Silicate-modified high-toughness and low-heat polymer grouting material for reinforcement

Abstract

The present invention relates to a silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, which belongs to the technical field of materials. About 60% by weight of the raw materials of the silicate modified grouting material of the present invention is the silicate modified aqueous solution, and about 40% is the structural flame retardant isocyanate, and main components of the polymer grouting material are classified into inorganic components according to the main total proportion. The silicate-modified high-toughness and low-heat polymer grouting material for reinforcement of the present invention has excellent flame retardancy and compressive performance, wherein a compressive strength is ≥60 MPa, an oxygen index is ≥30%, and a maximum reaction temperature is ≤100° C., an odor grade (80° C.) is ≤3.5, a fog test is ≤5 mg (no physical additive flame retardant diffuses to the environment), bonding is ≥3 MPa, a shear strength is ≥20 MPa, and a tensile strength is ≥20 MPa.

Claims

1. A silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, comprising: a modified isocyanate and a silicate-modified aqueous solution; wherein a weight ratio of the modified isocyanate and the silicate-modified aqueous solution is at a range of 1:(1.25-1.3); a content of P in the modified isocyanate is 4.4%, a content of N in the modified isocyanate is 7.9%, and a content of NCO % in the modified isocyanate is 11.9%; and a structural formula of the modified isocyanate is as follows: ##STR00009## wherein components of the silicate-modified aqueous solution comprises: liquid sodium silicate, water, and a catalyst; wherein the liquid sodium silicate accounts for 90-95% by weight of the silicate-modified aqueous solution; the water accounts for 5-8% by weight of the silicate-modified aqueous solution; and the catalyst accounts for 0.5-1.5% by weight of the silicate-modified aqueous solution.

2. The silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, as recited in claim 1, wherein the liquid sodium silicate is an aqueous solution of sodium silicate, and a Baume degree thereof is 40.

3. The silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, as recited in claim 1, wherein the liquid sodium silicate is 2451 by Qingdao Haiwan Chemical.

4. The silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, as recited in claim 1, wherein the catalyst is a diethylene glycol solution of triethylenediamine with a concentration of 33%.

5. The silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, as recited in claim 1, wherein the catalyst is 33 lv from Evonik Specialty Chemicals in Shanghai Co., Ltd.

6. The silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, as recited in claim 1, wherein the silicate-modified high-toughness and low-heat polymer grouting material for reinforcement is obtained by reacting the modified isocyanate and the silicate modified aqueous solution, and synthetic steps of the modified isocyanate comprises: (1) generating 2-carboxyethyl phenyl hypophosphite ethylene glycol ester by reacting 2-carboxyethyl phenyl hypophosphorous acid and ethylene glycol according to a mole ratio of 1:1, and a reaction equation is as follows: ##STR00010## (2) generating a phosphorus-containing dihydric alcohol intermediate by processing an addition reaction between the 2-carboxyethylphenyl ethylene glycol hypophosphite and propylene oxide; and a reaction equation is as follows: ##STR00011## (3) polymerizing the phosphorus-containing dihydric alcohol intermediate and TDI are to obtain a difunctional modified flame retardant isocyanate compound, and a synthesis reaction equation is as follows: ##STR00012##

7. A method for synthesizing the silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, as recited in claim 6, specifically comprising steps of: (1) sending the 2-carboxyethylphenyl hypophosphorous acid by Wuhan Hezhong Biochemical Manufacturing Co., Ltd. and the ethylene glycol into a reaction kettle according to a molar ratio of 1:1, performing esterification under catalysis of sulfuric acid or organotin at a temperature in a range of 105-110° C., distilling off water generated from a column overhead, and obtaining 2-carboxyethylphenyl ethylene glycol hypophosphite; (2) heating the 2-carboxyethylphenyl ethylene glycol hypophosphite to a temperature in a range between 100 and 110° C. in the reactor, adopting potassium hydroxide as a catalyst, slowly adding propylene oxide in a molar ratio of 1:1; wherein reaction pressure gradually rises in the reactor, but a maximum pressure is kept below a pressure of 2.5 kg, keeping a temperature in the kettle between a range of 100-115° C., is maintaining the pressure for 4 hours after the feeding is completed, keeping the temperature in the reactor at about 100° C., processing vacuum pumping to remove un-reacted small molecules, and obtaining the phosphorus-containing dihydric alcohol intermediate; (3) heating the reactor to 48° C.-52° C., firstly adding all of the TDI according to a molar ratio of phosphorus-containing dihydric alcohol intermediate: TDI=1:(3-4), and then adding all of the phosphorus-containing dihydric alcohol intermediate at a uniform speed; (4) heating the reactor to a temperature in a range of 78° C.-82° C., and then reacting for 1.9 h-2.2 h; (5) removing TDI which is excessive and not reacted by a thin film evaporator; (6) cooling the reactor to a temperature in a range of 48° C.-52° C., taking out from the reactor and obtaining the modified isocyanate containing 4.4% of P; 7.9% of N and 11.9% of NCO % after packaging; (7) mixing the modified isocyanate and the silicate-modified aqueous solution according to a mass ratio in a range of 1:(1.25-1.3) to obtain the silicate modified high-toughness and low-heat polymer grouting material for reinforcement.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

