catalyst into a reaction kettle, and reacting for 2-8 hours at the reaction temperature of 80-120 ℃ and under normal pressure to obtain an intermediate product;
2) carrying out sulfonation treatment and/or phosphorylation treatment on the intermediate product in the step 1).
As a preferable technical scheme, the unsaturated polyether is allyl alcohol polyether and/or allyl polyoxyethylene polyoxypropylene epoxy ether.
As a preferred technical scheme, the sulfonation treatment comprises the following steps:
dissolving potassium bisulfite and the intermediate product in a mixed solution of isopropanol and water, reacting at 70-80 ℃ for 2-6 hours, and discharging to obtain the potassium bisulfite-water mixed solution; the volume ratio of the isopropanol to the water is (2-10): 1.
as a preferred technical solution, the weight ratio of the potassium bisulfite to the intermediate product is 1:
(5～60)。
as a preferred embodiment, the phosphorylation treatment comprises the following steps:
adding the intermediate product and phosphoric acid into a reaction kettle, adding toluene accounting for 50-60 wt% of the total mass of the monomers for dissolving, carrying out heat preservation reaction at 90-100 ℃ for 3-5 hours under the condition of introducing nitrogen, and then treating to obtain the catalyst.
As a preferable technical scheme, the weight ratio of the intermediate product to the phosphoric acid is (8-30): 1.
the second aspect of the invention provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
125-150 parts of isocyanate
1.5-3 parts of a stabilizer;
the stabilizer is a foam stabilizer as described above that can be used in an all-water foaming system.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
It should be understood that other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about".
In order to solve the technical problems, the first aspect of the invention provides a foam stabilizer for an all-water foaming system, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the main raw materials for preparing the modified polyether grafted silicone surfactant comprise low-hydrogen silicone oil and unsaturated polyether, and the weight ratio of the low-hydrogen silicone oil to the unsaturated polyether is 1: (1-10).
The low hydrogen-containing silicone oil (PMHS) in the invention means that the tail end or the side chain of the main chain of the organic silicon polymer contains part or each chain link of active hydrogen atoms which can participate in crosslinking reaction, and the active hydrogen atoms can perform hydrosilylation reaction with monomer, oligomer or polymer containing unsaturated double bonds or triple bonds under the action of Pt catalyst to form graft, block or network copolymer.
In some embodiments, the low hydrogen silicone oil has a hydrogen content of 0.05 to 0.8 wt%.
The hydrogen content of the low hydrogen-containing silicone oil can be measured by a titration method, and the method specifically comprises the following steps: firstly, preparing 0.2mol/L acetic acid solution of bromine, then preparing 10% potassium iodide solution, and then preparing 0.1mol/L sodium thiosulfate solution. The concentration of sodium thiosulfate is calibrated, potassium dichromate is used for calibration, finally, 0.07g of hydrogen-containing silicone oil is sampled, 20ml of carbon tetrachloride is added into a 250ml iodine measuring flask, 10 ml of bromine acetic acid solution is added, after standing for 2 hours, 25 ml of potassium iodide is added, sodium thiosulfate which is just calibrated is used for titration to the end point, and then the hydrogen content can be calculated.
The low-hydrogen silicone oil can be purchased from the market or obtained by self-making
In some embodiments, the raw materials for preparing the low hydrogen silicone oil include octamethylcyclotetrasiloxane, hexamethyldisiloxane and high hydrogen silicone oil.
Preferably, the weight ratio of the octamethylcyclotetrasiloxane, the hexamethyldisiloxane and the high hydrogen-containing silicone oil is (20-1000): (1-32): 6-50).
Preferably, the preparation method of the low hydrogen-containing silicone oil comprises the following steps:
reacting octamethylcyclotetrasiloxane, hexamethyldisiloxane and high hydrogen-containing silicone oil at 30-80 deg.C for 4-12 hr under the action of acidic catalyst to obtain low hydrogen-containing silicone oil with hydrogen content of 0.05-0.8%.
