CN108409956B - 3, 4-diamino furo polyether polyol and preparation method thereof, and polyurethane rigid foam prepared from polyether polyol and preparation method thereof - Google Patents
3, 4-diamino furo polyether polyol and preparation method thereof, and polyurethane rigid foam prepared from polyether polyol and preparation method thereof Download PDFInfo
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Abstract
The invention discloses 3, 4-diamino furoxan polyether polyol and a preparation method thereof, and polyurethane rigid foam prepared from the polyether polyol and a preparation method thereof. The 3, 4-diamino furoxan polyether polyol is prepared by taking 3, 4-diamino furoxan as an initial raw material and carrying out addition reaction on the initial raw material and alkylene oxide; the polyurethane rigid foam comprises the following raw materials in mass ratio of 100: 12-23: 130-160 of combined polyether, a foaming agent and polyisocyanate, wherein the combined polyether contains 3, 4-diamino furo polyether polyol, and the foaming agent contains HFC-134 a. The novel polyether monomer using 3, 4-diamino furazane as an initiator has good compatibility with HFC-134a, and the prepared polyurethane foam has good dimensional stability and heat insulation performance at low density.
Description
Technical Field
The invention belongs to the field of new materials, relates to polyether polyol and polyurethane rigid foam, and particularly relates to 3, 4-diamino furoxan polyether polyol and a preparation method thereof, low-density and low-conductivity 134a system polyurethane rigid foam prepared from the polyether polyol and a preparation method thereof.
Background
The HCFC-141b is the most used hydrochlorofluorocarbon foaming agent, China forbids to use the HCFC-141b in 2020, and the foaming agents which can replace the HCFC-141b and have no destructive effect on the ozone layer are cyclopentane, HFC-245fa, HFC-134a, HFC-365a, LBA and the like.
Among them, HFC-134a (1,1,1, 2-tetrafluoroethane) is a foaming agent which does not contain chlorine atoms, does not damage the ozone layer and has good safety performance. The most common foaming system in China is a CP system, and CP and 134a are used as mixed foaming agents, so that the defects of high heat conductivity coefficient and poor strength of the CP system can be overcome. The boiling point of HFC-134a is-26 ℃, and the emulsification can be rapidly initiated in the early stage, so that the foam pores are finer and finer, thereby reducing the thermal conductivity. In addition, HFC-134a has very high vapor pressure, can keep very good dimensional stability under the condition of low density, when used for the preparation of materials such as refrigerator heat preservation, can reduce the perfusion volume, thus achieve the purpose of reducing the cost. But also due to the low boiling point characteristic of HFC-134a, the volatilization escape is easy to occur in the early stage of the reaction, and the overall performance of the foam is greatly influenced after the HFC-134a is lost, so that the HFC-134a cannot be widely applied.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides 3, 4-diamino furo polyether polyol and low-density and low-conductivity HFC-134a system polyurethane rigid foam using the polyether polyol as a raw material. The novel polyether monomer using the 3, 4-diamino furoxan as the initiator has good compatibility with HFC-134a, can wrap the HFC-134a quickly, prevents the volatilization of the HFC-134a, and ensures the excellent performance of the foam. The invention effectively improves the strength and the applicability of the polyurethane rigid foam prepared by adopting the HFC-134a foaming agent by using the novel polyether and adjusting the formula.
Meanwhile, the invention also provides a preparation method of the polyether polyol and the polyurethane rigid foam.
The technical scheme of the invention is as follows:
a3, 4-diamino furoxan polyether polyol has a structure shown in formula I:
wherein: x is an integer of 4 to 10;
r is H, C1-C6 alkyl.
Furthermore, the hydroxyl value of the 3, 4-diamino furoxan polyether polyol is 340-420 mgKOH/g, and the functionality is 3.6-4.4.
A preparation method of 3, 4-diamino furoxan polyether polyol shown in formula I comprises the following steps of taking 3, 4-diamino furoxan as an initial raw material, and carrying out addition reaction on the initial raw material and alkylene oxide to obtain the 3, 4-diamino furoxan polyether polyol, wherein the reaction formula is as follows:
preferably, the molar ratio of the 3, 4-diamino furoxan to the oxyalkylene is 1: 4-8, and the most preferable molar ratio is 1: 6;
preferably, the alkylene oxide is added into the reaction system in two times;
preferably, the alkylene oxide is propylene oxide and/or ethylene oxide, more preferably propylene oxide or a mixture of propylene oxide and ethylene oxide, most preferably propylene oxide.
