WO2019051886A1 - 胺基聚醚多元醇及其制备方法和应用 - Google Patents

胺基聚醚多元醇及其制备方法和应用 Download PDF

Info

Publication number
WO2019051886A1
WO2019051886A1 PCT/CN2017/103950 CN2017103950W WO2019051886A1 WO 2019051886 A1 WO2019051886 A1 WO 2019051886A1 CN 2017103950 W CN2017103950 W CN 2017103950W WO 2019051886 A1 WO2019051886 A1 WO 2019051886A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyether polyol
amine
polyol
phenylenediamine
catalyst
Prior art date
Application number
PCT/CN2017/103950
Other languages
English (en)
French (fr)
Inventor
沈周峰
朱霞林
蔡仲铭
Original Assignee
万华化学集团股份有限公司
万华化学（烟台）容威聚氨酯有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 万华化学集团股份有限公司, 万华化学（烟台）容威聚氨酯有限公司 filed Critical 万华化学集团股份有限公司
Publication of WO2019051886A1 publication Critical patent/WO2019051886A1/zh

Links

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
    • 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
    • C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino 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
    • 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
    • C08G65/2627—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 aromatic or arylaliphatic 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
    • 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
    • C08G65/2696—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 characterised by the process or apparatus used
    • 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
    • C08G2110/0025—Foam properties rigid

