Polymer expanding material used in infiltration or seepage watery environment and preparation method thereof

Abstract

The present invention relates to a polymer expanding material in infiltration or seepage multi-water environment and a preparation method thereof, belonging to a technical field of polymer expanding foam materials. The polymer expanding material includes the following parts of materials by weight: 20-30 parts of rosin polyester polyol, 20-50 parts of isocyanate, 20-40 parts of PhireGuard® MB-512, 5-10 parts of HFO-1233zd, 1-2 parts of surfactant, 0.01-1 part of catalyst, and 0.01 parts of benzoyl chloride. The present invention has high sand fixing body strength, fast curing speed, good elastoplasticity, good pouring property and permeability, and good expanding property, which is suitable for infiltration or seepage multi-water environment, especially for dam infiltration, piping, and other problems during construction and subsequent operation of water conservancy projects.

Claims

1. A preparation method of a polymer expanding material in infiltration or seepage watery environment, comprising steps of: 1) adding 20-30 parts of rosin polyester polyol, 20-50 parts of isocyanate, 20-40 parts of chloroalkyl polyphosphate ester and 1-2 parts of surfactant into a reaction kettle, and stirring mixtures well; 2) replacing air in the reaction kettle with nitrogen gas; 3) heating the reaction kettle to 70-80° C., from when keeping reacting for 1-3 hours; and 4) cooling the reaction kettle to 25-30° C.; and then adding 5-10 parts of 1-chloro-3,3,3-trifluoropropene (HFO-1233zd) 0.01-1 part of catalyst and 0.01 part of benzoyl chloride into the reaction kettle, and stirring obtained mixtures for 10-30 minutes.

2. The preparation method, as recited in claim 1, wherein the isocyanate is any one or a combination of two of polymethylene polyphenyl isocyanate, diphenylmethane diisocyanate, and toluene diisocyanate.

3. The preparation method, as recited in claim 1, wherein the surfactant is sorbitan monooleate.

4. The preparation method, as recited in claim 1, wherein the surfactant is sorbitan oleate.

5. The preparation method, as recited in claim 1, wherein the catalyst is 4,4′-(oxydi-2,1-ethanediyl)bismorpholine.

Description

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

(1) The technical solutions according to embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of all the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by a person of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

Embodiment 1

(2) According to the embodiment, a polymer expanding material used in infiltration or seepage watery environment comprises: 25 g rosin polyester polyol (produced by the Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, brand: JC-380), 6 g polymethylene polyphenyl isocyanate (produced by Wanhua Chemical Group Co., Ltd., brand: WANNATE® 2208), 25 g diphenylmethane diisocyanate (produced by Wanhua Chemical Group Co., Ltd., brand: MDI100), 35 g reactive flame retardant (produced by Jiangsu Yake Technology Co., Ltd., brand: PhireGuard® MB-512), 7 g physical foaming agent (HFO-1233zd), 1 g surfactant (EMALEX® SPO-100), 0.01 g benzoyl chloride (chemically pure), and 0.99 g catalyst (4,4′-(oxydi-2,1-ethanediyl)bismorpholine (HUNTSMAN®)).

(3) According to the embodiment, a preparation method comprises the following steps:

(4) 1) adding the measured rosin polyester polyol, isocyanate, PhireGuard® MB-512, and EMALEX® SPO-100 into a reaction kettle;

(5) 2) replacing the air in the reaction kettle with the nitrogen gas;

(6) 3) heating the reaction kettle to 75° C., from when keeping the reaction time for 2.5 hours; and

(7) 4) cooling the reaction kettle to 30° C.; adding the measured HFO-1233zd, catalyst and benzoyl chloride into the reaction kettle, and stirring the obtained mixtures for about 20 minutes.

Embodiment 2

(8) According to the embodiment, a polymer expanding material used in the infiltration or seepage watery environment comprises: 20 g rosin polyester polyol (produced by the Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, brand: JC-380), 50 g diphenylmethane diisocyanate (produced by Wanhua Chemical Group Co., Ltd., brand: MDI100), 20 g reactive flame retardant (produced by Jiangsu Yake Technology Co., Ltd., brand: PhireGuard® MB-512), 8.8 g physical foaming agent (HFO-1233zd), 1 g surfactant (EMALEX® SPO-100), 0.01 g benzoyl chloride (chemically pure), and 0.19 g catalyst (4,4′-(oxydi-2,1-ethanediyl)bismorpholine (HUNTSMAN®)).

(9) According to the embodiment, a preparation method comprises the following steps:

(10) 1) adding the measured rosin polyester polyol, isocyanate, PhireGuard® MB-512, and EMALEX® SPO-100 into a reaction kettle;

(11) 2) replacing the air in the reaction kettle with the nitrogen gas;

(12) 3) heating the reaction kettle to 70° C., from when keeping the reaction time for 1 hour; and

(13) 4) cooling the reaction kettle to 30° C.; adding the measured HFO-1233zd, catalyst and benzoyl chloride into the reaction kettle, and stirring the obtained mixtures for 25 minutes.