The preparation method of the 3, 4-diamino furoxan polyether polyol comprises the following steps:
1) mixing the 3, 4-diamino furoxan aqueous solution with partial olefin oxide, carrying out autocatalytic reaction for 1-4 h at the temperature of 60-80 ℃, and then heating to 80-120 ℃ for aging reaction for 1-4 h;
2) adding a potassium hydroxide aqueous solution into the system in the step 1), then carrying out vacuum dehydration for 2-6 h, adding the rest olefin oxide, continuing to react for 1-4 h, then heating to 100-140 ℃, and reacting for 1-4 h;
3) adding phosphoric acid aqueous solution into the system obtained in the step 2) to remove K ions, and obtaining the 3, 4-diamino furoxan polyether polyol.
Further, in the preparation method, the olefin oxide is added into the reaction system in two steps of step 1) and step 2), and the mass ratio of the olefin oxide in the step 1) to the olefin oxide in the step 2) is 1: 1-1.4, preferably 1: 1.15.
Further, in the above preparation method, the alkylene oxide in step 1) is added at a flow rate of 700 g/h; in the step 2), the alkylene oxide is added according to the flow rate of 500-700 g/h.
Further, in the above preparation method, in the step 2), the vacuum dehydration temperature is preferably 115 ℃; the temperature rise is preferably to 120 ℃.
Further, in the above preparation method, the concentration of the 3, 4-diamino furazane aqueous solution is 60 to 90 wt%, preferably 81 wt%; the concentration of the potassium hydroxide aqueous solution is 30-60 wt%, preferably 50 wt%; the concentration of the phosphoric acid aqueous solution is 30 to 70 wt%, preferably 50 wt%.
Further, in the preparation method, the molar ratio of the 3, 4-diamino furoxan to the potassium hydroxide and the phosphoric acid is 20-60: 1:1, and the aqueous solution is calculated by solute; preferably in a molar ratio of 30:1: 1.
The rigid polyurethane foam with low density and low conductivity of HFC-134a system is prepared from raw materials including combined polyether, a foaming agent and polyisocyanate, wherein the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 12-23: 130 to 160;
the foaming agent comprises HFC-134 a;
the combined polyether comprises a polyether composition, wherein the polyether composition comprises 3, 4-diamino furo polyether polyol.
Further, the foaming agent comprises the following components in parts by weight: 10-15 parts of CP foaming agent and 8-78 parts of HFC-134a 2.
Further, the composite polyether comprises the following components in parts by weight: 90-100 parts of polyether composition, 1.5-3 parts of surfactant, 2-4 parts of composite catalyst and 1-3 parts of water;
the polyether composition comprises, by weight, 10-45 parts of 3, 4-diamino furoxan polyether polyol, 20-55 parts of sucrose and glycerol polyether polyol, 10-30 parts of sorbitol polyether polyol and 10-25 parts of glycerol polyether polyol; preferably, the components in parts by weight are 20-35 parts of 3, 4-diamino furoxan polyether polyol, 30-50 parts of cane sugar and glycerol polyether polyol, 10-30 parts of sorbitol polyether polyol and 10-25 parts of glycerol polyether polyol;
preferably, the sucrose and glycerol polyether polyol is prepared by taking sucrose and glycerol as starting materials and carrying out addition reaction with propylene oxide, wherein the hydroxyl value is 380-440 mgKOH/g, and the functionality is 5.0-6.0.
Preferably, the sorbitol polyether polyol is prepared by taking sorbitol as an initial raw material and performing addition reaction with propylene oxide, and has a hydroxyl value of 400-460 mgKOH/g and a functionality of 5.7-6.4.
Preferably, the glycerol polyether polyol is prepared by taking glycerol as an initial raw material and carrying out addition reaction with propylene oxide, wherein the hydroxyl value is 180-240 mgKOH/g, and the functionality is 2.0-2.7.
Preferably, the surfactant is a silicone-based surfactant, more preferably a silicone surfactant, and most preferably at least one of silicone oil AK8805, silicone oil AK8830, silicone oil B8525, and silicone oil B8545.