The mass of the acidic catalyst is 0.5-6% of the sum of the mass of octamethylcyclotetrasiloxane, hexamethyldisiloxane and high-hydrogen-content silicone oil, and strong acid resin or acid clay is adopted.
In some embodiments, the method of preparing the modified polyether graft silicone surfactant comprises the steps of:
1) adding low-hydrogen silicone oil, unsaturated polyether, a dispersing agent and a complex metal catalyst into a reaction kettle, and reacting for 2-8 hours at the reaction temperature of 80-120 ℃ and under normal pressure to obtain an intermediate product;
2) carrying out sulfonation treatment and/or phosphorylation treatment on the intermediate product in the step 1).
The complex metal catalyst in the present invention may be any catalyst capable of causing Michael addition reaction between a carbon-carbon unsaturated double bond and a Si-H bond, such as platinum-rhodium complex, chloroplatinic acid, etc.
The dispersant of the invention has the main functions of effectively dispersing the components such as low-hydrogen silicone oil, unsaturated polyether, catalyst and the like, improving the reaction conversion rate, reducing the generation of side reaction and the like. The dispersant may be a small molecular weight polyether, a small molecular weight polyol, and the like, such as diethylene glycol, triethylene glycol, and the like.
In some embodiments, the unsaturated polyether is an allyl alcohol polyether and/or an allyl polyoxyethylene polyoxypropylene epoxy ether.
Preferably, the unsaturated polyether is allyl alcohol polyether and allyl polyoxyethylene polyoxypropylene epoxy ether, and the weight ratio of the allyl alcohol polyether to the allyl polyoxyethylene polyoxypropylene epoxy ether is 2: 1.
more preferably, the hydroxyl value (mgKOH/g) of the allyl alcohol polyether is 30-130, and products such as HMS-229R, HMS-232R, HMS-235R and the like of Huangjiang Huangma science and technology Limited can be selected. The weight average molecular weight of the allyl polyoxyethylene polyoxypropylene epoxy ether is 500-600, and the allyl polyoxyethylene polyoxypropylene epoxy ether can be purchased from HY series products of Nanjing Dingshan chemical industry Co.
In some embodiments, the sulfonation treatment includes the steps of:
dissolving potassium bisulfite and the intermediate product in a mixed solution of isopropanol and water, reacting at 70-80 ℃ for 2-6 hours, and discharging to obtain the potassium bisulfite-water mixed solution; the volume ratio of the isopropanol to the water is (2-10): 1.
in some embodiments, the weight ratio of potassium bisulfite to intermediate product is 1: (5-60).
In some embodiments, the phosphorylation process comprises the steps of:
adding the intermediate product and phosphoric acid into a reaction kettle, adding toluene accounting for 50-60 wt% of the total mass of the monomers for dissolving, carrying out heat preservation reaction at 90-100 ℃ for 3-5 hours under the condition of introducing nitrogen, and then treating to obtain the catalyst.
In some embodiments, the weight ratio of the intermediate product to phosphoric acid is (8-30): 1.
in the invention, the polyether graft modified organic silicone oil is sulfonated or phosphatized, so that the foam stabilizer has multiple functions. Due to the introduction of the sulfonic acid ester or the phosphoric acid ester group, the hydrophilicity of the polyether grafted organic silicon oil is improved, and the solvation between the organic silicon oil and the moisture value is improved, so that the stability of the foam stabilizer to foam is improved. In addition, due to the introduction of phosphate groups, when the foam material burns, phosphate components in the foam stabilizer are decomposed to generate a non-flammable liquid film of phosphoric acid, and the boiling point of the non-flammable liquid film can reach 300 ℃. Meanwhile, phosphoric acid is further dehydrated to generate metaphosphoric acid, and the metaphosphoric acid is further polymerized to generate polymetaphosphoric acid. In the process, the covering layer generated by phosphoric acid plays a covering effect, and the generated polymetaphosphoric acid is strong acid and is a strong dehydrating agent, so that the polymer is dehydrated and carbonized, the combustion process mode of the polymer is changed, and a carbon film is formed on the surface of the polymer to isolate air, thereby improving the foam stabilizing effect of the stabilizer and simultaneously playing a stronger flame retardant effect.
