CN112646106A - Composite polyether for environment-friendly flame-retardant polyurethane commercial beverage barrel and preparation method thereof - Google Patents
Composite polyether for environment-friendly flame-retardant polyurethane commercial beverage barrel and preparation method thereof Download PDFInfo
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- 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
- C08G18/4816—Two or more polyethers of different physical or chemical nature mixtures of two or more polyetherpolyols having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1808—Catalysts containing secondary or tertiary amines or salts thereof having alkylene polyamine groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/1816—Catalysts containing secondary or tertiary amines or salts thereof having carbocyclic groups
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/125—Water, e.g. hydrated salts
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- 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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/142—Compounds containing oxygen but no halogen atom
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08G2101/00—Manufacture of cellular products
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/10—Water or water-releasing compounds
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/12—Organic compounds only containing carbon, hydrogen and oxygen atoms, e.g. ketone or alcohol
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/18—Binary blends of expanding agents
- C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
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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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to environment-friendly flame-retardant combined polyether for a commercial polyurethane beverage barrel and a preparation method thereof. The combined polyether is prepared from a component A and a component B, wherein: the component A comprises the following components in percentage by weight: 15-20% of polyether polyol A; 15-20% of polyether polyol B; 20-30% of polyester polyol C; 1.5 to 2.5 percent of foam stabilizer; 2 to 3.5 percent of chemical foaming agent; 1.5 to 2.5 percent of catalyst; 25-33% of flame retardant; 4-8% of a physical foaming agent; the component B is as follows: polymeric diphenylmethane diisocyanate. The product prepared by the invention has good heat insulation performance, high flame retardance and higher strength, and can be better applied to the field of catering beverages.
Description
Technical Field
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to environment-friendly flame-retardant combined polyether for a commercial polyurethane beverage barrel and a preparation method thereof.
Background
Besides the requirement of taste, the local catering process needs more freshness and taste of the beverage. The traditional refrigerator and freezer has insufficient flexibility in mobile catering, and the heat-insulating barrel can be directly used on a dining table due to appropriate volume.
The polyurethane rigid foam plastic is widely used in the industries of household appliances, pipelines and buildings as an excellent heat insulation material, has the best heat insulation performance on the premise of the same heat insulation thickness compared with the traditional heat insulation materials such as polyphenyl foam and phenolic foam, and is a different choice for being used as a heat insulation barrel by combining the characteristics of light weight, good processability and high compactness of polyurethane foam. In order to avoid fire hazards, the catering industry also has certain flame retardant requirements, and the trend is to improve the flame retardant and fire retardant properties of polyurethane foam.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the composite polyether for the environment-friendly flame-retardant polyurethane commercial beverage barrel has good heat preservation performance and high flame retardance, and can be better applied to the field of catering beverages; meanwhile, the invention also provides a preparation method of the compound, which is simple, efficient, scientific and reasonable.
The composite polyether for the environment-friendly flame-retardant polyurethane commercial beverage barrel is prepared from a component A and a component B, wherein:
the component A comprises the following components in percentage by weight:
the component B is as follows:
polymeric diphenylmethane diisocyanate.
The polyether polyol A is polyether polyol with functionality of 4-5 and hydroxyl value of 400-430mgKOH/g, and is preferably INOVL R6001C produced by Shandong-Nonwei new material Co.
The polyether polyol INOVL R6001C contains certain oil, which is helpful for enhancing the intersolubility of the components of the combined polyether system, and the prepared combined polyether is transparent and clear in appearance. The R6001C polyether uses a reaction type catalyst in the synthesis process, the catalyst forms a block to be embedded into the polyether in the polyether synthesis process, on the other hand, the catalyst can be used for the combined polyether foaming reaction, and the combined polyether prepared by using the R6001C as a raw material has better mold release property.
The polyether polyol B is polyether polyol with the functionality of 5-6 and the hydroxyl value of 430-470mgKOH/g, and is preferably INOVL R8315 produced by Shandong-Nonwei new material Co.
The polyether polyol INOVL R8315 has higher functionality, forms a large amount of crosslinking frameworks with polymeric diphenylmethane diisocyanate in the reaction process to provide strength for polyurethane foam, and is beneficial to more uniform foam pore size and better wrapping property for foaming agent gas.