Preferably, the composite catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst to the trimerization catalyst is preferably 1: 2-8: 1-4;
preferably, the foaming catalyst is one or a mixture of more of pentamethyldiethylenetriamine, tetramethylhexanediamine and bis-dimethylaminoethylether in any proportion;
preferably, the gel catalyst is one or a mixture of more than one of dimethylbenzylamine, dimethylcyclohexane and triethylene diamine in any proportion;
preferably, the trimerization catalyst is hexahydrotriazine and/or potassium acetate.
Further, the polyisocyanate is polymeric MDI (polymethylene polyphenyl polyisocyanate), preferably polymeric MDI with NCO content of 30-32%; most preferred is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-2010 and polymeric MDI Wanhua PM-400.
The density of the low-density low-conductivity HFC-134a system polyurethane rigid foam is 25-35 kg/m3。
A preparation method of a low-density low-conductivity HFC-134a system polyurethane rigid foam comprises the following steps:
1) weighing the raw materials according to the proportion, uniformly mixing the polyether composition, the surfactant, the composite catalyst and water, and cooling to 10 ℃ to obtain the combined polyether;
2) cooling the foaming agent to below 10 ℃, adding the foaming agent into the combined polyether prepared in the step 1), and uniformly mixing;
3) mixing the mixture obtained in the step 2) with polyisocyanate, and foaming at high pressure to obtain the low-density and low-conductivity HFC-134a system polyurethane rigid foam.
Further, the high pressure foaming process in step 3) is carried out under the following conditions: the material temperature is 17-21 ℃, and the pressure is 100-150 bar (gauge pressure); preferably, the feed temperature is 19 ℃ and the pressure is 125bar (gauge).
Further, in the high-pressure foaming process in the step 3), the filling coefficient of the reaction mixture in the mold is 1.1-1.5, and the demolding time is less than or equal to 150 s.
The low-density low-conductivity HFC-134a system polyurethane rigid foam is mainly applied to the field of preparation of heat insulation materials, and is preferably used for preparation of materials such as refrigerator heat insulation layers and the like.
In the prior art, when the foaming agent of the polyurethane rigid foam is replaced by HFC-134a, due to the low boiling point of HFC-134a, the foaming agent is easy to escape in the early stage of foaming, nucleation is not easy to occur, the formation of foam cells is influenced, and in addition, the reduction of the low boiling point foaming agent also influences the strength of the foam to a certain extent. The novel 3, 4-diamino furoxan polyether polyol monomer adopted in the raw materials has hydrophilicity and lipophilicity, has good compatibility with HFC-134a, can completely wrap HFC-134a gas at the initial stage of reaction, and enables HFC-134a to uniformly permeate into foam pores, so that the foam pores are finer and finer, and the effect of optimizing heat conduction is achieved. In addition, the 3, 4-diamino furazolidone structure is regular, so that the rigidity of the foam is enhanced, the steric hindrance between molecules is increased, the autocatalysis effect is weakened, the flow is smoother, and the strength and the fluidity of the foam are facilitated. In addition, the selected surfactant has strong nucleating effect and good stability, and is beneficial to further reducing the thermal conductivity of the foam.
The technical scheme of the invention has the beneficial effects that:
1) the invention greatly improves the fluidity of the foam in the foaming process of the HFC-134a system polyurethane rigid foam by using the novel 3, 4-diamino furoxan polyether polyol, optimizing the formula and the like. The 3, 4-diamino furoxan polyether polyol can effectively optimize the strength and heat conduction of low-density foam, and after the catalyst is reasonably matched, the balance of foaming reaction and gel reaction can be kept, and the reaction of the polyether polyol and polyisocyanate and the polymerization reaction of the polyisocyanate can be promoted in the later reaction period, so that the aims of promoting the post-curing reaction of the foam, reducing the content of polyisocyanate components and improving the bonding force are fulfilled.
2) The polyurethane rigid foam prepared by the invention adopts HFC-134a as an environment-friendly foaming agent, and has no damage to an ozone layer. Due to the addition of the HFC-134a foaming agent, the heat conductivity value of the polyurethane hard foam is obviously reduced, the heat insulation performance is improved, and when the HFC-134a foaming agent is used for manufacturing the insulation board of the refrigerator and the freezer, the power consumption can be reduced, and the aim of saving energy is effectively fulfilled. In addition, the polyurethane rigid foam prepared by the invention has better dimensional stability under the condition of low density.