[0034] The technical solutions in the embodiments of the present invention will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Example 1

[0035] According to a preferred embodiment of the present invention, a silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, comprises: a modified isocyanate and a silicate-modified aqueous solution; wherein a weight ratio of the modified isocyanate and the silicate-modified aqueous solution is at a range of 1:(1.25-1.3); a content of P in the modified isocyanate is 4.4%, a content of N in the modified isocyanate is 7.9%, and a content of NCO % in the modified isocyanate is 11.9%; and a structural formula of the modified isocyanate is as follows:

##STR00005##

[0036] Components of the silicate-modified aqueous solution comprises: liquid sodium silicate, water, and a catalyst; wherein the liquid sodium silicate accounts for 90-95% by weight of the silicate-modified aqueous solution; the water accounts for 5-8% by weight of the silicate-modified aqueous solution; and the catalyst accounts for 0.5-1.5% by weight of the silicate-modified aqueous solution. The liquid sodium silicate is an aqueous solution of sodium silicate, and a Baume degree thereof is 40. The liquid sodium silicate is 2451 by Qingdao Haiwan Chemical. The catalyst is a diethylene glycol solution of triethylenediamine with a concentration of 33%. The catalyst is 33 lv from Evonik Specialty Chemicals (Shanghai) Co., Ltd.

[0037] According to the preferred embodiment of the present invention, a method for synthezing the silicate-modified high-toughness and low-heat polymer grouting material for reinforcement, which is characterized in that the silicate-modified high-toughness and low-heat polymer grouting material for reinforcement is obtained by reacting the modified isocyanate and the silicate modified aqueous solution, and synthetic steps of the modified isocyanate comprises:

[0038] (1) generating 2-carboxyethyl phenyl hypophosphite ethylene glycol ester by reacting 2-carboxyethyl phenyl hypophosphorous acid and ethylene glycol according to a mole ratio of 1:1, and a reaction equation is as follows:

##STR00006##

[0039] (2) generating a phosphorus-containing dihydric alcohol intermediate by processing an addition reaction between the 2-carboxyethylphenyl ethylene glycol hypophosphite and propylene oxide; and a reaction equation is as follows:

##STR00007##

[0040] (3) polymerizing the phosphorus-containing dihydric alcohol intermediate and TDI are to obtain a difunctional modified flame retardant isocyanate compound, and a synthesis reaction equation is as follows:

##STR00008##

[0041] A specific synthesizing process of the silicate-modified high-toughness and low-heat polymer grouting material for reinforcement comprising steps of:

[0042] (1) sending the 2-carboxyethylphenyl hypophosphorous acid by Wuhan Hezhong Biochemical Manufacturing Co., Ltd. and the ethylene glycol into a reaction kettle according to a molar ratio of 1:1, performing esterification under catalysis of sulfuric acid or organotin at a temperature in a range of 105-110° C., distilling off water generated from a column overhead, and obtaining 2-carboxyethylphenyl ethylene glycol hypophosphite;

[0043] (2) heating the 2-carboxyethylphenyl ethylene glycol hypophosphite to a temperature in a range between 100 and 110° C. in the reactor, adopting potassium hydroxide as a catalyst, slowly adding propylene oxide in a molar ratio of 1:1; wherein reaction pressure gradually rises in the reactor, but a maximum pressure is kept below a pressure of 2.5 kg, keeping a temperature in the kettle between a range of 100-115° C., is maintaining the pressure for 4 hours after the feeding is completed, keeping the temperature in the reactor at about 100° C., processing vacuum pumping to remove un-reacted small molecules, and obtaining the phosphorus-containing dihydric alcohol intermediate;

[0044] (3) heating the reactor to 48° C.-52° C., firstly adding all of the TDI according to a molar ratio of phosphorus-containing dihydric alcohol intermediate: TDI=1:(3-4), and then adding all of the phosphorus-containing dihydric alcohol intermediate at a uniform speed;

[0045] (4) heating the reactor to a temperature in a range of 78° C.-82° C., and then reacting for 1.9 h-2.2 h;

[0046] (5) removing TDI which is excessive and not reacted by a thin film evaporator;

[0047] (6) cooling the reactor to a temperature in a range of 48° C.-52° C., taking out from the reactor and obtaining the modified isocyanate containing 4.4% of P; 7.9% of N and 11.9% of NCO % after packaging;

[0048] (7) mixing the modified isocyanate and the silicate-modified aqueous solution according to a mass ratio in a range of 1:(1.25-1.3) to obtain the silicate modified high-toughness and low-heat polymer grouting material for reinforcement.

Test Examples

[0049] A specific example of a modified isocyanate compound of the present invention in this test example to the grouting material is as follows.

[0050] A formulation of aqueous silicate is as follows:

TABLE-US-00001 2451 (Silicate Aqueous 92 Solution, by Qingdao Haiwan) Water 7.5 A33 (Catalyst, Evonik 0.5 Specialty Chemicals (Shanghai) Co., Ltd.) Total 100

[0051] Mix and stir 130 parts of the silicate aqueous solution mentioned above and 100 parts of the isocyanate component of each example in the following table to prepare a grouting material.