The second aspect of the invention provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
125-150 parts of isocyanate
1.5-3 parts of a stabilizer;
the stabilizer is a foam stabilizer as described above that can be used in an all-water foaming system.
The combined polyether comprises polyether polyol, 2.0-5.0 wt% of a catalyst and 1-8 wt% of water, wherein the percentage is the proportion of each component based on the total mass of the combined polyether.
In the present invention, the specific type of the all-water polyether polyol composition is not particularly limited, and all-water polyether polyol BT-328W, all-water polyether polyol B607, all-water polyether polyol B705, etc. of Boshi, Zhongshan may be used.
The specific type of the polyether polyol is not particularly limited in the invention, and YD-380, YD-450BC, YD-480, YD-889, YD-1050, YD-4110, YD-4114, YD-8238 and the like of the chemical group of northeast of Hebei province can be adopted.
The catalyst is an amine catalyst. As the amine catalyst, bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine, dimethylcyclohexylamine, triethylenediamine, 1,3, 5-tris (dimethylaminopropyl) -hexahydrotriazine, N-dimethylbenzylamine and the like can be used. And sodium/potassium fatty acid (soap base including sodium/potassium laurate, sodium/potassium myristate, sodium/potassium palmitate, sodium/potassium stearate), etc.
The chemical blowing agent may be water.
The isocyanate in the present invention is not particularly limited as long as the isocyanate group index is 90 to 120. Examples of the isocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, aliphatic triisocyanates, and polyisocyanates.
Examples of the aliphatic diisocyanate include propylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, 1, 2-propylene diisocyanate, 1, 2-butylene diisocyanate, 2, 3-butylene diisocyanate, 1, 3-butylene diisocyanate, 2, 4, 4-or 2, 2, 4-trimethyl 1, 6-hexamethylene diisocyanate, and methyl 2, 6-diisocyanatohexanoate. Examples of the alicyclic diisocyanate include 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, 3-isocyanatomethyl-3, 5, 5-trimethylcyclohexane isocyanate (also known as isophorone diisocyanate), 4' -methylenebis (cyclohexyl isocyanate), methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, 1, 3-bis (isocyanatoethyl) cyclohexane, 1, 4-bis (isocyanatoethyl) cyclohexane, 2, 5-or 2, 6-bis (isocyanatomethyl) Norbornane (NBDI), mixtures thereof and the like.
Examples of the aromatic diisocyanate include: 2, 4-tolylene diisocyanate and 2, 6-tolylene diisocyanate, and isomer mixtures of the aforementioned tolylene diisocyanates, 4 ' -diphenylmethane diisocyanate, 2, 4 ' -diphenylmethane diisocyanate and 2, 2 ' -diphenylmethane diisocyanate, and arbitrary isomer mixtures of the aforementioned diphenylmethane diisocyanates, tolylene diisocyanates, p-phenylene diisocyanates, naphthalene diisocyanates, and the like. Examples of the aliphatic triisocyanate include 1,3, 6-triisocyanate methylhexane and the like. Examples of the polyisocyanate include polymethylene polyphenyl polyisocyanates and polyisocyanates derived from the diisocyanate compounds. Examples of the polyisocyanate derived from the diisocyanate include isocyanurate polyisocyanates, biuret polyisocyanates, urethane polyisocyanates, allophanate polyisocyanates, and carbodiimide polyisocyanates. MDI is preferably used.
The method for preparing the rigid polyurethane foam of the present invention is not particularly limited, and the rigid polyurethane foam may be prepared by foaming according to a conventional method known to those skilled in the art.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the raw materials used are commercially available from national chemical reagents, unless otherwise specified.