Detailed Description
The technical solutions of the present invention are further described by the following specific examples, but the scope of the present invention is not limited thereto, and variations or substitutions of the same or similar technical features within the technical scope of the present invention are included.
The sources of the main materials and reagents of the examples of the invention are shown in table 1:
TABLE 1
Polyether polyol A: sucrose and glycerol polyether polyol is prepared by the addition reaction of sucrose and glycerol which are used as initiators and propylene oxide, and has a hydroxyl value of 380-440 mgKOH/g and a functionality of 5.0-6.0.
Polyether polyol B: the sorbitol polyether polyol is prepared by performing addition reaction on sorbitol serving as an initiator and propylene oxide, and has a hydroxyl value of 400-460 mgKOH/g and a functionality of 5.7-6.4.
Polyether polyol C: the 3, 4-diamino furazan polyether polyol is prepared by the addition reaction of 3, 4-diamino furazan serving as an initiator and propylene oxide or ethylene oxide, and has a hydroxyl value of 340-420 mgKOH/g and a functionality of 3.6-4.4.
Polyether polyol D: the glycerol polyether polyol is prepared by the addition reaction of glycerol serving as an initiator and propylene oxide, and has a hydroxyl value of 180-240 mgKOH/g and a functionality of 2.0-2.7.
Polyether polyol C1: the o-tolylenediamine polyether polyol is prepared by addition reaction of o-tolylenediamine serving as an initiator and propylene oxide, and has a hydroxyl value of 340-420 mgKOH/g and a functionality of 3.6-4.4.
Example 1
A preparation method of 3, 4-diamino furoxan polyether polyol comprises the following steps:
1) adding water (135g) and 3, 4-diamino furoxan (530g) into a reaction kettle, performing nitrogen replacement pressure test, starting stirring and heating to 90 ℃ to obtain a 3, 4-diamino furoxan aqueous solution, then adding 1035g of propylene oxide according to the flow rate of 700g/h, performing autocatalytic reaction for 1h, then heating to 115 ℃ and performing aging reaction for 1 h;
2) adding 20g (with the concentration of 50 wt%) of potassium hydroxide aqueous solution into the system in the step 1), dehydrating for 2h under vacuum at 110 ℃, adding 970g of residual propylene oxide according to the flow rate of 600g/h, continuing to react for 1h, and then heating to 120 ℃ and reacting for 1 h;
3) at this time, 35g of a 50 wt% phosphoric acid aqueous solution was added to remove K ions, to obtain 3, 4-diaminofurazan polyether polyol having a hydroxyl value of 346mgKOH/g and a functionality of 3.8.
Example 2
The preparation method of the 3, 4-diamino furo polyether polyol comprises the following steps:
1) adding water (135g) and 3, 4-diamino furo (530g) into a reaction kettle, performing nitrogen replacement pressure test, starting stirring and heating to 90 ℃, maintaining for 1 hour to obtain a 3, 4-diamino furo water solution, then adding 828g of epoxy olefin (the mass ratio of propylene oxide to ethylene oxide is 8:2) according to the flow rate of 700g/h, performing autocatalytic reaction for 2 hours, then heating to 100 ℃, and performing aging reaction for 2 hours;
2) adding 20g (with the concentration of 50 wt%) of potassium hydroxide aqueous solution into the system in the step 1), dehydrating for 2h under vacuum at the temperature of 110 ℃, adding 776g of residual epoxy olefin (the mass ratio of propylene oxide to ethylene oxide is 8:2) according to the flow rate of 600g/h, continuously reacting for 2h, then heating to 120 ℃ and reacting for 1 h;
3) at this time, 35g of a 50 wt% phosphoric acid aqueous solution was added to remove K ions, to obtain 3, 4-diaminofurazan polyether polyol having a hydroxyl value of 361mgKOH/g and a functionality of 4.1.