The polyester polyol C has the functionality of 2, and the polyester polyol with the hydroxyl value of 170-180mgKOH/g is preferably the polyester polyol B175 produced by Shandong Monoway New Material Co.
The polyester polyol B175 uses a large amount of phthalic anhydride as a raw material in polyester synthesis, so that a large amount of aromatic heterocyclic rings are contained in a polyester structure, the flame retardant property is remarkably improved when a large amount of aromatic heterocyclic rings and other five-membered heterocyclic rings are contained in polyol in the combustion inhibition process of a polyurethane foam structure, and a carbonized layer is formed in the combustion process to further inhibit the longitudinal spread of combustion.
The foam stabilizer is an SI-C surfactant, preferably a foam stabilizer B8870 produced by Shanghai Texaco Special chemical company. The foam stabilizer B8870 can promote the uniform dispersion of various components in the component A, and is also beneficial to the uniform and fine foam pores formed during the reaction of the A, B component, so that the polyurethane foam has good fluidity and heat insulation performance.
The chemical foaming agent is water, preferably deionized water.
The catalyst is a mixture of pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, N-dimethylbenzylamine, TMR-2 (Wignengndessic) and 75% potassium acetate solution.
The flame retardant is a mixture of TCPP (tris (1-chloro-2-propyl) phosphate) and TEP (triethyl phosphate) in a mass ratio of 1:1.
The physical foaming agent is methyl formate, and is preferably Ecomate methyl formate foaming agent produced by Foam Supplies company. With the change of rigid polyurethane foaming agent, methyl formate is one of the most potential alternative foaming agents due to the outstanding advantages of zero ODP and zero GWP. Methyl formate is used as a physical foaming agent, so that the good heat insulation of polyurethane foam is guaranteed, and the flame-retardant and fireproof performance of the foam is improved, so that the prepared drink barrel has good heat insulation and flame-retardant performances.
The preparation method of the combined polyether for the environment-friendly flame-retardant polyurethane commercial beverage barrel comprises the following steps:
(1) preparation of component A: sequentially adding the weighed polyether polyol A, polyether polyol B, polyester polyol C, foam stabilizer, chemical foaming agent, catalyst, flame retardant and physical foaming agent into a reaction kettle, stirring for 0.5-1 hour at normal temperature, and fully mixing;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: and B is 1:1.4-1.5, uniformly mixed by a high-pressure foaming machine, and injected into a mold to produce the commercial beverage barrel.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, through the synergistic cooperation of the polyether polyol A, the polyether polyol B and the polyester polyol C with the raw materials, the combined polyether has better demolding property, higher strength, flame retardance and heat-insulating property.
2. The catalyst system adopted by the invention is reasonably matched by adjusting the dosage, and sufficient foaming power is provided at the initial stage in the reaction process of the A, B component, so that the foam has better fluidity and can be better filled into a mold; the foam prepared by fully crosslinking the two components in the middle stage has higher strength and uniform pore size of the cells, and the excessive isocyanate groups in the total system in the later stage form a terpolymer under the action of a catalyst, so that a flame-retardant group is provided for polyurethane foam to improve the overall flame-retardant property.
3. The flame retardant adopted by the invention is a mixture of TCPP (tris (1-chloro-2-propyl) phosphate) and TEP (triethyl phosphate) in a ratio of 1:1, the mixing according to the proportion is the optimal matching of flame retardance and cost, and meanwhile, the viscosity of the selected polyol in the combined polyether is higher, the system viscosity can be reduced after the mixture of TCPP and TEP is added, and the A, B components can be uniformly mixed.
4. The physical foaming agent adopted by the invention is methyl formate, belongs to an environment-friendly foaming agent, is the only foaming agent which simultaneously meets the conditions of zero ODP, zero GWP and no VOC in the foaming agents which are put into use at present, accords with the development trend of the foaming agent, and can greatly reduce CO by replacing HFCs single ton foaming agent2On the other hand, methyl formate has good solubility in polyol, has lower saturated vapor pressure than HFC-245, and has improvement effect on the storage stability, thermal conductivity and compressive strength of foam.
