Structural flame retardant high strength low exothermic polymer grouting material for consolidating

Abstract

A structural flame retardant high strength low exothermic polymer grouting material for consolidating, belonging to a technical field of polyurethane material, is produced by combined the polyether polyol and the modified isocyanate in a weight ratio of 100:(100-160), leading to internal reaction temperature ≤100° C., strength ≥60 mPa, bonding ≥3 mPa, oxygen index ≥28% while no halogen and no effect on water quality, odor level (80° C.) ≤3.5, and fog test ≤5 mg (which means no physical additive flame retardant is diffused into the environment). In particular, with no halogen, which is known as environmental hormones, in the plasticizers, there will be less combustion smoke, wherein the present invention will not release corrosive or irritating hydrogen halide gas, nor produce toxic carcinogens polybrominated benzoxins and polybrominated dibenzofurans, thereby avoiding the long-term impact of the material on the environment.

Claims

1. A structural flame retardant high strength low exothermic polymer grouting material for consolidating, consisting of: a modified isocyanate component and a polyol component which are polymerized together, wherein a mass ratio of the modified isocyanate component to the polyol component is (100-160):100; a structural formula of the modified isocyanate component is: ##STR00009## the polyol component comprises: polyether polyol which adopts 6-functionality sorbitol as an initiator, 4,4′-bis-sec-butylaminodiphenylmethane, silicone oil, and a reactive catalyst, wherein the polyether polyol which adopts the 6-functionality sorbitol as the initiator accounts for 50-70% of a total weight of the polyol component; 4,4′-bis-sec-butylaminodiphenylmethane accounts for 25-45% of the total weight of the polyol component; the silicone oil accounts for 1-3% of the total weight of the polyol component; and the reactive catalyst accounts for 2-4% of the total weight of the polyol component.

2. The structural flame retardant high strength low exothermic polymer grouting material for consolidating, as recited in claim 1, wherein the modified isocyanate component has a P content of 4.4%, an N content of 7.9%, and an NCO % content of 11.9%.

3. The structural flame retardant high strength low exothermic polymer grouting material for consolidating, as recited in claim 1, wherein the polyether polyol which adopts the 6-functionality sorbitol as the initiator is a highly active polyether with the sorbitol as the initiator and propylene oxide as a polymerized monomer.

4. The structural flame retardant high strength low exothermic polymer grouting material for consolidating, as recited in claim 3, wherein the polyether polyol which adopts the 6-functionality sorbitol as the initiator adopts YD6482 from Hebei Yadong Chemical Group Co., Ltd. or NJ-6207 from Jurong Ningwu New Material Development Co., Ltd.

5. The structural flame retardant high strength low exothermic polymer grouting material for consolidating, as recited in claim 3, wherein the silicone oil is polydimethylsiloxane, which adopts L6950 from Momentive High-tech Materials Group.

6. The structural flame retardant high strength low exothermic polymer grouting material for consolidating, as recited in claim 1, wherein the reactive catalyst adopts Dabco T from Evonik Specialty Chemicals (Shanghai) Co., Ltd.

7. A method for synthesizing the structural flame retardant high strength low exothermic polymer grouting material for consolidating as recited in claim 1, comprising a step of polymerizing a modified isocyanate component with a polyol component, wherein a method for synthesizing the modified isocyanate component comprises steps of: 1) esterifying 2-carboxyethyl phenyl hypophosphorous acid and ethylene glycol with a molar ratio of 1:1, so as to obtain 2-carboxyethyl phenyl hypophosphite ethylene glycol, wherein a reaction equation is: ##STR00010## 2) performing an addition reaction to the 2-carboxyethyl phenyl hypophosphite ethylene glycol and propylene oxide with a molar ratio of 1:1, so as to generate a phosphorus-containing diol intermediate, wherein a reaction equation is: ##STR00011## and 3) polymerizing the phosphorus-containing diol intermediate and TDI to obtain a difunctional modified flame retardant isocyanate compound, wherein a reaction equation is: ##STR00012##

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0039] Technical solutions in experimental examples of the present invention will be clearly and completely described below. Obviously, the experimental examples described are only a part of all possible ones of the present invention. Based on the following experimental examples of the present invention, all other experimental examples obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.