Example 3
A low-density low-conductivity HFC-134a system polyurethane rigid foam comprises the following raw materials:
the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 15: 150, specifically:
the composite polyether comprises the following components: 91.4 parts of polyether composition, 3 parts of surfactant, 3.4 parts of composite catalyst and 2.2 parts of distilled water;
foaming agent: CP 11 parts, HFC-134a 4 parts;
polyisocyanate: and polymerized MDI Wanhua PM-200150 parts.
In the combined polyether:
the polyether composition comprises 15 parts by weight of 3, 4-diamino furoxan polyether polyol (prepared in example 2): 51.4 parts of sucrose and glycerol polyether polyol (with a hydroxyl value of 385mgKOH/g and a functionality of 5.3), 20 parts of sorbitol polyether polyol (with a hydroxyl value of 432mgKOH/g and a functionality of 5.8) and 5 parts of glycerol polyether polyol (with a hydroxyl value of 192mgKOH/g and a functionality of 2.3);
surfactant (b): 85253 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethyl cyclohexylamine, the trimerization catalyst is potassium acetate, and the foaming catalyst is pentamethyl diethylenetriamine: dimethyl cyclohexylamine: potassium acetate 1:5:1 (mass ratio).
The preparation method of the polyurethane hard foam comprises the following steps:
1) weighing the raw materials according to the proportion, uniformly mixing the polyether composition, the surfactant, the composite catalyst and water, and cooling to 10 ℃ to obtain the combined polyether;
2) cooling the foaming agent to below 10 ℃, adding the foaming agent into the combined polyether prepared in the step 1), and uniformly mixing;
3) and (3) mixing the mixture obtained in the step 2) with polyisocyanate, foaming at high pressure, wherein the material temperature is 19 ℃, the pressure is 125bar (gauge pressure), the filling coefficient of the reaction mixture in a mould is 1.2, and the demoulding time is 150s, so that the low-density and low-conductivity HFC-134a system polyurethane rigid foam is prepared.
Example 4
A low-density low-conductivity HFC-134a system polyurethane rigid foam comprises the following raw materials:
the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 15: 150, specifically:
the composite polyether comprises the following components: 91.7 parts of polyether composition, 3 parts of surfactant, 3.1 parts of composite catalyst and 2.2 parts of distilled water;
foaming agent: CP 11 parts, HFC-134a 4 parts;
polyisocyanate: and polymerized MDI Wanhua PM-200150 parts.
In the combined polyether:
the polyether composition comprises 30 parts by weight of 3, 4-diamino furoxan polyether polyol (prepared in example 2): 36.7 parts of sucrose and glycerol polyether polyol (with a hydroxyl value of 385mgKOH/g and a functionality of 5.3), 20 parts of sorbitol polyether polyol (with a hydroxyl value of 432mgKOH/g and a functionality of 5.8) and 5 parts of glycerol polyether polyol (with a hydroxyl value of 192mgKOH/g and a functionality of 2.3);
surfactant (b): 85253 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethyl cyclohexylamine, the trimerization catalyst is potassium acetate, and the foaming catalyst is pentamethyl diethylenetriamine: dimethyl cyclohexylamine: potassium acetate 1:4:1 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 3.
Example 5
A low-density low-conductivity HFC-134a system polyurethane rigid foam comprises the following raw materials:
the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 14: 150, specifically:
the composite polyether comprises the following components: 92 parts of polyether composition, 3 parts of surfactant, 2.8 parts of composite catalyst and 2.2 parts of distilled water;
foaming agent: CP 11 parts, HFC-134a 3 parts;
polyisocyanate: and polymerized MDI Wanhua PM-200150 parts.
In the combined polyether:
the polyether composition comprises 35 parts by weight of 3, 4-diamino furoxan polyether polyol (prepared in example 2): 32 parts of sucrose and glycerol polyether polyol (with a hydroxyl value of 412mgKOH/g and a functionality of 5.7), 20 parts of sorbitol polyether polyol (with a hydroxyl value of 408mgKOH/g and a functionality of 6.2) and 5 parts of glycerol polyether polyol (with a hydroxyl value of 210mgKOH/g and a functionality of 2.6);
surfactant (b): 85253 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is triethylene diamine, the trimerization catalyst is potassium acetate, and the foaming catalyst is pentamethyl diethylenetriamine: triethylene diamine: potassium acetate 1:4:1.2 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 3.