5. The preparation method is simple and easy to operate, and is beneficial to large-scale production.
Detailed Description
The present invention will be further described with reference to the following examples.
All the raw materials used in the examples are commercially available unless otherwise specified.
Example 1
(1) Preparing a component A, 200kg, respectively weighing polyether polyol A: INOVL R6001C (shandong-novei new materials ltd) 33.8kg, polyether polyol B: 31.2kg of INOVL R8315 (shandong-norway new materials limited), polyester polyol C: 51.1kg of B175 (Shandong-Nonwei polyurethane Co., Ltd.), 4.06kg of foam stabilizer B8870 (Yingchunggsai), 5.46kg of deionized water, catalyst: 0.13kg of pentamethyldiethylenetriamine, 0.59kg of N, N-dimethylcyclohexylamine, 1.16kg of N, N-dimethylbenzylamine, 0.81kg of TMR-2 (Wiegendulisate), 2.09kg of a mixture of 75% potassium acetate solution, 58kg of flame retardant (TCPP mixed with TEP at a ratio of 1: 1), and 11.6kg of methyl formate as a physical foaming agent.
And sequentially adding the weighed polyether polyol A, polyether polyol B, polyester polyol C, a foam stabilizer, a chemical foaming agent, a catalyst, a flame retardant and a physical foaming agent into a reaction kettle, stirring for 0.5 hour at normal temperature, and fully mixing.
(2) And 300kg of component B polymeric diphenylmethane diisocyanate.
(3) The component A and the component B are uniformly mixed and injected into a mold through a high-pressure machine according to the weight ratio of 1:1.5, and the quality index of the prepared product is shown in table 1.
Example 2
(1) Preparing a component A, 200kg, respectively weighing polyether polyol A: INOVL R6001C (shandong-novei new materials ltd) 34.2kg, polyether polyol B: INOVL R8315 (shandong-norway new materials ltd) 34.2kg, polyester polyol C: 45.6kg of B175 (Shandong-Nonwei polyurethane Co., Ltd.), 3.76kg of foam stabilizer B8870 (Yingchunggsai), 5.13kg of deionized water, and catalyst: 0.11kg of pentamethyldiethylenetriamine, 0.46kg of N, N-dimethylcyclohexylamine, 1.15kg of N, N-dimethylbenzylamine, 0.68kg of TMR-2 (Wiegendulisate), 1.71kg of a mixture of 75% potassium acetate solution, 62.7kg of flame retardant (TCPP mixed with TEP at a ratio of 1: 1), and 10.3kg of methyl formate as a physical foaming agent.
And sequentially adding the weighed polyether polyol A, polyether polyol B, polyester polyol C, a foam stabilizer, a chemical foaming agent, a catalyst, a flame retardant and a physical foaming agent into a reaction kettle, stirring for 0.5 hour at normal temperature, and fully mixing.
(2) And the component B comprises 280kg of polymeric diphenylmethane diisocyanate.
(3) The component A and the component B are uniformly mixed and injected into a mold through a high-pressure machine according to the weight ratio of 1:1.4, and the quality index of the prepared product is shown in table 1.
Example 3
(1) Preparing a component A, 200kg, respectively weighing polyether polyol A: INOVL R6001C (shandong-novei new materials ltd) 31.8kg, polyether polyol B: 31.8kg of INOVL R8315 (shandong-norway new materials limited), polyester polyol C: 58.7kg of B175 (Shandong-Nowegian polyurethane Co., Ltd.), 4.03kg of foam stabilizer B8870 (winning DONGDEGUSAI), 4.89kg of deionized water, and catalyst: pentamethyldiethylenetriamine 0.06kg, N-dimethylcyclohexylamine 0.24kg, N-dimethylbenzylamine 1.01kg, TMR-2 (Wiegendulcoside) 0.98kg, a mixture of 75% potassium acetate solution 1.59kg, flame retardant (TCPP mixed with TEP at a ratio of 1: 1) 55.1kg, and physical foaming agent methyl formate 9.8 kg.
And sequentially adding the weighed polyether polyol A, polyether polyol B, polyester polyol C, a foam stabilizer, a chemical foaming agent, a catalyst, a flame retardant and a physical foaming agent into a reaction kettle, stirring for 0.5 hour at normal temperature, and fully mixing.