[0052] Isocyanate components in each test example:

TABLE-US-00002 Text Text Text Text example example example example Name 1 2 3 4 Isocyanate PM200 (Wanhua 100 0 0 74 component Chemical Group Co., Ltd.) 100LL (Wanhua 0 100 0 0 Chemical Group Co., Ltd.) Difunctional 0 0 100 0 Modified Flame Retardant Isocyanate Compounds Tep 0 0 0 26

[0053] The isocyanates corresponding to the above Test examples 1, 2, 3, and 4 according to the formula fractions in the above table are equal in weight, and fully react with the silicate aqueous solution in a weight ratio of 100:130.

[0054] The flame retardant and physical properties of each Test example are as follows:

TABLE-US-00003 Text Text Text Text ex- ex- ex- ex- ample ample ample ample Name 1 2 3 4 Flame retardant Oxygen Index (%) 28.1 28.0 29.2 28.9 properties Physical Maximum reaction 113 112 89 96 properties temperature (° C.) Compressive 46 41 45 33 strength (MPa) Maximum 31 33 48 41 compression set (%) Bond strength, MPa 3.3 3.1 4.2 2.6 Environmental Odor level (80° C.) 4 4 4 5 performance Fog test (/ mg) 5.64 5.89 5.56 68

[0055] Flame Retardant Properties and Physical Properties Test Standard: AQ1089-2020.

[0056] Odor level test standard: VDA270:1992;

[0057] Fog test standard: Q/ZK JS 364-201903.

[0058] In Test Example 3, identical quality of modified isocyanate is used instead of Pm200 on the basis of Test Example 1. Everything else remains unchanged. The OI is increased from 28.1 to 29.2, wherein 1.1 is increased. The reaction temperature decreased from 113° C. to 89° C. The compressive strength is 46 MPa and 45 MPa respectively, with little change. The compression set increased from 31% to 48%, indicating that the toughness of the material has improved significantly, and the bond strength is also increased from 3.3 MPa to 4.2 MPa. The odor level is 4, with o change. Fog test is from 5.64 mg to 5.56 mg, there is little change, indicating that the modified isocyanate has apparent advantages in flame retardancy, maximum reaction temperature, toughness and bond strength.

[0059] In Test Example 3, identical quality of modified isocyanate is used instead of 100 LL on the basis of Test Example 2. Everything else remains unchanged. The OI is increased from 28.0 to 29.2, wherein 1.2 is increased. The reaction temperature decreased from 112° C. to 89° C. The compressive strength is raised from 41 MPa and 45 MPa. The compression set increased from 33% to 48%, indicating that the toughness of the material has improved significantly, and the bond strength is also increased from 3.1 MPa to 4.2 MPa. The odor level is 4, with o change. Fog test is dropped from 5.89 mg to 5.56 mg, there is small change, indicating that comparing with the 100 LL, the modified isocyanate has apparent advantages in flame retardancy, maximum reaction temperature, toughness and bond strength.

[0060] In Test Example 4, 26 parts of a flame retardant of tep is used to replace PM200 of an identical quality on the basis of Test Example 1. Everything else remains unchanged. OI is increased from 28.1 to 28.9, a maximum reaction temperature is decreased from 113° C. to 96° C., with a decrease of 17° C. Compressive strength is decreased from 46 MPa to 33 Mpa. A maximum compressive deformation is increased from 31% to 41%, a bond strength decreased from 3.3 Mpa to 2.6 MPa, an odor level increased from 4 to 5, and a fog test value is increased from 6.34 mg to 68 mg, with an increase of 10 times, indicating that adding a flame retardant to improve the flame retardant performance will reduce the reaction temperature, compressive strength, and bonding strength, improve the flame retardant performance and toughness, and reduce the environmental protection performance of the material.

[0061] In Test example 4, Pm200 is used as isocyanate on the basis of Test Example 3, and flame retardant of tep is add at the same time, in such a manner that phosphorus content of the system is consistent. A maximum reaction temperature is increased from 89° C. to 96° C., and a compressive strength is reduced from 45 Mpa to 33 Mpa. A maximum deformation is reduced from 48% to 41%. Bond strength is reduced from 4.2 Mpa to 2.6 Mpa, an odor level is increased from 4 to 5. A fog test value is increased from 5.56 to 68, with an increase of 13 times, indicating that use of modified isocyanate improves the flame retardant properties have great advantages in controlling reaction temperature, improving material compressive strength, bonding strength, material toughness and improving environmental performance.

[0062] One skilled in the art will understand that the embodiment of the present invention as shown in the drawings and described above is exemplary only and not intended to be limiting.

[0063] It will thus be seen that the objects of the present invention have been fully and effectively accomplished. Its embodiments have been shown and described for the purposes of illustrating the functional and structural principles of the present invention and is subject to change without departure from such principles. Therefore, this invention includes all modifications encompassed within the spirit and scope of the following claims.