Example 6
A low-density low-conductivity HFC-134a system polyurethane rigid foam comprises the following raw materials:
the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 15: 143, specifically:
the composite polyether comprises the following components: 91.7 parts of polyether composition, 3 parts of surfactant, 3.1 parts of composite catalyst and 2.2 parts of water;
foaming agent: 10 parts of CP, 5 parts of HFC-134 a;
polyisocyanate: and polymerized MDI Wanhua PM-2010143 parts.
In the combined polyether:
the polyether composition comprises 30 parts by weight of 3, 4-diamino furoxan polyether polyol (prepared in example 1): 36.7 parts of sucrose and glycerol polyether polyol (with a hydroxyl value of 412mgKOH/g and a functionality of 5.7), 20 parts of sorbitol polyether polyol (with a hydroxyl value of 430mgKOH/g and a functionality of 5.8) and 5 parts of glycerol polyether polyol (with a hydroxyl value of 210mgKOH/g and a functionality of 2.6);
surfactant (b): silicone oil AK 88053 parts (Demei chemical industry).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is triethylene diamine, the trimerization catalyst is hexahydrotriazine, and the foaming catalyst is pentamethyl diethylenetriamine: triethylene diamine: hexahydrotriazine 1:6:1 (mass ratio).
The preparation of polyurethane rigid foam was the same as in example 3.
Example 7
A low-density low-conductivity HFC-134a system polyurethane rigid foam comprises the following raw materials:
the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 15: 143, specifically:
the composite polyether comprises the following components: 92 parts of polyether composition, 3 parts of surfactant, 2.8 parts of composite catalyst and 2.2 parts of water;
foaming agent: CP 11 parts, HFC-134a 4 parts;
polyisocyanate: 150 parts of polymeric MDI Wanhua PM-400.
In the combined polyether:
the polyether composition consisted of 45 parts by weight of 3, 4-diamino furoxan polyether polyol (prepared in example 1): 22 parts of sucrose and glycerol polyether polyol (with a hydroxyl value of 420mgKOH/g and a functionality of 5.6), 20 parts of sorbitol polyether polyol (with a hydroxyl value of 430mgKOH/g and a functionality of 5.8) and 5 parts of glycerol polyether polyol (with a hydroxyl value of 224mgKOH/g and a functionality of 2.0);
surfactant (b): 85253 parts of silicone oil B (Meiji chart).
Composite catalyst: the foaming catalyst is pentamethyl diethylenetriamine, the gel catalyst is dimethylcyclohexylamine, the trimerization catalyst is hexahydrotriazine, and the foaming catalyst is pentamethyl diethylenetriamine: dimethyl cyclohexylamine: hexahydrotriazine (mass ratio) 1:4.5: 1.
The preparation of polyurethane rigid foam was the same as in example 3.
Table 2: examples 3-7 raw Material composition (parts by weight) and Performance parameters of polyurethane rigid foams
Note: the foam density, the compression strength, the heat conductivity coefficient and the bonding strength are determined according to the national standard:
foam core density test according to standard: GB/T6343-2009;
foam thermal conductivity test according to standard: GB/T10295-;
foam compression strength test according to the standard: GB/T8813-;
foam adhesion test according to the standard: GB/T2790-1995.
Comparative example 1
In example 4, the 3, 4-diaminofuroxan polyether polyol was replaced with the same parts by weight of o-tolylenediamine polyether polyol (hydroxyl value: 385mgKOH/g, functionality: 4.0), and the other conditions were the same as in example 4.
Comparative example 2
The polyether composition does not contain 3, 4-diamino furoxan polyether polyol, the total weight part of the polyether composition is unchanged, and the weight ratio of the sucrose and glycerol polyether polyol to the sorbitol polyether polyol and the glycerol polyether polyol is unchanged. The other conditions were the same as in example 4.
Comparative example 3
The CP blowing agent and HFC-134a mixture were replaced with CP blowing agent at the same weight parts as the blowing agent, and the other conditions were the same as in example 4.
The properties of the rigid polyurethane foams prepared in comparative examples 1 to 3 are shown in Table 3:
TABLE 3
Claims (24)
1. A3, 4-diamino furoxan polyether polyol has a structure shown in formula I:
wherein: x is an integer of 4 to 10;
r is H, C1-C6 alkyl.