Examples
Example 1A foam stabilizer for an all-water foaming system is provided, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding 50g of low-hydrogen silicone oil, 95g of unsaturated polyether, 20g of diethylene glycol and 5mg of platinum-rhodium complex solution into a reaction kettle, and reacting for 4 hours at the reaction temperature of 110 ℃ and normal pressure to obtain an intermediate product;
2) sulfonating the intermediate product in the step 1): dissolving potassium bisulfite and the intermediate product in a mixed solution of isopropanol and water, reacting for 4 hours at 80 ℃, and then distilling out the mixed solvent by reduced pressure to obtain the potassium bisulfite-water mixed solution.
The unsaturated polyether is allyl alcohol polyether HMS-229R (hydroxyl value is about 130) of Huangjiang Huangma chemical company Limited; the volume ratio of the isopropanol to the water is 2: 1; the weight ratio of the potassium bisulfite to the intermediate product is 1: 20.
the preparation method of the low hydrogen-containing silicone oil comprises the following steps:
100g of octamethylcyclotetrasiloxane, 5.6g of hexamethyldisiloxane, 30.6g of methyl high hydrogen silicone oil with hydrogen content of 1.55% and 8g of acid clay are added into a reaction kettle, heated to 45 ℃ and reacted for 12 hours to obtain low hydrogen silicone oil with hydrogen content of 0.35%.
The embodiment also provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
Isocyanate 125
1.5 of a stabilizing agent;
the stabilizer is a foam stabilizer which can be used in an all-water foaming system as described above; the all-water combined polyether adopts all-water combined polyether BT-328W (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city; the isocyanate is MDI.
Example 2A foam stabilizer for an all-water foaming system is provided, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding 50g of low-hydrogen silicone oil, 181g of unsaturated polyether, 35g of diethylene glycol and 16.5mg of platinum-rhodium complex into a reaction kettle, and reacting for 3 hours at the reaction temperature of 120 ℃ and normal pressure to obtain an intermediate product;
2) carrying out phosphorylation treatment on the intermediate product in the step 1): adding the intermediate product and phosphoric acid into a reaction kettle, adding toluene accounting for 50 wt% of the total mass of the monomers for dissolving, carrying out heat preservation reaction at 90 ℃ for 5 hours under the condition of introducing nitrogen, and then carrying out reduced pressure distillation and purification on a crude product at 80 ℃ and 0.08MPa to obtain the catalyst.
The unsaturated polyether is allyl polyoxyethylene polyoxypropylene epoxy ether, and is purchased from HY series products (molecular weight is 800) of Nanjing Bell chemical industry Limited company; the weight ratio of the intermediate product to the phosphoric acid is 27: 1.
the preparation method of the low hydrogen-containing silicone oil comprises the following steps:
100g of octamethylcyclotetrasiloxane, 3.4g of hexamethyldisiloxane, 27.5g of methyl high hydrogen silicone oil with 1.55% hydrogen content and 8g of acid clay are added into a reaction kettle, heated to 45 ℃ and reacted for 12 hours to obtain the low hydrogen silicone oil with 0.32% hydrogen content.
The embodiment also provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
Isocyanate 135
A stabilizer 2;
the stabilizer is a foam stabilizer which can be used in an all-water foaming system as described above; the all-water combined polyether adopts all-water combined polyether B607 (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city; the isocyanate is MDI.
Example 3A foam stabilizer for an all-water foaming system is provided, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding 50g of low-hydrogen silicone oil, 155g of unsaturated polyether, 24g of diglycol and 12.5mg of platinum-rhodium complex into a reaction kettle, and reacting for 3 hours at the reaction temperature of 120 ℃ and normal pressure to obtain an intermediate product;
2) carrying out phosphorylation treatment on the intermediate product in the step 1): adding the intermediate product and phosphoric acid into a reaction kettle, adding toluene accounting for 50 wt% of the total mass of the monomers for dissolving, carrying out heat preservation reaction at 90 ℃ for 5 hours under the condition of introducing nitrogen, and then carrying out reduced pressure distillation and purification on a crude product at 80 ℃ and 0.08MPa to obtain the catalyst.