Embodiment 1

[0040] The embodiment 1 provides a structural flame retardant high strength low exothermic polymer grouting material for consolidating, consisting of: a modified isocyanate component and a polyol component which are polymerized together, wherein a mass ratio of the modified isocyanate component to the polyol component is (100-160):100; a structural formula of the modified isocyanate component is:

##STR00005##

[0041] the modified isocyanate component has a P content of 4.4%, an N content of 7.9%, and an NCO % content of 11.9%;

[0042] the polyol component comprises: polyether polyol which adopts 6-functionality sorbitol as an initiator, 4,4′-bis-sec-butylaminodiphenylmethane, silicone oil, and a reactive auxiliary agent, wherein the polyether polyol which adopts the 6-functionality sorbitol as the initiator accounts for 50-70% of a total weight of the polyol component; 4,4′-bis-sec-butylaminodiphenylmethane accounts for 25-45% of the total weight of the polyol component; the silicone oil accounts for 1-3% of the total weight of the polyol component; and the reactive auxiliary agent accounts for 2-4% of the total weight of the polyol component.

[0043] The polyether polyol which adopts the 6-functionality sorbitol as the initiator is a highly active polyether with the sorbitol as the initiator and propylene oxide as a polymerized monomer. The polyether polyol which adopts the 6-functionality sorbitol as the initiator adopts YD6482 from Hebei Yadong Chemical Group Co., Ltd. or NJ-6207 from Jurong Ningwu New Material Development Co., Ltd.

[0044] The 4,4′-bis-sec-butylaminodiphenylmethane is a liquid sec-diamine. Since the hydrogen atom on each amino group is replaced by a sec-butyl group, the combination of the active hydrogen atom and the sec-butyl group in the limited space generated many unique properties, and the amino moiety forms a urea bond that affects the hard segment. It is attached to the polymer, neither leaching nor precipitation, and the alkyl group increases the solubility of the diamine, making it mixable with almost any polyol and polyamine.

[0045] The auxiliary agent comprises a material surfactant and a reactive catalyst, the surfactant accounts for 1-3% of the total weight of the polyol, and the reactive catalyst accounts for 2-4% of the total weight of the polyol. The silicone oil is polydimethylsiloxane, which adopts L6950 from Momentive High-tech Materials Group. The reactive catalyst mainly adopts Dabco T from Evonik Specialty Chemicals (Shanghai) Co., Ltd.

[0046] The embodiment 1 also provides a method for synthesizing the structural flame retardant high strength low exothermic polymer grouting material for consolidating, comprising a step of polymerizing a modified isocyanate component with a polyol component, wherein a method for synthesizing the modified isocyanate component comprises steps of:

[0047] 1) esterifying 2-carboxyethyl phenyl hypophosphorous acid and ethylene glycol with a molar ratio of 1:1, so as to obtain 2-carboxyethyl phenyl hypophosphite ethylene glycol, wherein a reaction equation is:

##STR00006##

[0048] 2) performing an addition reaction to the 2-carboxyethyl phenyl hypophosphite ethylene glycol and propylene oxide with a molar ratio of 1:1, so as to generate a phosphorus-containing diol intermediate, wherein a reaction equation is:

##STR00007##

and

[0049] 3) polymerizing the phosphorus-containing diol intermediate and TDI to obtain a difunctional modified flame retardant isocyanate compound, wherein a reaction equation is:

##STR00008##

[0050] Specific synthesis process of the modified isocyanate comprises steps of:

[0051] 1) putting 2-carboxyethylphenyl hypophosphorous acid (Wuhan Hezhong Biochemical Manufacturing Co., Ltd.) and ethylene glycol into a reaction kettle at a molar ratio of 1:1, and then esterifying at 105-110° C. under catalysis of sulfuric acid or organotin to generate the 2-carboxyethyl phenyl hypophosphite ethylene glycol, wherein resulting water is distilled off from a top of the reaction kettle;