Definitions

  • the present invention relates to an amine-based polyether polyol and a process for the preparation thereof, and to a process for preparing a polyurethane foam using the amine-based polyether polyol.
  • Polyether polyols are widely used in the preparation of polyurethane rigid foams and can be used as insulation materials in refrigerators, freezers, cold storages and the like.
  • the polyether polyol currently used is o-toluenediamine polyether polyol, and the price of its raw material o-toluenediamine has risen all the way in recent years, resulting in excessive cost. Therefore, it is imperative to develop alternatives. While phenylenediamine, especially o-phenylenediamine, is close to o-toluenediamine due to its structure and properties, it is expected to be developed as an alternative.
  • the preparation process of the ortho-phenylenediamine-based polyether polyols known at present is almost always prepared by adding o-phenylenediamine at a high temperature (melting point of 103 ° C) and then adding an oxidized olefin.
  • a high temperature melting point of 103 ° C
  • stirring cannot be started, and the initial melting of o-phenylenediamine is as long as several hours to several dozen hours, the production efficiency is low, and the cost is too high.
  • the stirring cannot be turned on, and the local temperature of the raw material is too high, and side reactions such as carbonization and decomposition occur, and finally the final product has a darker color and poor quality.
  • o-phenylenediamine will undergo serious sublimation. Some of the o-phenylenediamine will adhere to the reactor wall after sublimation, and it will not participate in the reaction, which not only causes loss of raw materials but also affects the final product index and quality. In addition, the attachment of o-phenylenediamine to the wall of the vessel may cause difficulties in cleaning the reactor and affect the production of the next kettle product.
  • the polyether polyol is also used in the preparation of the polyether polyol, resulting in structural irregularities, low viscosity and the like, resulting in the final polyurethane product index, especially demolding,
  • the K value and compressive strength are not as good as those of the o-toluenediamine polyether.
  • CN200980108998.4 discloses a method for synthesizing polyether polyol by using o-phenylenediamine as an initiator, which requires melting o-phenylenediamine at a high temperature, and the initial reaction temperature is high, causing inability to start stirring, and there are many vices. Reaction, and easy to cause loss of raw materials, obtained
  • the polyether polyol is used in the polyether polyol which is not as good as the original toluene diamine as an initiator.
  • the present invention provides a novel method for preparing an amine-based polyether polyol, which can avoid the high-temperature melting step, improve production efficiency, reduce cost, and obtain a high-quality product.
  • a first aspect of the present invention provides a method for preparing an amine-based polyether polyol, wherein an aqueous solution of an amine is subjected to an autocatalytic reaction with a portion of an olefin oxide, followed by adding a catalyst, and adding the remaining oxidized olefin to an amine for epoxidation;
  • the amine contains 90% by mass or more of phenylenediamine.
  • the present invention does not require high temperature melting in the early stage of the reaction.
  • the phenylenediamine is at least one of o-phenylenediamine, m-phenylenediamine and p-phenylenediamine, and more preferably o-phenylenediamine.
  • the amine is dissolved in water as an initial solvent, and the amine is preferably 90% by mass or more of o-phenylenediamine and 10% by mass or less of other amine compounds.
  • Other amine compounds may include m-phenylenediamine, p-phenylenediamine, and the like.
  • the amine is a high purity (mass ratio greater than 99%) o-phenylenediamine.
  • the autocatalytic reaction may be carried out at 130 ° C or lower in the autocatalytic reaction stage; more preferably, the autocatalytic reaction of the present invention may be carried out at a lower temperature, preferably below 105 ° C; further Preferably, the autocatalytic reaction of the present invention can also be carried out at a lower temperature, for example, below 95 ° C, or below 90 ° C, or at 70-95 ° C.
  • the present invention employs an aqueous solution of an amine and an olefin oxide for autocatalytic reaction, and the initial reaction can be controlled at a relatively low temperature (for example, below 105 ° C, below 90 ° C, or preferably from 70 to 95 ° C; more preferably, the amine More preferably, o-phenylenediamine is used.
  • the autocatalytic reaction is carried out at a temperature below 100 ° C in an autocatalytic reaction.
  • the reaction temperature may be raised to 100 ° C or higher to carry out an aging reaction, preferably 100 to 115 ° C, and the length of the aging reaction is preferably 0.5 to 1 h, but it is not necessary to carry out the aging reaction.
  • the present invention is an autocatalytic reaction of phenylenediamine, and water does not participate in the reaction.
  • the dehydration operation is carried out before the catalyst is added, or the dehydration operation is carried out before the addition of the oxidized olefin after the catalyst is added, thereby avoiding water participating in the subsequent reaction, reducing the occurrence of side reactions, and making the quality of the water to the final product. No effect.
  • the initiator is an aqueous solution of an amine
  • the initial reaction temperature can be carried out at a relatively low temperature, which reduces the sublimation of the raw material and avoids the loss of the raw material, thereby facilitating the obtaining of a structurally regular and highly viscous product.
  • the properties of the subsequently prepared rigid polyurethane foam can be improved.
  • the amine is epoxidized with the remaining alkylene oxide at a temperature of from 100 ° C to 170 ° C, more preferably at a temperature of from 110 to 130 ° C; in some preferred embodiments,
  • the reaction pressure can be controlled at 0.1-10 bar.
  • the molar ratio of a portion of the alkylene oxide to amine added prior to catalyst addition is from 1 to 4:1, preferably from 3 to 3.8:1.
  • the amine polyether polyol has an equivalent weight of from 50 to 200, preferably from 80 to 125, per active hydrogen atom.
  • the ratio of the amount of the amine to the olefin oxide can be determined based on the equivalent.
  • the oxidized olefin is one or a mixture of two of propylene oxide and ethylene oxide, more preferably propylene oxide.
  • the catalyst in the present invention may be a strong base or an amine catalyst, and the amount of the catalyst is preferably from 0.2 to 0.4% by weight based on the weight of the polyether polyol product. If a strong base is used as the catalyst, the catalyst is preferably removed after completion of the reaction, and the removal method is a conventional means in the art and will not be described again; for example, the catalyst can be removed by adding an appropriate amount of phosphoric acid and dehydrating filtration. The amine catalyst can be retained or removed as appropriate.
  • the strong base may be an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, barium hydroxide or the like.
  • the amine catalyst may be, for example, methylimidazole, N,N-dimethylcyclohexylamine, trimethylamine or the like.
  • the adduct prepared by the method of the present invention has an average of 3.5-4 hydroxyl groups, 0-0.5 secondary amino groups, and 0-0.05 primary amino groups per molecule. It is more likely that the adduct will have an average of 3.8-4 hydroxyl groups per molecule, 0-0.2 secondary amino groups, 0-0.01 primary amino groups. It is more likely that the adduct will have an average of 3.9-4 hydroxyl groups per molecule, 0-0.1 secondary amino groups, and 0-0.001 primary amino groups.
  • an aminopolyether polyol obtained by the above production method.
  • the aminopolyether polyol prepared by the present invention may have a viscosity at 25 ° C of from 5,000 to 100,000 cps, preferably from 20,000 to 50,000 cps, more preferably from 30,000 to 4,000 cps.
  • a third aspect of the present invention provides a polyol composition for producing a polyurethane foam, the polyol composition comprising 10% by mass or more of the aminopolyether polyol as described above, more preferably Containing 30-60% by mass of the aminopolyether polyol as described above.
  • the polyol composition may also contain only the aminopolyether polyols described above.
  • the polyol composition further contains one or more of a polyester polyol and other polyether polyols.
  • the polyester polyol can be used as an additional polyol.
  • the other polyether polyol may contain a polyether polyol which is an initiator (or initiator), and the initiator may be, for example, an alkylene glycol (eg, ethylene glycol, propylene glycol, 1, 4).
  • the other polyether polyol comprises a polyether polyol having sucrose as an initiator (or as a starter), preferably in an amount of 15-40% by mass, more preferably, of the polyol composition. It is 20-40% by mass, and more preferably 25-35% by mass.
  • the other polyether polyols may also include one or more of oleyl ether and a polyether polyol starting with MDA-100.
  • the oil ether is a fatty acid ester-containing polyol, and the initiator is preferably sucrose, diethylene glycol and various fatty acid esters, by adding propylene oxide or epoxy B. Alkane or a mixture of the two.
  • the fatty acid esters may include various animal and vegetable fats, and some chemical synthetic fatty acid esters, such as palm oil, castor oil, soybean oil, linseed oil, and purified waste oil.
  • the amount of the oleyl ether is preferably from 5 to 40% by mass, more preferably from 5 to 30% by mass, still more preferably from 10 to 20% by mass, still more preferably from 10 to 15% by mass.
  • the polyether polyol starting from MDA-100 is an adduct of 4,4'-diaminodiphenylmethane with propylene oxide/ethylene oxide or a mixture of the two, preferably in an amount of a polyol composition. 0 to 30% by mass, more preferably 10 to 30% by mass, still more preferably 15 to 25% by mass.
  • the other polyether polyol is a mixture of one or more of oleyl ether, a polyether polyol having sucrose as a starter, and a polyether polyol having MDA-100 as a starter.
  • the polyol composition comprises the following components by mass percentage: 30-60% of the amino polyether polyol described above, polyether polyol 15-40 with sucrose as the initiator %, polyether polyol having MDA-100 as a starting agent 0-30% (more preferably 10-30%), and oleyl ether 5-40%.
  • the cost can be effectively controlled, and a better product viscosity can be obtained, and the obtained product can also perform well.
  • a fourth aspect of the invention provides a method of preparing a polyurethane foam, comprising the steps of:
  • the mixture is placed under conditions such that the mixture reacts to expand and solidify to form a rigid polyurethane foam.
  • the specific process operation for preparing the rigid polyurethane foam is a conventional technical means in the art, and is not particularly limited. The conventional operation can be carried out by referring to preparing a constant temperature mold having a desired size and shape, and the mold has one or A plurality of material injection ports, and usually one or more air outlet holes in the mold, and then the above mixture is injected into the mold, and the mixture is reacted and expanded in the mold cavity to form a polyurethane foam.
  • the polyisocyanate is used in an amount of from 1.0 to 1.3, preferably from 1.1 to 1.2, based on the equivalent of the polyol composition; and the amount of the blowing agent is from 10 to 20 parts, preferably based on 100 parts by weight of the polyol composition. 13-17 parts; based on 100 parts by weight of polyol
  • the composition is used in an amount of from 1 to 4 parts, preferably from 1.5 to 3 parts; based on 100 parts by weight of the polyol composition, the surfactant is used in an amount of from 0.01 to 6 parts, preferably from 2 to 4 parts.
  • the polyisocyanate may include at least one of an aromatic, aliphatic, and alicyclic polyisocyanate.