The weight ratio of the intermediate product to the phosphoric acid is 16: 1; the unsaturated polyether is a mixture of allyl alcohol polyether HMS-232R (hydroxyl value is about 75) of Huangjiang Huangma chemical industry Co., Ltd and HY series allyl polyoxyethylene polyoxypropylene epoxy ether (molecular weight is 550) of Nanjing Zhongshan chemical industry Co., Ltd, and the weight ratio is 2: 1.
the preparation method of the low hydrogen-containing silicone oil comprises the following steps:
100g of octamethylcyclotetrasiloxane, 3.4g of hexamethyldisiloxane, 27.5g of methyl high hydrogen silicone oil with 1.55% hydrogen content and 8g of acid clay are added into a reaction kettle, heated to 45 ℃ and reacted for 12 hours to obtain the low hydrogen silicone oil with 0.32% hydrogen content.
The embodiment also provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
Isocyanate 135
A stabilizer 2;
the stabilizer is a foam stabilizer which can be used in an all-water foaming system as described above; the all-water combined polyether adopts all-water combined polyether B705 (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city. The isocyanate is MDI.
Example 4A foam stabilizer for an all-water foaming system is provided, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding 50g of low-hydrogen silicone oil, 155g of unsaturated polyether, 24g of diglycol and 12.5mg of platinum-rhodium complex into a reaction kettle, and reacting for 3 hours at the reaction temperature of 120 ℃ and normal pressure to obtain an intermediate product;
2) carrying out phosphorylation treatment on the intermediate product in the step 1): adding the intermediate product and phosphoric acid into a reaction kettle, adding toluene accounting for 50 wt% of the total mass of the monomers for dissolving, carrying out heat preservation reaction at 90 ℃ for 5 hours under the condition of introducing nitrogen, and then carrying out reduced pressure distillation and purification on a crude product at 80 ℃ and 0.08MPa to obtain the catalyst.
The weight ratio of the intermediate product to the phosphoric acid is 16: 1; the unsaturated polyether is a mixture of allyl alcohol polyether HMS-229R (hydroxyl value is about 130) of Huangjiang Huangma chemical Co., Ltd and HY series allyl polyoxyethylene polyoxypropylene epoxy ether (molecular weight is 550) of Nanjing Zhongshan chemical Co., Ltd, and the weight ratio is 2: 1.
the low-hydrogen silicone oil is methyl high-hydrogen silicone oil, and the hydrogen content is 1.55%.
The embodiment also provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
Isocyanate 135
A stabilizer 2;
the stabilizer is a foam stabilizer which can be used in an all-water foaming system as described above; the all-water combined polyether adopts all-water combined polyether B705 (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city. The isocyanate is MDI.
Example 5A foam stabilizer for an all-water foaming system is provided, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding 50g of low-hydrogen silicone oil, 155g of unsaturated polyether, 24g of diglycol and 12.5mg of platinum-rhodium complex into a reaction kettle, and reacting for 3 hours at the reaction temperature of 120 ℃ and normal pressure to obtain an intermediate product;
2) carrying out phosphorylation treatment on the intermediate product in the step 1): adding the intermediate product and phosphoric acid into a reaction kettle, adding toluene accounting for 50 wt% of the total mass of the monomers for dissolving, carrying out heat preservation reaction at 90 ℃ for 5 hours under the condition of introducing nitrogen, and then carrying out reduced pressure distillation and purification on a crude product at 80 ℃ and 0.08MPa to obtain the catalyst.
The weight ratio of the intermediate product to the phosphoric acid is 16: 1; the unsaturated polyether is a mixture of allyl alcohol polyether HMS-229R (hydroxyl value is about 130) of Huangjiang Huangma chemical Co., Ltd and HY series allyl polyoxyethylene polyoxypropylene epoxy ether (molecular weight is 550) of Nanjing Zhongshan chemical Co., Ltd, and the weight ratio is 2: 1.
the preparation method of the low hydrogen-containing silicone oil comprises the following steps:
100g of octamethylcyclotetrasiloxane, 27.5g of methyl high hydrogen silicone oil with 1.55% hydrogen content and 8g of acid clay are added into a reaction kettle, and the mixture is heated to 45 ℃ and reacts for 12 hours to obtain the catalyst.