2. A process for the preparation of 3, 4-diamino furoxan polyether polyol as claimed in claim 1, wherein: 3, 4-diamino furoxan is used as an initial raw material to prepare 3, 4-diamino furoxan polyether polyol through addition reaction with alkylene oxide, wherein the reaction formula is as follows:
3. the method according to claim 2, wherein the molar ratio of 3, 4-diamino furoxan to alkylene oxide is 1: 4-8.
4. The process according to claim 3, wherein the molar ratio of 3, 4-diaminofuroxan to alkylene oxide is 1: 6.
5. The process according to claim 2, wherein the alkylene oxide is added to the reaction system in two portions.
6. The process according to claim 2, wherein the alkylene oxide is propylene oxide and/or ethylene oxide.
7. The method of claim 2, wherein the steps comprise:
1) mixing the 3, 4-diamino furoxan aqueous solution with partial olefin oxide, carrying out autocatalytic reaction for 1-4 h at the temperature of 60-80 ℃, and then heating to 80-120 ℃ for aging reaction for 1-4 h;
2) adding a potassium hydroxide aqueous solution into the system in the step 1), then carrying out vacuum dehydration for 2-6 h, adding the rest olefin oxide, continuing to react for 1-4 h, then heating to 100-140 ℃, and reacting for 1-4 h;
3) adding phosphoric acid aqueous solution into the system obtained in the step 2) to remove potassium ions, and obtaining the 3, 4-diamino furoxan polyether polyol.
8. The method of claim 7, wherein:
the mass ratio of the olefin oxide in the step 1) to the olefin oxide in the step 2) is 1: 1-1.4; in the step 1), the alkylene oxide is added according to the flow rate of 700 g/h; in the step 2), the alkylene oxide is added according to the flow rate of 500-700 g/h;
in the step 2), the vacuum dehydration temperature is 115 ℃; heating to 120 ℃;
the concentration of the 3, 4-diamino furazane aqueous solution is 60-90 wt%; the concentration of the potassium hydroxide aqueous solution is 30-60 wt%; the concentration of the phosphoric acid aqueous solution is 30-70 wt%;
the molar ratio of the 3, 4-diamino furoxan to the potassium hydroxide and the phosphoric acid is 20-60: 1:1, and the aqueous solution is calculated by solute.
9. The method of claim 8, wherein: the mass ratio of the olefin oxide in the step 1) to the olefin oxide in the step 2) is 1: 1.15.
10. The method of claim 8, wherein: the concentration of the 3, 4-diamino furazane aqueous solution is 81 wt%; the concentration of the potassium hydroxide aqueous solution is 50 wt%; the concentration of the phosphoric acid aqueous solution was 50 wt%.
11. The method of claim 8, wherein: the molar ratio of the 3, 4-diamino furoxan to the potassium hydroxide to the phosphoric acid is 30:1: 1.
12. A rigid polyurethane foam characterized by: the preparation raw materials of the polyurethane rigid foam comprise combined polyether, a foaming agent and polyisocyanate, wherein the mass ratio of the combined polyether to the foaming agent to the polyisocyanate is 100: 12-23: 130 to 160;
the foaming agent comprises HFC-134 a;
the combined polyether comprises a polyether composition, wherein the polyether composition comprises the 3, 4-diamino furoxan polyether polyol in claim 1 or the 3, 4-diamino furoxan polyether polyol prepared by the method in any one of claims 2 to 11.
13. The rigid polyurethane foam according to claim 12, wherein: the foaming agent comprises the following components in parts by weight: 10-15 parts of CP foaming agent and 2-8 parts of HFC-134 a;
the composite polyether comprises the following components in parts by weight: 90-100 parts of polyether composition, 1.5-3 parts of surfactant, 2-4 parts of composite catalyst and 1-3 parts of water;
the polyisocyanate is polymeric MDI.
14. The rigid polyurethane foam according to claim 13, wherein: the polyisocyanate is polymeric MDI with NCO content of 30-32%.
15. The rigid polyurethane foam according to claim 14, wherein: the polyisocyanate is one or more of polymeric MDI Wanhua PM-200, polymeric MDI Wanhua PM-2010 and polymeric MDI Wanhua PM-400.