  • aromatic polyisocyanates such as 2,4- and/or 2,6-toluene diisocyanate, various isomers of diphenylmethane diisocyanate, hexahydrotoluene diisocyanate, methoxyphenyl-2,4 - Diisocyanate, hydrogenated MDI, polymethylene polyphenyl isocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, toluene-2,4,6-triisocyanate, and the like.
  • a preferred polyisocyanate is a polymeric MDI which is a mixture of polymethylene polyphenyl polyisocyanates of monomeric MDI.
  • the blowing agent used may be water or at least one physical blowing agent.
  • the physical blowing agent may be a mixture of one or more of a hydrocarbon, an alkane, a fluorocarbon, a dialkyl ether, and the like.
  • a more preferred blowing agent may be a CP (cyclopentane) blowing agent.
  • the catalyst used in the preparation of the polyurethane foam may include various amines or organotin catalysts. It preferably includes a tertiary amine catalyst such as triethylenediamine, dimethylbenzylamine, pentamethyldiethylenetriamine, dimethylethylamine, N-alkyldimethylamine compound and the like.
  • a tertiary amine catalyst such as triethylenediamine, dimethylbenzylamine, pentamethyldiethylenetriamine, dimethylethylamine, N-alkyldimethylamine compound and the like.
  • the surfactant used may be selected from the alkali metal and amine salts of fatty acids, castor oil, ricinoleic acid, siloxane-oxyalkylene polymers or copolymers, oxyethylated alkylphenols, peanut oil , paraffin, fatty alcohol, etc. Organosiloxanes are preferred.
  • the preparation method of the amino-based polyether polyol provided by the invention has no high-temperature melting step, can greatly save production time, improve production efficiency and reduce cost. Compared with the traditional high-temperature melting of o-phenylenediamine to produce amine-based polyether polyols, it can save about 5 hours of production time and increase production efficiency by nearly one-fifth.
  • the present invention can carry out an autocatalytic reaction (initial reaction) at a relatively low temperature, and the temperature can be controlled even below 95 ° C, which can avoid many problems caused by a high initial reaction temperature and can reduce side reactions. Since the initial reaction is an autocatalytic reaction and can be carried out at a relatively low temperature, many disadvantages caused by high-temperature melting can be avoided, thereby obtaining a high-performance product having not only a lower K value but also a higher compressive strength. And also has superior release properties. At the same time, the obtained product has a lighter shade, a regular structure and a high viscosity.
  • the polyurethane-based polyether polyol produced by the process of the invention has a rigid polyurethane foam which is not inferior in overall performance to the foam of the conventional o-toluenediamine polyether, even in certain properties. It is also stronger than previous products.
  • the polyether polyol prepared by the process of the invention can completely replace the original o-toluenediamine polyether, and can even give the product a better K value, compressive strength and mold release performance.
  • the polyurethane foam prepared by the invention can be used for producing thermal insulation layers of refrigerators, refrigerators, refrigerated containers, water heaters and the like.
  • GB/T 12008.3-2009 is used to determine the hydroxyl value of polyether polyols
  • GB/T10008.7-2010 is used to determine the viscosity of polyether polyols
  • GB/T9724-2007 is used to determine the pH of polyether polyols
  • GB/T12008.4-2009 is used to determine the K + of polyether polyols
  • GB/T22313-2008 is used to determine the moisture of polyether polyols.
  • GB/T 8813-2008 is used to test the strength of foam.
  • Example 1 is a comparative example in which a polyether polyol was prepared using o-phenylenediamine, and o-phenylenediamine was melted by a high-temperature melting method.
  • O-phenylenediamine (570 g, 5 mol) was added to the reaction vessel, and the test pressure was replaced by nitrogen.
  • the temperature of the kettle was set to 110 ° C, and the stirring was heated for 1 h (this period of time was found to be more than 6 hours to complete the melting).
  • the olefin oxide (specifically propylene oxide) was metered in at a flow rate of 800 g/h until a total of 1015 g (17.5 mol) of alkylene oxide was added to the reaction vessel. Then continue the reaction for 2 h. Then add 20g of potassium hydroxide aqueous solution (concentration is 50wt%). The water was removed by vacuum at 115 ° C for 2 h.
  • the residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1189 g (20.5 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h. At this time, 35 g of an aqueous phosphoric acid solution having a mass concentration of 50% was added to remove K ions, thereby obtaining a final product polyol.
  • the resulting polyol had an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.65 per molecule, a secondary amine group content of 0.27, a primary amine group content of less than 0.04, and a viscosity of 18416 cps at 25 °C.
  • Example 2 is an example of the preparation of an amine polyether polyol using the process of the present invention.
  • the autocatalytic reaction was carried out for 1 h, and then the temperature was raised to 105 ° C and the aging reaction was carried out for 1 h. Then, 20 g (concentration: 50% by weight) aqueous potassium hydroxide solution was added. The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1189 g (20.5 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h.
  • the resulting amino polyether polyol has an equivalent weight of 89 per active hydrogen atom, a hydroxyl group content of 3.84 per molecule, a secondary amine group content of 0.108, a primary amine group content of less than 0.003, and a viscosity at 25 ° C. 34553cps.
  • Example 3 is an example of the preparation of an amino polyether polyol using the process of the present invention.
  • the autocatalytic reaction was carried out for 1 h, and then the temperature was raised to 105 ° C and the aging reaction was carried out for 1 h. Then, 20 g (concentration: 50% by weight) aqueous potassium hydroxide solution was added. The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1189 g (20.5 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h.
  • the resulting amino polyether polyol has an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.87 per molecule, a secondary amine group content of 0.106, a primary amine group content of less than 0.002, and a viscosity at 25 ° C. 35822cps.
  • Example 4 is an example of the preparation of an amino polyether polyol using the process of the present invention.
  • the autocatalytic reaction was carried out for 1 h, and then the temperature was raised to 105 ° C and the aging reaction was carried out for 1 h. Then, 20 g (concentration: 50% by weight) aqueous potassium hydroxide solution was added. The water was removed by vacuum at 115 ° C for 2 h. The residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1,102 g (19 mol) of alkylene oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h.
  • the resulting amino polyether polyol has an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.85 per molecule, a secondary amine group content of 0.107, a primary amino group content of less than 0.003, and a viscosity at 25 ° C. 37462cps.
  • Example 5 is a comparative example, using o-toluenediamine production commonly used in the prior art. Polyol, in order to make a better comparison with Example 2, solvent water was introduced in this Example 5, and in the prior art, no solvent was often added. This embodiment specifically follows the steps as follows:
  • the residual olefin oxide was metered in at a flow rate of 600 g/h until an additional 1328 g (22.9 mol) of olefin oxide was added. After the reaction was continued for 1 h, the temperature was raised to 120 ° C and further reacted for 1 h. At this time, 35 g of a 50 wt% aqueous phosphoric acid solution was added to remove K ions, and the final product polyol was obtained by treatment.
  • the resulting polyol had an equivalent weight of 90 relative to each active hydrogen atom, a hydroxyl group content of 3.65 per molecule, a secondary amine group content of 0.088, a primary amine group content of less than 0.002, and a viscosity at 25 ° C of 25633 cps.
  • Example 1 Comparing Example 1 with Example 2, in Example 1, the o-phenylenediamine was melted at a high temperature without solvent addition, and it was found that the initial reaction could not be stirred during the preparation, and the obtained product was darker than that of Example 2. And the viscosity is far below the requirement, much lower than the product of Example 2. It was also found in the amplification experiment that the melting time of o-phenylenediamine in Example 1 needs to be more than 6 hours; and in the case of the amplification experiment of Example 2, there is no case where the dissolution time is prolonged excessively (when the temperature is raised to 90 ° C) It takes only 1 hour to completely dissolve).
  • Example 5 Comparing Example 5 with Example 2, the o-toluenediamine of Example 5 was used in the prior art to prepare a polyether polyol, usually without solvent (including water).
  • water was introduced therein, and it was found that the performance of the o-toluenediamine polyether polyol prepared by the prior art anhydrous process was significantly reduced, and the viscosity was much lower than that of the existing anhydrous process. Due to the introduction of water, the side reaction is increased.
  • Example 2 of the present invention although water was introduced as a solvent, the properties of the product were superior, and the viscosity was comparable to that of the conventional polyether polyol prepared by o-toluenediamine.
  • Examples 6-12 are examples of the preparation of rigid polyurethane foams. Adopt the following table 1 The formulation produced the rigid polyurethane foam of Examples 6-12, wherein the formulations of the examples also contained a polyisocyanate (not shown in Table 1), and the polyisocyanate was used in an amount of 1.2 times the polyol equivalent.
  • the rigid polyurethane foams of Examples 6-12 were prepared by the following method: Mixture of Table 1 and polyisocyanate (temperature control 21 ° C), using a high pressure machine injection molding machine (Krauss Maffei RSC 16/16) at 180-220 m/ The rate of s is processed, and then injected into a mold of constant temperature (35 ° C) to carry out a reaction, which is expanded and solidified to form a rigid polyurethane foam.
  • Example 6 the o-toluenediamine polyether polyol used in Example 6 was obtained by using substantially the same procedure as in Example 5, and the preparation process was different only in that no water was added.
  • the formulations of Examples 6-12 are shown in Table 1. The temperature of each component before mixing was controlled at 21 °C.
  • the oleyl ether is: a fatty acid ester-containing polyol, and the NJ-4110D produced by Jurong Ningwu Co., Ltd. is specifically used in the examples.
  • the sucrose-initiated polyol is: sucrose and a small amount of water-initiated polyol, and the specific example used is NJ-8238 produced by Jurong Ningwu Company.
  • MDA-100 initiated polyol made of 4'4-diaminodiphenylmethane as a starter by addition of propylene oxide, hydroxyl value, 360 mgKOH/g.
  • the specific preparation process can be carried out by referring to the method for preparing the polyether polyol in Example 1, except that the o-phenylenediamine in Example 1 is replaced with 4'4-diaminodiphenylmethane.
  • Mixed catalyst a mixture of dibutyltin dilaurate, triethylenediamine, N,N-dimethylcyclohexylamine in a mass ratio of 1:1.2:1.2.
  • Polyisocyanate PM-200, produced by Wanhua Chemical.
  • Foaming agent CP cyclopentane, melon cyclopentane chemical production.
  • the foams prepared in Examples 6-12 were measured for cream time, gel time, free rise density, compressive strength, thermal conductivity, and demolding for 5 minutes. The test results are shown in Table 2.
  • Examples 8, 9, and 10 had better compressive strength, demolding expansion, approximate thermal conductivity, and free rise density than those of Example 6 and Example 7.
  • Example 11 had much worse compressive strength, thermal conductivity, and demolding expansion than Example 6.
  • Example 12 has superior compressive strength and thermal conductivity than Example 6 and Examples 8, 9, and 10.