The embodiment also provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
Isocyanate 135
A stabilizer 2;
the stabilizer is a foam stabilizer which can be used in an all-water foaming system as described above; the all-water combined polyether adopts all-water combined polyether B705 (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city. The isocyanate is MDI.
Example 6The preparation raw materials of the polyurethane rigid foam material comprise the following components in parts by weight:
all-water combined polyether 100
Isocyanate 135
A stabilizer 2;
the stabilizer is H-3565B of the Zhongshan Dong drastic chemical industry; the all-water combined polyether adopts all-water combined polyether B705 (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city. The isocyanate is MDI.
Example 7A foam stabilizer for an all-water foaming system is provided, wherein the foam stabilizer is a modified polyether grafted organic silicon surfactant; the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding 50g of low-hydrogen silicone oil, 155g of unsaturated polyether, 24g of diglycol and 12.5mg of platinum-rhodium complex into a reaction kettle, and reacting for 3 hours at the reaction temperature of 120 ℃ and under normal pressure to obtain the catalyst.
The unsaturated polyether is a mixture of allyl alcohol polyether HMS-229R (hydroxyl value is about 130) of Huangjiang Huangma chemical Co., Ltd and HY series allyl polyoxyethylene polyoxypropylene epoxy ether (molecular weight is 550) of Nanjing Zhongshan chemical Co., Ltd, and the weight ratio is 2: 1.
the preparation method of the low hydrogen-containing silicone oil comprises the following steps:
100g of octamethylcyclotetrasiloxane, 3.4g of hexamethyldisiloxane, 27.5g of 202 methyl high hydrogen silicone oil with 1.55% hydrogen content and 8g of acid clay are added into a reaction kettle, heated to 45 ℃ and reacted for 12 hours to obtain the low hydrogen silicone oil with 0.32% hydrogen content.
The embodiment also provides a polyurethane rigid foam material, which comprises the following components in parts by weight:
all-water combined polyether 100
Isocyanate 135
A stabilizer 2;
the stabilizer is a foam stabilizer which can be used in an all-water foaming system as described above; the all-water combined polyether adopts all-water combined polyether B705 (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city. The isocyanate is MDI.
Comparative example 1The preparation raw materials of the polyurethane rigid foam material comprise the following components in parts by weight:
all-water combined polyether 100
Isocyanate 135
A stabilizer 2;
the stabilizer is a silicone surfactant B8444; the all-water combined polyether adopts all-water combined polyether B705 (comprising polyether polyol, catalyst and water) of Technology limited company of Boshi in Zhongshan city. The isocyanate is MDI.
Evaluation of Performance
The physical properties of the foam stabilizers which can be used in the all-water foaming system are compared, and the transparency of the foam stabilizers is subjectively compared according to the transparency, so that the foam stabilizers which can be used in the all-water foaming system and are provided in examples 1-3 are good in transparency, and the foam stabilizers in examples 4, 5 and 7 are good in transparency.
The cream time, gel time, tack free time and free foam density of the rigid polyurethane foam were measured at the same material temperature and ambient temperature during the foaming process, and the results are shown in the following table.
TABLE 1 comparison of Activity tables
The flowability of the stabilizers provided in the examples and comparative examples is compared, and parameters such as thermal conductivity, cell structure of foam surface (whether large bubbles exist on the surface, whether the cells are uniform and whether the structure is regular are judged to judge whether the cell structure is good or bad, and the evaluation is 1-5, wherein the cells on the surface of 1 grade are the least regular and the worst, and the surface performance of 5-point foam is the best) are tested, and the results are shown in the following table.