[0052] 2) heating the 2-carboxyethyl phenyl hypophosphite ethylene glycol to between 100-110° C. in reaction kettle, using potassium hydroxide a catalyst, and slowly adding propylene oxide at a molar ratio of 1:1; gradually raising a reaction pressure in the reaction kettle and keeping a maximum pressure below 2.5 kg; keeping a temperature in the reaction kettle between 100-115° C., and maintaining the pressure for 4 hours after adding materials; then keeping the temperature in the reaction kettle at about 100° C., and removing unreacted small molecules by vacuum, to obtain the phosphorus-containing diol intermediate;

[0053] 3) heating the reaction kettle to 48° C.-52° C., firstly add all the TDI according to a molar ratio of phosphorus-containing diol intermediate: TDI=1:(3-4), and then adding all the phosphorus-containing diol intermediate at a constant speed;

[0054] 4) heating the reaction kettle to 78° C.-82° C., and then reacting for 1.9 h-2.2 h;

[0055] 5) removing unreacted excess TDI through a film evaporator; and

[0056] 6) cooling the reaction kettle to 48° C.-52° C., then discharging and packaging to obtain a product with a P content of 4.4%, an N content of 7.9%, and an NCO % content of 11.9%.

Experimental Examples 1-4

[0057] According to the experimental examples 1-4, the combined polyether polyol formula is as follows:

TABLE-US-00001 Weight Name percentage YD6482 (polyether polyol, Hebei Yadong Chemical Group 60 Co., Ltd.) 4,4′-bis-sec-butylaminodiphenylmethane (Wanhua Chemical 36 Group Co., Ltd.) L6950 (silicone oil, Momentive High-tech Materials Group) 1 Dabco T (catalyst, Evonik Specialty Chemicals (Shanghai) 2.5 Co., Ltd.) PC 46 (catalyst, Evonik Specialty Chemicals (Shanghai) 0.5 Co., Ltd.) Total 100

[0058] 100 parts of the above-mentioned combined polyether polyol were mixed and stirred with the total parts of the isocyanate component and the physical flame retardant component of each experimental example in the following table, to prepare the product.

[0059] The isocyanate components and additive flame retardant components of each experimental example are as follows:

TABLE-US-00002 Experimental Experimental Experiment Experimental Name example 1 example 2 example 3 example 4 Isocyanate PM 200 (Wanhua 100 100 0 0 component Chemical Group Co., Ltd.) Modified 0 0 100 160 isocyanate compound Physical TCPP (flame 0 60 0 0 flame retardant, retardant Zhejiang component Wansheng Co., Ltd.) Total parts of isocyanate 100 160 100 160 component and physical flame retardant component

[0060] Performance of each experimental example is as follows:

TABLE-US-00003 Experimental Experimental Experimental Experimental Name example 1 example 2 example 3 example 4 Flame Phosphorus 0 2.17 2.20 2.71 retardancy content in foam % Oxygen 18.5 27.9 28.4 30.2 Index % Environmental Odor rating 3.5 4.5 3.5 3.5 performance (80° C.) Fog test/mg 4.45 51.84 4.62 4.13 Physical Specific gravity 1.08 1.11 1.08 1.09 properties Compressive 56 41 61 67 strength mPa

[0061] Odor level test standard: VDA270:1992.

[0062] Fog test: Q/ZK JS 364-201903.

[0063] Compared with the experimental example 1, the experimental example 2 added 60 parts of physical flame retardant component TCPP while the other conditions were remained. The oxygen index increased from 18.5%, which was not flame retardant, to 27.9%, which was flame retardant. At the same time, the odor level (80° C.) increased from 3.5 to 4.5, the fog test increased from 4.45 mg to 51.84 mg, and the compressive strength decreased from 56 mPa to 41 mPa. It can be seen that the physical flame retardant component TCPP brought foam retardancy, but seriously affected the environmental protection performance and compressive strength of the material.

[0064] Compared with the experimental example 1, the experimental example 3 did not add the physical flame retardant TCPP. The oxygen index increased from 18.5%, which was not flame retardant, to 28.4%, which was flame retardant. At the same time, there was not much change in the odor levels (80° C.), which were 3.5 and 3.5 respectively, and there was also not much change in the compressive strengths, which were 56 mPa and 61 mPa respectively. It can be seen that the modified isocyanate can improve the flame retardancy of polyurethane foam without adding the flame retardants, so as to avoid reducing the environmental protection indexes by the flame retardants. The conflict of high flame retardancy and environmental protection indexes such as low odor was resolved.