16. The rigid polyurethane foam according to claim 13, wherein: the polyether composition comprises, by weight, 10-45 parts of 3, 4-diamino furoxan polyether polyol, 20-55 parts of sucrose and glycerol polyether polyol, 10-30 parts of sorbitol polyether polyol and 10-25 parts of glycerol polyether polyol.
17. The rigid polyurethane foam according to claim 16, wherein: the polyether composition comprises, by weight, 20-35 parts of 3, 4-diamino furoxan polyether polyol, 30-50 parts of sucrose and glycerol polyether polyol, 10-30 parts of sorbitol polyether polyol and 10-25 parts of glycerol polyether polyol.
18. The rigid polyurethane foam according to claim 13, wherein:
the surfactant is a silicon surfactant;
the composite catalyst comprises a foaming catalyst, a gel catalyst and a trimerization catalyst, wherein the mass ratio of the foaming catalyst to the gel catalyst to the trimerization catalyst is 1: 2-8: 1-4.
19. The rigid polyurethane foam according to claim 18, wherein: the surfactant is an organic silicon surfactant.
20. The rigid polyurethane foam according to claim 19, wherein: the surfactant is at least one of silicone oil AK8805, silicone oil AK8830, silicone oil B8525 and silicone oil B8545.
21. The rigid polyurethane foam according to claim 18, wherein: the foaming catalyst is one or a mixture of more than one of pentamethyldiethylenetriamine, tetramethylhexamethylenediamine and bis-dimethylaminoethylether in any proportion;
the gel catalyst is one or a mixture of more than one of dimethylbenzylamine, dimethylcyclohexane and triethylene diamine in any proportion;
the trimerization catalyst is hexahydrotriazine and/or potassium acetate.
22. A method for preparing the rigid polyurethane foam according to any one of claims 13 to 21, comprising the steps of:
1) weighing the raw materials according to the proportion, uniformly mixing the polyether composition, the surfactant, the composite catalyst and water, and cooling to 10 ℃ to obtain the combined polyether;
2) cooling the foaming agent to below 10 ℃, adding the foaming agent into the combined polyether prepared in the step 1), and uniformly mixing;
3) and (3) mixing the mixture obtained in the step 2) with polyisocyanate, and foaming at high pressure to obtain the rigid polyurethane foam.
23. The method of claim 22, wherein: the high-pressure foaming process in the step 3) has the following conditions: the material temperature is 17-21 ℃, and the gauge pressure is 100-150 bar; in the high-pressure foaming process, the filling coefficient of the reaction mixture in the mold is 1.1-1.5, and the demolding time is less than or equal to 150 s.
24. The method of claim 23, wherein: the conditions are as follows: the material temperature is 19 ℃, and the gauge pressure is 125 bar.
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| CN111647191B (en) * | 2020-05-14 | 2022-11-08 | 万华化学（宁波）容威聚氨酯有限公司 | Low-conductivity foaming agent composition, polyurethane rigid foam and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443134A (en) * | 2011-09-16 | 2012-05-09 | 广东万华容威聚氨酯有限公司 | Polyurethane rigid foam and preparation method thereof |
| CN106496494A (en) * | 2016-10-28 | 2017-03-15 | 合肥华凌股份有限公司 | A kind of low-density, polyurethane foam of low heat conductivity and preparation method thereof |
| CN107177028A (en) * | 2017-06-13 | 2017-09-19 | 合肥华凌股份有限公司 | Combined polyether, polyurethane foam and its preparation method and application |
| CN107501517A (en) * | 2017-09-11 | 2017-12-22 | 合肥华凌股份有限公司 | Polyurethane foam and its production and use |
-
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102443134A (en) * | 2011-09-16 | 2012-05-09 | 广东万华容威聚氨酯有限公司 | Polyurethane rigid foam and preparation method thereof |
| CN106496494A (en) * | 2016-10-28 | 2017-03-15 | 合肥华凌股份有限公司 | A kind of low-density, polyurethane foam of low heat conductivity and preparation method thereof |
| CN107177028A (en) * | 2017-06-13 | 2017-09-19 | 合肥华凌股份有限公司 | Combined polyether, polyurethane foam and its preparation method and application |
| CN107501517A (en) * | 2017-09-11 | 2017-12-22 | 合肥华凌股份有限公司 | Polyurethane foam and its production and use |
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