TABLE 2 flowability comparison
It can be seen from the above table that the foam stabilizers of examples 1 to 3 are excellent in stabilizing effect. The polyurethane foam material has lower free foam density and shorter non-stick time, can be used for preparing corresponding polyurethane foam materials at a higher production speed, does not have the phenomena of cracking inside the foam materials and the like, can save time and preparation cost, and improves the production efficiency. In addition, when the foam stabilizer in the embodiments 1 to 3 is applied to a polyurethane foam material, the foam in the production process can be well stabilized, the foam has higher foam height and higher foam weight, and the uniform cell density and regular cell structure size of the material in the foaming process are represented from the side. In addition, the table shows that the stabilizing agents in the embodiments 1-3 have higher flow index and better foam surface performance.
Finally, it should be understood that the above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (2)
1. A foam stabilizer for an all-water foaming system is characterized in that the foam stabilizer is a modified polyether grafted organic silicon surfactant; the main raw materials for preparing the modified polyether grafted silicone surfactant comprise low-hydrogen silicone oil and unsaturated polyether, and the weight ratio of the low-hydrogen silicone oil to the unsaturated polyether is 1: (1-10);
the hydrogen content of the low-hydrogen silicone oil is 0.05-0.8 wt%;
the raw materials for preparing the low hydrogen-containing silicone oil comprise octamethylcyclotetrasiloxane, hexamethyldisiloxane and high hydrogen-containing silicone oil;
the preparation method of the modified polyether grafted organosilicon surfactant comprises the following steps:
1) adding low-hydrogen silicone oil, unsaturated polyether, a dispersing agent and a complex metal catalyst into a reaction kettle, and reacting for 2-8 hours at the reaction temperature of 80-120 ℃ and under normal pressure to obtain an intermediate product;
2) carrying out sulfonation treatment and/or phosphorylation treatment on the intermediate product in the step 1);
the unsaturated polyether is allyl alcohol polyether and/or allyl polyoxyethylene polyoxypropylene epoxy ether, and the hydroxyl value of the allyl alcohol polyether is 75 mgKOH/g;
the sulfonation treatment comprises the following steps:
dissolving potassium bisulfite and the intermediate product in a mixed solution of isopropanol and water, reacting at 70-80 ℃ for 2-6 hours, and discharging to obtain the potassium bisulfite-water mixed solution; the volume ratio of the isopropanol to the water is (2-10): 1;
the weight ratio of the potassium bisulfite to the intermediate product is 1: (5-60);
the phosphorylation treatment comprises the following steps:
adding the intermediate product and phosphoric acid into a reaction kettle, adding toluene accounting for 50-60 wt% of the total mass of the monomers for dissolving, carrying out heat preservation reaction at 90-100 ℃ for 3-5 hours under the condition of introducing nitrogen, and then carrying out treatment to obtain the product;
the weight ratio of the intermediate product to phosphoric acid is (8-30): 1.
2. the polyurethane rigid foam material is characterized by comprising the following components in parts by weight:
all-water combined polyether 100
125-150 parts of isocyanate
1.5-3 parts of a stabilizer;
the stabilizer is the foam stabilizer of claim 1 which can be used in an all-water foaming system.
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| CN111116922A (en) * | 2019-12-30 | 2020-05-08 | 江苏奥克化学有限公司 | Preparation method and application of phosphorus-containing polyether modified organic silicon flatting agent |
| CN111328821A (en) * | 2020-03-03 | 2020-06-26 | 上海悦联生物科技有限公司 | Bactericide composition containing pyraclostrobin and mancozeb |
| CN113881419B (en) * | 2020-07-02 | 2023-04-07 | 中国石油化工股份有限公司 | Foam liquid discharging agent composition for high-condensate gas well and preparation method and application thereof |
| CN113105664B (en) * | 2021-03-17 | 2022-11-01 | 珠海东诚新材料股份有限公司 | Polyurethane foam stabilizer |
| CN115044217A (en) * | 2022-06-29 | 2022-09-13 | 成都交通投资集团有限公司 | High-viscoelasticity modified asphalt suitable for diversified climates |
| CN115073745B (en) * | 2022-07-01 | 2023-09-15 | 安徽恒光聚氨酯材料有限公司 | Environment-friendly antioxidant modified silicone oil and preparation method thereof |
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