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

本发明提供一种胺基聚醚多元醇及其制备方法和应用。本发明提供的胺基聚醚多元醇的制备方法，包括如下步骤：将胺的水溶液与一部分氧化烯烃进行自催化反应，之后加入催化剂，加入剩余的氧化烯烃与胺进行环氧化反应；所述胺中含有90％(质量)以上的苯二胺。本发明提供的胺基聚醚多元醇的制备方法，采用苯二胺的水溶液，可避免高温熔融步骤，在生产上可节省生产时间，提升生产效率，且起始反应可控在相对较低的温度进行，可获得高性能产品，具有低K值、高强度和优越的脱模性能。

Description

胺基聚醚多元醇及其制备方法和应用 技术领域
本发明涉及一种胺基聚醚多元醇及其制备方法，还涉及利用该胺基聚醚多元醇制备聚氨酯泡沫体的方法。
背景技术
众所周知，聚醚多元醇被广泛用于制备聚氨酯硬质泡沫材料，可作为绝热材料用于冰箱、冰柜、冷库等产品中。
目前常用的聚醚多元醇为邻甲苯二胺聚醚多元醇，由于其原材料邻甲苯二胺的价格近年来一路上涨，导致成本过高。因此，研发其替代品势在必行。而苯二胺特别是邻苯二胺因其结构和性能与邻甲苯二胺接近，有望开发为一种替代品。
目前所知的邻苯二胺基聚醚多元醇的制备工艺几乎都是将邻苯二胺高温熔融(熔点103℃)后加成氧化烯烃来制备。这种方法由于熔融温度过高，导致无法启动搅拌，初期熔融邻苯二胺的时间多达几个小时至十几个小时，生产效率低下，成本过高。另外，由于需高温熔融，导致搅拌无法开启，进而会造成原料局部温度过高，发生碳化、分解等副反应，最后也会导致最终产品色度较深、品质较差。同时在高温状态下，邻苯二胺会发生严重的升华现象，部分邻苯二胺升华后附着于反应釜壁上，无法参与反应，不仅造成原料损失而且影响最终产品指标和品质。此外因邻苯二胺附着于釜壁上还会对反应釜的清洗造成困难，影响下一釜产品的生产。在后续聚氨酯泡沫的应用中，也会因为制备聚醚多元醇时采用了高温起始反应而造成其存在结构不规整、低粘度等缺陷，从而导致最终聚氨酯产品的各项指标特别是脱模、K值和压缩强度不如邻甲苯二胺聚醚制备的聚氨酯产品。
CN200980108998.4公开了一种使用邻苯二胺作为引发剂合成聚醚多元醇的方法，该方法需在高温下熔融邻苯二胺，起始反应温度高，造成无法开启搅拌，存在较多副反应，且容易造成原料损失，得到的 聚醚多元醇用于现有聚氨酯泡沫体系性能上不如邻甲苯二胺为引发剂制备的聚醚多元醇。
另外，在现有的涉及多元胺制备聚醚多元醇的合成方法中，极少有用到溶剂的，且也从未有用水作为溶剂的。因为一般情况下，水的加入会参与环氧烯烃的反应，生成小分子醇，严重影响产品品质。
发明内容
本发明为弥补现有技术中存在的不足，提供一种新颖的胺基聚醚多元醇的制备方法，可避免高温熔融步骤，提高生产效率，降低成本，并获得高品质的产品。
本发明为达到其目的，采用的技术方案如下：
本发明第一方面提供一种胺基聚醚多元醇的制备方法，将胺的水溶液与一部分氧化烯烃先进行自催化反应，之后加入催化剂，加入剩余的氧化烯烃与胺进行环氧化反应；所述胺中含有90％(质量)以上的苯二胺。本发明在反应前期无需高温熔融。
本发明优选的，所述苯二胺为邻苯二胺、间苯二胺、对苯二胺中的至少一种，更优选为邻苯二胺。
本发明在制备胺基聚醚多元醇时，用水作为初期溶剂溶解胺，所述胺优选为含有90％(质量)以上的邻苯二胺和10％(质量)以下的其他胺类化合物，所述其他胺类化合物可以包括间苯二胺、对苯二胺等等。在更优方案中，所述胺为高纯度(质量比大于99％)的邻苯二胺。
本发明的优选方案中，在自催化反应阶段，自催化反应可在130℃以下进行；更优选的，本发明的自催化反应可在更低的温度下进行，优选在105℃以下进行；进一步优选的，本发明的自催化反应还可在更低的温度进行，例如95℃以下、或90℃以下、或70-95℃进行。本发明采用胺的水溶液和氧化烯烃进行自催化反应，起始反应可控制在在相对低温下进行(例如105℃以下、90℃以下，或者可优选为70-95℃；更优选方案中，胺更优选采用邻苯二胺。在进一步的优选方案中，自催化反应若在低于100℃的温度下进行，在自催化反应之 后，且在加入催化剂之前，还可将反应温度升高至100℃以上进行老化反应，优选100-115℃，老化反应的时长优选在0.5-1h，但是，并非必须进行该老化反应。
本发明在反应初期，为苯二胺的自催化反应，水不参与反应。在更优方案中在所述催化剂加入前进行脱水操作，或在催化剂加入后剩余的氧化烯烃加入前进行脱水操作，从而避免水参与后续反应，减少副反应的发生，使得水对最终产品的品质不产生影响。本发明在起始反应阶段，起始剂为胺的水溶液，起始反应温度可以在相对低温下进行，减少了原料的升华，避免原料损失，从而有利于得到结构规整和高粘的产品，进而可以提高后续制备的硬质聚氨酯泡沫体的性能。
本发明中的优选实施方案中，所述胺与剩余的氧化烯烃在100℃-170℃进行环氧化反应，更优选为在110-130℃进行环氧化反应；在部分优选实施方式中，反应压力可以控制在0.1-10bar。
本发明优选方案中，催化剂加入前，先加入的一部分氧化烯烃与胺的摩尔比为1-4：1，优选为3-3.8：1。
本发明优选的，所述胺基聚醚多元醇相对于每一活性氢原子的当量为50-200，优选为80-125。反应体系中，胺和氧化烯烃的用量比例根据该当量就可确定。
本发明优选的，所述氧化烯烃为环氧丙烷、环氧乙烷中的一种或两种的混合物，更优选为环氧丙烷。
本发明中所述催化剂可以为强碱或胺类催化剂，催化剂的用量优选为聚醚多元醇产物重量的0.2-0.4％。若使用强碱作为催化剂，在反应完成后，优选除去该催化剂，除去方法为本领域常规手段，不再赘述；例如可以通过加入适量磷酸、脱水过滤除去该催化剂。而胺类催化剂则可保留或视情况除去。其中，所述的强碱可以是碱金属氢氧化物，例如氢氧化钠、氢氧化钾、氢氧化铯等。所述的胺类催化剂，例如可以是甲基咪唑、N,N-二甲基环己胺、三甲胺等。
现有的一般工艺制成的邻苯二胺和氧化烯烃的加合物，因一部分胺氢在典型的烷氧化条件下不能被完全氧化，这导致形成具有平均羟基、少量仲胺基和伯胺基的产物。因此每个分子平均具有3-4个羟基， 每个分子具有0-1个仲氨基，每个分子具有0-0.1个伯氨基。而本发明可以保证初始反应(或起始反应)在较低温度下进行，可以有效减少产物中仲胺基和伯胺基的量。采用本发明的方法制备的加合物的每个分子平均具有3.5-4个羟基，0-0.5个仲氨基，0-0.05个伯氨基。更有可能得到的加合物，每个分子平均具有3.8-4个羟基，0-0.2个仲氨基，0-0.01个伯氨基。更有可能得到的加合物，每个分子平均具有3.9-4个羟基，0-0.1个仲氨基，0-0.001个伯氨基。
本发明第二方面提供一种采用上文所述的制备方法制得的胺基聚醚多元醇。
本发明制备的胺基聚醚多元醇在25℃下的粘度，可以在5000-100000cps，优选在20000-50000cps，更优选在30000-40000cps。
本发明第三方面提供一种用于制备聚氨酯泡沫体的多元醇组合物，所述多元醇组合物中含有10％(质量)以上的如上文所述的胺基聚醚多元醇，更优选为含有30-60％(质量)的如上文所述的胺基聚醚多元醇。当然，所述多元醇组合物中也可以只含有上文所述的胺基聚醚多元醇。