(2) 290kg of diphenylmethane diisocyanate was polymerized as the B component.
(3) The component A and the component B are uniformly mixed and injected into a die by a high-pressure machine according to the weight ratio of 1:1.45, and the quality index of the prepared product is shown in table 1.
Comparative example 1 (without addition of flame retardant)
(1) Preparing a component A, 200kg, respectively weighing polyether polyol A: INOVL R6001C (shandong-novei new materials ltd) 50.8kg, polyether polyol B: INOVL R8315 (shandong-norway new materials ltd) 50.8kg, polyester polyol C: 67.8kg of B175 (Shandong-Nowegian polyurethane Co., Ltd.), 4.24kg of foam stabilizer B8870 (winning DONGDEGUSAI), 4.58kg of deionized water, and catalyst: pentamethyldiethylenetriamine 0.48kg, N-dimethylcyclohexylamine 1.69kg, N-dimethylbenzylamine 1.69kg, TMR-2 (Wiegendulcis) 1.02kg, and a physical foaming agent methyl formate 16.9 kg.
And sequentially adding the weighed polyether polyol A, polyether polyol B, polyester polyol C, a foam stabilizer, a chemical foaming agent, a catalyst, a flame retardant and a physical foaming agent into a reaction kettle, stirring for 0.5 hour at normal temperature, and fully mixing.
(2) And 300kg of component B polymeric diphenylmethane diisocyanate.
(3) The component A and the component B are uniformly mixed and injected into a mold through a high-pressure machine according to the weight ratio of 1:1.5, and the quality index of the prepared product is shown in table 1.
TABLE 1 foam product quality test data for examples 1-3 and comparative example 1
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (10)
1. The utility model provides an environmental protection flame retardant type polyurethane commercial beverage bucket is with composite polyether which characterized in that: is prepared from a component A and a component B, wherein:
the component A comprises the following components in percentage by weight:
the component B is as follows:
polymeric diphenylmethane diisocyanate.
2. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the polyether polyol A is polyether polyol with the functionality of 4-5 and the hydroxyl value of 400-430 mgKOH/g.
3. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the polyether polyol B is polyether polyol with the functionality of 5-6 and the hydroxyl value of 430-470 mgKOH/g.
4. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the polyester polyol C is a polyester polyol with the functionality of 2 and the hydroxyl value of 170-180 mgKOH/g.
5. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the foam stabilizer is an SI-C surfactant.
6. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the chemical foaming agent is water.
7. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the catalyst is a mixture of pentamethyldiethylenetriamine, N-dimethylcyclohexylamine, N-dimethylbenzylamine, TMR-2 and 75% potassium acetate solution.
8. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the flame retardant is a mixture of tri (1-chloro-2-propyl) phosphate and triethyl phosphate according to the mass ratio of 1:1.
9. The polyether block for the environmentally friendly flame retardant polyurethane commercial beverage can according to claim 1, wherein: the physical foaming agent is methyl formate.
10. A method for preparing the environment-friendly flame-retardant polyurethane combined polyether for commercial beverage barrels as claimed in any one of claims 1 to 9, which is characterized in that: the method comprises the following steps:
(1) preparation of component A: sequentially adding the weighed polyether polyol A, polyether polyol B, polyester polyol C, foam stabilizer, chemical foaming agent, catalyst, flame retardant and physical foaming agent into a reaction kettle, stirring for 0.5-1 hour at normal temperature, and fully mixing;
(2) preparation of the component B: weighing polymeric diphenylmethane diisocyanate for later use;
(3) when in use, the component A and the component B are mixed according to the proportion of A: and B is 1:1.4-1.5, uniformly mixed by a high-pressure foaming machine, and injected into a mold to produce the commercial beverage barrel.
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| CN117510779A (en) * | 2023-11-30 | 2024-02-06 | 廊坊全振化工开发有限公司 | Combined polyether for polyisocyanurate shell, shell and preparation method |
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| CN117510779A (en) * | 2023-11-30 | 2024-02-06 | 廊坊全振化工开发有限公司 | Combined polyether for polyisocyanurate shell, shell and preparation method |
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Application publication date: 20210413 |