[0065] Compared with the experimental example 2, the experimental example 3 kept basically the same P content in the foam while there was not much change in the oxygen index. However, since the experimental example 2 added 60 parts of the physical flame retardant component TCPP as the flame Retardant and the plasticizer, the odor level (80° C.) increased to 4.5, the fog test increased to 51.84 mg, and the compressive strength decreased to 41 mPa. It can be seen that compared with the physical flame retardant TCPP, the modified isocyanate has significant advantages in environmental protection and compressive strength.

[0066] Compared with the experimental example 2, the experimental example 4 kept the total parts below 260 while the oxygen index increased from 27.9% to 30.2%, the odor level (80° C.) decreased from 4.5 to 3.5, the fog test decreased from 51.84 to 4.13 mg, and the compressive strength increased from 41 mPa to 67 mPa. It further indicated that compared with the physical flame retardant TCPP, the modified isocyanate has significant advantages in environmental protection and compressive strength.

Experiment Examples 5-6

[0067] Compared with that of the experimental example 4, the combined polyether polyol formula in the experimental examples 5-6 is as follows:

TABLE-US-00004 Experimental Experimental Experimental Name example 4 example 5 example 6 YD6482 (polyether polyol, 60 36 80 Hebei Yadong Chemical Group Co., Ltd.) 4,4′-bis-sec- 36 60 16 butylaminodiphenylmethane (Wanhua Chemical Group Co., Ltd.) L6950 (silicone oil, 1 1 1 Momentive High-tech Materials Group) Dabco T (catalyst, Evonik 2.5 2.5 2.5 Specialty Chemicals (Shanghai) Co., Ltd.) PC 46 (catalyst, Evonik 0.5 0.5 0.5 Specialty Chemicals (Shanghai) Co., Ltd.) Total 100 100 100

[0068] 100 parts of the above-mentioned combined polyether polyol were mixed and stirred with 150 parts of the 3-functionality modified isocyanate component, to prepare the foam product.

[0069] Flame retardancy and environmental performance of each experimental example are as follows:

TABLE-US-00005 Experimental Experimental Experimental Name example 4 example 5 example 6 Flame Phosphorus 2.71 2.71 2.71 retardancy content in foam % Oxygen 30.2 30.7 30.0 Index % Environmental Odor rating 3.5 3.5 3.5 performance (80° C.) Fog test/mg 4.13 4.68 4.41 Physical Specific 1.09 1.13 1.07 properties gravity Compressive 67 55 57 strength mPa

[0070] According to the experimental examples 5 and 6, the ratio of YD6482 to 4,4′-bis-sec-butylaminodiphenylmethane in the white material formula was changed from 5:3 to 3:5 and 5:1 respectively without changing the isocyanate component. As a result, the compressive strengths were 55 mPa and 57 mPa, respectively, which were obviously changed. The reason of this may be: when the ratio of YD6482:4,4′-bis-sec-butylaminodiphenylmethane is about 5:3, the foam strength reaches the maximum value. At this ratio, the hard segments in the foam are reticulated intersecting continuous phases, while the soft segments are transformed into dispersed phases and dispersed among the hard segments. The reasonable degree of microphase separation and hard segment domain size of the material leads to a high compressive strength. In the experimental example 6, the proportion of the 4,4′-bis-sec-butylaminodiphenylmethane was too small, so the soft segments were reticulated intersecting continuous phases, while the hard segments were transformed into a dispersed phase and dispersed among the soft segments, leading to poor compressive strength of the foam. In the experimental example 5, the proportion of the 4,4′-bis-sec-butylaminodiphenylmethane was too large, so the average functionality of the combined polyether polyol was low, while the foam cross-linking density was insufficient, leading to poor compressive strength of the foam.

[0071] Last but not least, it should be noted that the above are only preferred embodiments of the present invention, and are not intended to be limiting. Although the present invention has been described in detail with reference to the experimental examples, the technical solutions described can be modified or equivalently replaced in part. The present invention is described in detail above, but is not limit thereto. Those skilled in the art should understand that various modifications or deformations made on the basis of the technical solutions of the present invention without creative work are still within the protection scope of the present invention.