作为一种优选方案，所述多元醇组合物中还含有聚酯多元醇、其他聚醚多元醇中的一种或多种。在部分方案中，聚酯多元醇可以作为额外的多元醇使用。所述的其他聚醚多元醇，可以含有以如下物质为引发剂(或起始剂)的聚醚多元醇，引发剂例如可以是亚烷基二醇(如乙二醇、丙二醇、1，4-丁二醇等)，二醇醚(如二甘醇、三甘醇等)，甘油，三羟甲基丙烷，季戊四醇，山梨醇，蔗糖等类似化合物；引发剂还可以是含有伯/仲氨基的化合物，如乙二胺，二乙醇胺，邻甲苯二胺等类似化合物。较为优选的，所述的其他聚醚多元醇包括以蔗糖为引发剂(或称为起始剂)的聚醚多元醇，用量优选为多元醇组合物的15-40％(质量)，更优选为20-40％(质量)，进一步更优选为25-35％(质量)。
所述其他聚醚多元醇也可以包括油醚、和以MDA-100为起始剂的聚醚多元醇中的一种或多种。其中油醚即含脂肪酸酯的多元醇，引发剂优选为蔗糖、二甘醇和各类脂肪酸酯，通过加合环氧丙烷或环氧乙 烷或两者的混合物而成。其中的脂肪酸酯可以包括各类动植物脂肪，和一些化工合成脂肪酸酯，例如：棕榈油，蓖麻油，大豆油，亚麻油，提纯后的地沟油等。油醚的用量优选占多元醇组合物的5-40％(质量)，更优选5-30％(质量)，进一步优选10-20％(质量)，更进一步优选10-15％(质量)。以MDA-100起始的聚醚多元醇为4,4’-二氨基二苯基甲烷与环氧丙烷/环氧乙烷或两者的混合物的加合物，用量优选为多元醇组合物的0-30％(质量)，更优选为10-30％(质量)，更进一步优选为15-25％(质量)。
进一步优选的，所述其他聚醚多元醇为油醚、以蔗糖为起始剂的聚醚多元醇、以MDA-100为起始剂的聚醚多元醇中的一种或多种的混合。
更为优选的，所述多元醇组合物包括如下质量百分比的各组分：上文所述的胺基聚醚多元醇30-60％、以蔗糖为起始剂的聚醚多元醇15-40％、以MDA-100为起始剂的聚醚多元醇0-30％(更优选为10-30％)、油醚5-40％。采用优选组合，可有效控制成本，并获得较佳的产品粘度，制得的产品性能也很好。
本发明第四方面提供一种制备聚氨酯泡沫体的方法，包括如下步骤：
1)形成含有如下组分的混合物：如前文所述的多元醇组合物、至少一种发泡剂、至少一种多异氰酸酯、至少一种催化剂、至少一种表面活性剂；
2)将混合物置于使混合物反应膨胀固化形成硬质聚氨酯泡沫体的条件下。制备硬质聚氨酯泡沫体的具体工艺操作为本领域常规技术手段，对此不作特别限定，其常规操作可参考如下方式进行：准备一个恒温的具有所需尺寸和形状的模具，该模具具有一个或多个物料注入口，且通常在模具上有一个或多个出气孔，然后将上述混合物注入该模具，混合物在模具空腔内反应膨胀，形成聚氨酯泡沫体。
本发明优选方案中，多异氰酸酯的用量为基于多元醇组合物当量的1.0-1.3，优选为1.1-1.2；基于100重量份的多元醇组合物，发泡剂的用量为10-20份，优选为13-17份；基于100重量份的多元醇 组合物，催化剂的用量为1-4份，优选为1.5-3份；基于100重量份的多元醇组合物，表面活性剂的用量为0.01-6份，优选为2-4份。
所述多异氰酸酯，可以包括芳族、脂族和脂环族多异氰酸酯中的至少一种。优选为芳族多异氰酸酯，如2,4-和/或2,6-甲苯二异氰酸酯、二苯甲烷二异氰酸酯的各种异构体，六氢甲苯二异氰酸酯，甲氧基苯基-2,4-二异氰酸酯，氢化MDI，多亚甲基多苯基异氰酸酯，3,3’-二甲氧基-4,4’-联苯二异氰酸酯，甲苯-2,4,6-三异氰酸酯等。优选的多异氰酸酯是聚合MDI，它是单体MDI的多亚甲基多苯基多异氰酸酯的混合物。
所使用的发泡剂可以是水或至少一种物理发泡剂。物理发泡剂可以是烃、烷烃、氟烃、二烷基醚等中的一种或多种的混合物。较为优选的发泡剂可以选用CP(环戊烷)发泡剂。
制备聚氨酯泡沫体所使用的催化剂可以包括各种胺类、或有机锡类催化剂。优选包括叔胺催化剂，如三亚乙基二胺，二甲基苄胺，五甲基二亚乙基三胺，二甲基乙基胺，N-烷基二甲基胺化合物等等。
所使用的表面活性剂可以选自脂肪酸的碱金属盐和胺盐，蓖麻油，蓖麻油酸，硅氧烷-氧基亚烷基聚合物或共聚物，氧乙基化烷基酚类，花生油，石蜡，脂肪醇等。优选有机硅氧烷。
本发明提供的技术方案具有如下有益效果：
本发明提供的胺基聚醚多元醇的制备方法，没有高温熔融步骤，可大幅节省生产时间，提高生产效率，降低成本。和传统的采用邻苯二胺高温熔融生产胺基聚醚多元醇相比，在生产上大约可节省5h左右的生产时间，提升近1/5的生产效率。
本发明可以在较低的温度下进行自催化反应(起始反应)，该温度甚至可以控制在95℃以下，可以避免因起始反应温度高所带来的诸多问题，可减少副反应。由于起始反应为自催化反应，且可在相对低的温度下进行，可避免高温熔融所带来的诸多弊端，从而获得高性能的产品，不仅具有较低的K值，较高的压缩强度，而且还有优越的脱模性能。同时，所制得的产品更具有较浅的色度，且结构规整，粘度高。
采用本发明的工艺生产的胺基聚醚多元醇，制备出的硬质聚氨酯泡沫体在总体性能上并不逊色于传统的邻甲苯二胺聚醚所制得的泡沫体，甚至在某些性能上还强于此前的产品。本发明工艺制备的聚醚多元醇可完美替代原有邻甲苯二胺聚醚，甚至还可赋予产品更优的K值、压缩强度和脱模性能。本发明所制备的聚氨酯泡沫体可用于生产冰箱、冷柜、冷藏集装箱、热水器等的保温隔热层。
具体实施方式
为了更好的理解本发明的技术方案，下面结合实施例进一步阐述本发明的内容，但本发明的内容并不仅仅局限于以下实施例。
以下实施例中所使用的或可能使用的测试方法介绍如下：
1、用于多元醇性质的测试方法
GB/T 12008.3-2009用于测定聚醚多元醇的羟值；
GB/T10008.7-2010用于测定聚醚多元醇的粘度；
GB/T9724-2007用于测定聚醚多元醇的pH；
GB/T12008.4-2009用于测定聚醚多元醇的K+；
GB/T22313-2008用于测定聚醚多元醇的水分。
2、用于泡沫体性质的测试方法
QB/JH用于测试泡沫体的脱模性能；
GB/T 10295－2009用于测试泡沫体的K因子；
GB/T 8813-2008用于测试泡沫体的强度。
实施例1
实施例1为采用邻苯二胺制备聚醚多元醇的对比实施例，采用高温熔融法熔化邻苯二胺。按照如下步骤进行：
将邻苯二胺(570g，5mol)加入到反应釜中，氮气置换试压，设置釜温110℃，开启搅拌加热1h(该时长在放大实验中，发现要达到6小时以上才能完成熔融)。按流量800g/h计量加入氧化烯烃(具体采用的是环氧丙烷)，直到总计加入1015g(17.5mol)氧化烯烃到反应釜中。然后继续反应2h。之后添加20g氢氧化钾水溶液(浓度为 50wt％)。在115℃下脱真空除水2h。按流量600g/h计量加入剩余氧化烯烃，直到额外加入1189g(20.5mol)氧化烯烃。继续反应1h后升温到120℃再反应1h。此时添加35g的质量浓度为50％的磷酸水溶液除去K离子，得到最终产物多元醇。所得多元醇相对于每一活性氢原子的当量为90，每个分子的羟基含量为3.65，仲胺基含量为0.27，伯胺基含量为小于0.04，在25℃下的粘度为18416cps。
实施例2
实施例2为采用本发明工艺制备胺基聚醚多元醇的实施例。按照如下步骤进行：
将水(135g，7.5mol)和邻苯二胺(570g，5mol)加入到反应釜中，氮气置换试压，开启搅拌加热到90℃，当温度升到90℃时即可获得邻苯二胺的水溶液(而在放大实验中，也只需在温度升到90℃后继续搅拌1h就能完全溶解)。按流量800g/h计量加入氧化烯烃(本实施例具体采用的是环氧丙烷)，直到总计加入1015g(17.5mol)氧化烯烃到反应釜中。自催化反应1h，之后升温到105℃再进行老化反应1h。之后添加20g(浓度为50wt％)氢氧化钾水溶液。在115℃下脱真空除水2h。按流量600g/h计量加入剩余氧化烯烃，直到额外加入1189g(20.5mol)氧化烯烃。继续反应1h后升温到120℃再反应1h。此时添加35g的浓度50wt％的磷酸水溶液除去K离子，处理得到最终产物胺基聚醚多元醇。所得胺基聚醚多元醇相对于每一活性氢原子的当量为89，每个分子的羟基含量为3.84，仲胺基含量为0.108，伯胺基含量为小于0.003，在25℃下的粘度为34553cps。
实施例3
实施例3为采用本发明工艺制备胺基聚醚多元醇的实施例。按照如下步骤进行：
将水(135g，7.5mol)和邻苯二胺(570g，5mol)加入到反应釜中，氮气置换试压，开启搅拌加热到85℃，当温度升到85℃时即可获得邻苯二胺的水溶液(而在放大实验中，也只需在温度升到85℃后 继续搅拌1.5h就能完全溶解)。按流量700g/h计量加入氧化烯烃(本实施例具体采用的是环氧丙烷)，直到总计加入1015g(17.5mol)氧化烯烃到反应釜中。自催化反应1h，之后升温到105℃再进行老化反应1h。之后添加20g(浓度为50wt％)氢氧化钾水溶液。在115℃下脱真空除水2h。按流量600g/h计量加入剩余氧化烯烃，直到额外加入1189g(20.5mol)氧化烯烃。继续反应1h后升温到120℃再反应1h。此时添加35g的浓度50wt％的磷酸水溶液除去K离子，处理得到最终产物胺基聚醚多元醇。所得胺基聚醚多元醇相对于每一活性氢原子的当量为90，每个分子的羟基含量为3.87，仲胺基含量为0.106，伯胺基含量为小于0.002，在25℃下的粘度为35822cps。
实施例4
实施例4为采用本发明工艺制备胺基聚醚多元醇的实施例。按照如下步骤进行：
将水(135g，7.5mol)和邻苯二胺(570g，5mol)加入到反应釜中，氮气置换试压，开启搅拌加热到90℃，当温度升到90℃时即可获得邻苯二胺的水溶液(而在放大实验中，也只需在温度升到90℃后继续搅拌1h就能完全溶解)。按流量800g/h计量加入氧化烯烃(本实施例具体采用的是环氧丙烷)，直到总计加入1102g(19mol)氧化烯烃到反应釜中。自催化反应1h，之后升温到105℃再进行老化反应1h。之后添加20g(浓度为50wt％)氢氧化钾水溶液。在115℃下脱真空除水2h。按流量600g/h计量加入剩余氧化烯烃，直到额外加入1102g(19mol)氧化烯烃。继续反应1h后升温到120℃再反应1h。此时添加35g的浓度50wt％的磷酸水溶液除去K离子，处理得到最终产物胺基聚醚多元醇。所得胺基聚醚多元醇相对于每一活性氢原子的当量为90，每个分子的羟基含量为3.85，仲胺基含量为0.107，伯胺基含量为小于0.003，在25℃下的粘度为37462cps。
实施例5
实施例5为对比实施例，采用现有技术中常用的邻甲苯二胺生产 多元醇，为了和实施例2进行更好的对比，该实施例5中引入了溶剂水，而在现有技术中往往不加入溶剂。本实施例具体按照如下步骤操作：
将水(135g，7.5mol)和邻甲苯二胺(630g，5.16mol)加入到反应釜中，氮气置换试压，开启搅拌加热到90℃。按流量800g/h计量加入氧化烯烃，直到总计加入930g(16mol)氧化烯烃到反应釜中。反应1h后升温到105℃再反应1h。之后添加20g(浓度50wt％)氢氧化钾水溶液。在115℃下脱真空除水2h。按流量600g/h计量加入剩余氧化烯烃，直到额外加入1328g(22.9mol)氧化烯烃。继续反应1h后升温到120℃再反应1h。此时添加35g的浓度为50wt％的磷酸水溶液除去K离子，处理得到最终产物多元醇。所得多元醇相对于每一活性氢原子的当量为90，每个分子的羟基含量为3.65，仲胺基含量为0.088，伯胺基含量为小于0.002，在25℃下的粘度为25633cps。
比较实施例1和实施例2，实施例1中不加溶剂高温熔融邻苯二胺，在制备过程中发现起始反应无法开启搅拌，制得的产品相比于实施例2色度也较深，且粘度也远远达不到要求，远低于实施例2的产品。在放大实验中还发现，实施例1中邻苯二胺的熔融时长需达到6小时以上；而对实施例2进行放大实验，则并未出现溶解时间延长过多的情形(在升温至90℃后只需1h即可完全溶解)。
比较实施例5和实施例2，实施例5中的邻甲苯二胺在现有技术中用于制备聚醚多元醇时，通常不加溶剂(包括水)。而实施例5中将水引入其中，发现相比于现有无水工艺制备的邻甲苯二胺聚醚多元醇，其性能明显下降，粘度远低于现有无水工艺制备的产品，这是由于水的引入造成副反应增多而导致的。但是，本发明的实施例2中，虽然引入了水作为溶剂，但是其产品性能却更胜一筹，粘度和传统的邻甲苯二胺制备的聚醚多元醇相当。
实施例6-12
实施例6-12为制备硬质聚氨酯泡沫体的实施例。采用如下表1 的配方生产实施例6-12的硬质聚氨酯泡沫体，其中，各实施例的配方中还含有多异氰酸酯(在表1中未示出)，多异氰酸酯的用量为基于多元醇当量的1.2倍。实施例6-12的硬质聚氨酯泡沫体通过如下方法制备：将表1中的混合物和多异氰酸酯(控温21℃)，用高压机注塑机(Krauss Maffei RSC 16/16)以180-220m/s的速率进行加工，然后注入恒温(35℃)的模具中进行反应，膨胀固化形成硬质聚氨酯泡沫体。
其中，实施例6中所用的邻甲苯二胺聚醚多元醇，是通过采用和实施例5基本相同的工艺制得，其制备工艺的不同仅在于没有加入水。实施例6-12的配方见表1所示，各组分混合前温度均控制在21℃。
表1
Figure PCTCN2017103950-appb-000001
Figure PCTCN2017103950-appb-000002
实施例6-12所用的原料说明如下：
油醚为：含脂肪酸酯的多元醇，实施例中具体采用的是句容宁武公司生产的NJ-4110D。
蔗糖引发的多元醇为：蔗糖和少量水起始的多元醇，实施例中所用具体为句容宁武公司生产的NJ-8238。
MDA-100引发的多元醇：为以4‘4-二氨基二苯基甲烷作为起始剂，通过加合环氧丙烷制成，羟值，360mgKOH/g。其具体制备工艺可参照实施例1中制备聚醚多元醇的方法进行，不同仅在于将实施例1中的邻苯二胺替换为4‘4-二氨基二苯基甲烷。
表面活性剂：L6863硅油，迈图公司生产。
混合催化剂：二丁基锡二月桂酸酯、三乙烯二胺、N,N-二甲基环己胺按质量比例1：1.2：1.2的混合物。
多异氰酸酯：PM-200，万华化学生产。
发泡剂CP：环戊烷，美龙环戊烷化工生产。
对实施例6-12制得的泡沫体测量乳白时间、凝胶时间、自由起发密度、压缩强度、导热系数、5min脱模。检测结果参见表2。
表2
Figure PCTCN2017103950-appb-000003
Figure PCTCN2017103950-appb-000004
根据检测结果，实施例8、9、10具有比实施例6和实施例7更优的的压缩强度、脱模膨胀，近似的导热系数和自由起发密度。实施例11具有比实施例6差得多的压缩强度、导热系数和脱模膨胀。实施例12具有比实施例6和实施例8、9、10更优的压缩强度和导热系数。
本领域技术人员可以理解，在本说明书的教导之下，可对本发明做出一些修改或调整。这些修改或调整也应当在本发明权利要求所限定的范围之内。

Claims (18)

  1. 一种胺基聚醚多元醇的制备方法，其特征在于，将胺的水溶液与一部分氧化烯烃先进行自催化反应，之后加入催化剂，加入剩余的氧化烯烃与胺进行环氧化反应；
    所述胺中含有90％(质量)以上的苯二胺。
  2. 根据权利要求1所述的胺基聚醚多元醇的制备方法，其特征在于，所述苯二胺为邻苯二胺、间苯二胺、对苯二胺中的至少一种。
  3. 根据权利要求1或2所述的胺基聚醚多元醇的制备方法，其特征在于，所述胺中含有90％(质量)以上的邻苯二胺和10％(质量)以下的其他胺类化合物；优选的，所述胺为邻苯二胺。
  4. 根据权利要求1-3任一项所述的胺基聚醚多元醇的制备方法，其特征在于，所述自催化反应在130℃以下进行，优选在105℃以下进行，进一步优选在95℃以下进行；
  5. 根据权利要求4所述的胺基聚醚多元醇的制备方法，其特征在于，所述自催化反应在低于100℃的温度下进行，在自催化反应之后，且在加入催化剂之前，升温至100℃以上进行老化反应，优选升温至100-115℃进行老化反应。
  6. 根据权利要求1-5任一项所述的胺基聚醚多元醇的制备方法，其特征在于，所述剩余的氧化烯烃与胺在100℃-170℃进行环氧化反应，优选为在110-130℃进行环氧化反应。
  7. 根据权利要求1-6任一项所述的胺基聚醚多元醇的制备方法，其特征在于，在所述催化剂加入前进行脱水操作，或在催化剂加入后剩余的氧化烯烃加入前进行脱水操作。
  8. 根据权利要求1-7任一项所述的胺基聚醚多元醇的制备方法，其特征在于，先加入的一部分氧化烯烃与胺的摩尔比为1-4：1，优选为3-3.8：1。
  9. 根据权利要求1-8任一项所述的胺基聚醚多元醇的制备方法，其特征在于，所述胺基聚醚多元醇相对于每一活性氢原子的当量为50-200，优选为80-125。
  10. 根据权利要求1-9任一项所述的胺基聚醚多元醇的制备方法，其特征在于，所述氧化烯烃为环氧丙烷、环氧乙烷中的一种或两种的混合物。
  11. 根据权利要求1-10任一项所述的胺基聚醚多元醇的制备方法，其特征在于，所述催化剂为强碱或胺类催化剂；优选的，所述催化剂的用量为聚醚多元醇产物重量的0.2-0.4％。
  12. 根据权利要求1-11任一项所述的胺基聚醚多元醇的制备方法，其特征在于，所述制备方法制得的加合物的每个分子平均具有3.5-4个羟基，0-0.5个仲氨基，0-0.05个伯氨基。
  13. 一种采用权利要求1-12任一项所述的制备方法制得的胺基聚醚多元醇。
  14. 一种用于制备聚氨酯泡沫体的多元醇组合物，其特征在于，所述多元醇组合物中含有10％(质量)以上的如权利要求13所述的胺基聚醚多元醇。
  15. 根据权利要求14所述的用于制备聚氨酯泡沫体的多元醇组合物，其特征在于，所述多元醇组合物中还含有聚酯多元醇和其他聚醚多元醇中的一种或多种；
    优选的，所述其他聚醚多元醇为油醚、以蔗糖为起始剂的聚醚多元醇、以MDA-100为起始剂的聚醚多元醇中的一种或多种的混合。
  16. 根据权利要求15所述的用于制备聚氨酯泡沫体的多元醇组合物，其特征在于，所述多元醇组合物包括如下质量百分比的各组分：权利要求13所述的胺基聚醚多元醇30-60％、以蔗糖为起始剂的聚醚多元醇15-40％、以MDA-100为起始剂的聚醚多元醇0-30％、油醚5-40％；
    优选的，在多元醇组合物中，以MDA-100为起始剂的聚醚多元醇所占的质量百分比为10-30％。
  17. 一种制备聚氨酯泡沫体的方法，其特征在于，包括如下步骤：
    1)形成含有如下组分的混合物：如权利要求14-16任一项所述的多元醇组合物、至少一种发泡剂、至少一种多异氰酸酯、至少一种催化剂、至少一种表面活性剂；
    2)将混合物置于使混合物反应膨胀固化形成硬质聚氨酯泡沫体 的条件下。
  18. 根据权利要求17所述的制备聚氨酯泡沫体的方法，其特征在于，多异氰酸酯的用量为基于多元醇组合物当量的1.0-1.3；基于100重量份的多元醇组合物，发泡剂、催化剂、表面活性剂的用量依次分别为10-20份、1-4份、0.01-6份。
PCT/CN2017/103950 2017-09-15 2017-09-28 胺基聚醚多元醇及其制备方法和应用 WO2019051886A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710833985.XA CN107513157B (zh) 2017-09-15 2017-09-15 胺基聚醚多元醇及其制备方法和应用
CN201710833985.X 2017-09-15

Publications (1)

Publication Number Publication Date
WO2019051886A1 true WO2019051886A1 (zh) 2019-03-21

Family

ID=60725414

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/103950 WO2019051886A1 (zh) 2017-09-15 2017-09-28 胺基聚醚多元醇及其制备方法和应用

Country Status (2)

Country Link
CN (1) CN107513157B (zh)
WO (1) WO2019051886A1 (zh)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109485843B (zh) * 2018-09-11 2021-03-09 万华化学（宁波）容威聚氨酯有限公司 一种氨基聚醚多元醇及其制备方法、一种聚氨酯硬质泡沫及其制备方法
CN111019113B (zh) * 2019-12-05 2023-03-03 万华化学（宁波）容威聚氨酯有限公司 用于纯lba体系的氨基聚醚多元醇及其制备方法和使用其制备的聚氨酯硬质泡沫
CN112375198B (zh) * 2020-10-28 2022-09-06 山东一诺威聚氨酯股份有限公司 低气味高性能车门内饰板组合料及其制备方法
CN115246919B (zh) * 2021-11-26 2023-12-22 佳化化学科技发展（上海）有限公司 一种聚氨酯灌浆材料及其制备方法和应用
CN114874425B (zh) * 2022-05-13 2023-10-13 万华化学（宁波）有限公司 一种胺基聚醚多元醇及其制备方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701477A (en) * 1983-07-13 1987-10-20 Chardonol, Division Of Freeman Corporation Low viscosity aromatic polyols and methods for their preparation
US20020120026A1 (en) * 2000-12-20 2002-08-29 Schilling Steven L. Co-initiated polyols useful for the production of rigid polyurethane foams
CN101970534A (zh) * 2008-01-17 2011-02-09 陶氏环球技术公司 绝热的基于基异氰酸酯的泡沫体
CN102203158A (zh) * 2008-11-06 2011-09-28 旭有机材工业株式会社 聚氨酯泡沫体用发泡性组合物及聚氨酯泡沫体
US20130204047A1 (en) * 2010-03-13 2013-08-08 Bayer Intellectual Property Gmbh Method for producing polyther polyols
CN104311813A (zh) * 2014-10-11 2015-01-28 淄博德信联邦化学工业有限公司 抗氧化聚醚多元醇及其制备方法
CN106589344A (zh) * 2016-12-01 2017-04-26 浙江皇马科技股份有限公司 一种不饱和聚醚的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19521058A1 (de) * 1995-06-09 1996-12-12 Basf Ag Verfahren zur Herstellung von Aromaten enthaltenden Polyetherpolyolen
WO2006055396A1 (en) * 2004-11-17 2006-05-26 Dow Global Technologies, Inc. Acid blocked, amine based, autocatalytic polyols and polyurethane foams made therefrom
CN101054436A (zh) * 2006-04-11 2007-10-17 江阴友邦化工有限公司 具有催化活性的聚醚多元醇的制备方法
WO2012133812A1 (ja) * 2011-03-30 2012-10-04 旭硝子株式会社 ポリエーテルポリオールおよび軟質ポリウレタンフォームの製造方法、ならびにシート
EP2694564B1 (de) * 2011-04-07 2015-06-17 Basf Se Verfahren zur herstellung von pu-hartschaumstoffen
WO2015155098A1 (en) * 2014-04-09 2015-10-15 Basf Se Process for the continuous production of polyether polyols

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4701477A (en) * 1983-07-13 1987-10-20 Chardonol, Division Of Freeman Corporation Low viscosity aromatic polyols and methods for their preparation
US20020120026A1 (en) * 2000-12-20 2002-08-29 Schilling Steven L. Co-initiated polyols useful for the production of rigid polyurethane foams
CN101970534A (zh) * 2008-01-17 2011-02-09 陶氏环球技术公司 绝热的基于基异氰酸酯的泡沫体
CN102203158A (zh) * 2008-11-06 2011-09-28 旭有机材工业株式会社 聚氨酯泡沫体用发泡性组合物及聚氨酯泡沫体
US20130204047A1 (en) * 2010-03-13 2013-08-08 Bayer Intellectual Property Gmbh Method for producing polyther polyols
CN104311813A (zh) * 2014-10-11 2015-01-28 淄博德信联邦化学工业有限公司 抗氧化聚醚多元醇及其制备方法
CN106589344A (zh) * 2016-12-01 2017-04-26 浙江皇马科技股份有限公司 一种不饱和聚醚的制备方法

Also Published As

Publication number Publication date
CN107513157B (zh) 2021-02-02
CN107513157A (zh) 2017-12-26

Similar Documents

Publication Publication Date Title
WO2019051886A1 (zh) 胺基聚醚多元醇及其制备方法和应用
CN110885435B (zh) 高官能度聚醚多元醇的制备方法
CN109485843B (zh) 一种氨基聚醚多元醇及其制备方法、一种聚氨酯硬质泡沫及其制备方法
CN108047442B (zh) 一种硬质泡沫复合聚醚多元醇及其制备方法
CN113024794B (zh) 能够与异氰酸酯反应的组合物及其制备的聚氨酯材料
JP2001503804A (ja) アミン開始ポリエーテルポリオール、及びその製造方法
CN112062945B (zh) 一种高官能度聚醚多元醇及其制备方法
WO2009043301A1 (fr) Procédé de préparation de polyol polyéther et application du produit préparé
CN111320737B (zh) 聚氨酯原料组合物、聚氨酯硬泡的制备方法及其用途
CN111363134B (zh) H12mda聚醚酯多元醇、制备方法、应用和聚氨酯硬质泡沫
CN101970534A (zh) 绝热的基于基异氰酸酯的泡沫体
CN102040732A (zh) 聚醚多元醇交联剂的制备方法
KR20150128977A (ko) 단쇄 dmc-촉매화 출발물질로부터의 염기-촉매화 장쇄 활성 폴리에테르
CN109970962B (zh) 葡萄糖酸起始聚酯醚多元醇及其在聚氨酯硬泡中的应用
CN112920397B (zh) 聚醚多元醇及其制备方法
WO2024016743A1 (zh) 硬质聚氨酯泡沫、其制备方法及包含硬质聚氨酯泡沫的保温材料、冰箱或冰柜
CN114516954A (zh) 聚醚多元醇及聚氨酯泡沫
EP3880734B1 (en) Water processes for producing polyether polyols from solid polyhydroxyl compounds
JPH02199111A (ja) ポリウレタン製造用触媒組成物
CN114085371B (zh) 含有苯酰胺基的聚醚多元醇、聚氨酯泡沫体及其制备方法
JP3031695B2 (ja) ポリオキシアルキレンポリオール及びその利用
CN113817154B (zh) 一种聚醚多元醇及制备方法和由其制备的聚氨酯泡沫
CN115466382B (zh) 一种醇胺起始聚醚、聚氨酯开孔慢回弹海绵及制备方法
CN117304471A (zh) 一种硬泡聚醚多元醇的制备方法
CN117720714A (zh) 一种高官能度、低粘度聚醚多元醇的制备方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17925215

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17925215

Country of ref document: EP

Kind code of ref document: A1