Embodiment 3

(14) According to the embodiment, a polymer expanding material used in the infiltration or seepage watery environment comprises: 30 g rosin polyester polyol (produced by the Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, brand: JC-380), 15.6 g polymethylene polyphenyl isocyanate (produced by Wanhua Chemical Group Co., Ltd., brand: WANNATE® 2208), 20 g toluene diisocyanate (produced by Wanhua Chemical Group Co., Ltd.), 22 g reactive flame retardant (produced by Jiangsu Yake Technology Co., Ltd., brand: PhireGuard® MB-512), 10 g physical foaming agent (HFO-1233zd), 2 g surfactant (EMALEX® SPO-100), 0.01 g benzoyl chloride (chemically pure), and 0.39 g catalyst (4,4′-(oxydi-2,1-ethanediyl)bismorpholine (HUNTSMAN®)).

(15) According to the embodiment, a preparation method comprises the following steps:

(16) 1) adding the measured rosin polyester polyol, isocyanate, PhireGuard® MB-512, and EMALEX® SPO-100 into a reaction kettle;

(17) 2) replacing the air in the reaction kettle with the nitrogen gas;

(18) 3) heating the reaction kettle to 80° C., from when keeping the reaction time for 2.3 hours; and

(19) 4) cooling the reaction kettle to 25° C.; adding the measured HFO-1233zd, catalyst and benzoyl chloride to the reaction kettle, and stirring the obtained mixtures for 20 minutes.

Embodiment 4

(20) According to the embodiment, a polymer expanding material used in the infiltration or seepage watery environment comprises: 30 g rosin polyester polyol (produced by the Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry, brand: JC-380), 5 g polymethylene polyphenyl isocyanate (produced by Wanhua Chemical Group Co., Ltd., brand: WANNATE® 2208), 17.8 g diphenylmethane diisocyanate (produced by Wanhua Chemical Group Co., Ltd., brand: MDI100), 40 g reactive flame retardant (produced by Jiangsu Yake Technology Co., Ltd., brand: PhireGuard® MB-512), 5 g physical foaming agent (HFO-1233zd), 1.5 g surfactant (EMALEX® SPO-100), 0.01 g benzoyl chloride (chemically pure), and 0.69 g catalyst (4,4′-(oxydi-2,1-ethanediyl)bismorpholine (HUNTSMAN®)).

(21) According to the embodiment, a preparation method comprises the following steps:

(22) 1) adding the measured rosin polyester polyol, isocyanate, PhireGuard® MB-512, and surfactant into a reaction kettle, and stirring the mixtures well;

(23) 2) replacing the air in the reaction kettle with the nitrogen gas;

(24) 3) heating the reaction kettle to 80° C., from when keeping the reaction time for 1 hour; and

(25) 4) cooling the reaction kettle to 30° C.; adding the measured HFO-1233zd, catalyst and benzoyl chloride into the reaction kettle, and stirring the obtained mixtures for 30 minutes.

(26) The physical and mechanical properties of the polymer expanding materials used in the infiltration or seepage watery environment mentioned in the above four embodiments and a conventional polymer expanding material are listed in Table 1.

(27) TABLE-US-00001 TABLE 1 The comparison between the Physical and mechanical properties of the polymer expanding materials used in the infiltration or seepage watery environment of the present invention and that of a conventional polymer expanding material conventional polymer Physical expanding property Unit Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 material Anhydrous Visual Uniform Uniform Uniform Uniform Uniform environment inspection yellow foam yellow foam yellow foam yellow foam yellow foam grouting appearance Anhydrous Kg/m.sup.3  213 143 94 247 52 environment grouting density Anhydrous mPa 2.24 1.79 0.91 2.98 0.32 environment grouting compressive strength Anhydrous Permeable/ Impermeable Impermeable Impermeable Impermeable Impermeable environment impermeable grouting water permeability Anhydrous Times 6.10 9.09 13.83 5.26 21.54 environment grouting expansion rate Seepage Visual Uniform Uniform Uniform Uniform Uniform multi-water inspection yellow foam yellow foam yellow foam yellow foam yellow foam environment grouting appearance Seepage Kg/m3.sup.  162.60 86.67 49.74 202.46 17 multi-water environment grouting density Seepage mPa 1.84 0.83 0.37 2.21 0.03 multi-water environment grouting compressive strength Seepage Permeable/ Impermeable Impermeable Impermeable Impermeable Permeable multi-water impermeable environment grouting water permeability Seepage Times 8.00 15.00 26.14 6.42 61.67 multi-water environment grouting expansion rate Ratio of — 1.31 1.65 1.89 1.22 2.86 grouting expansion rates in anhydrous environment and infiltration or seepage multi-water environment

(28) In the above embodiments, the polyol and the isocyanate are prepolymerized in the reaction kettle before grouting, so that the polyol can fully reacted with the isocyanate, wherein the remaining isocyanate then reacts with water in the infiltration environment during grouting. The rosin polyester polyol with the hydroxyl value of 350-450 mgKOH/g and viscosity of 5000-12000 mPa.Math.s (25° C.), the PhireGuard® MB-512 and some other materials are used to provide the raw material with high density (specific gravity of ≥1.3 kg/m3) and high viscosity (≥7000 mPa.Math.s (25° C.)). The HFO-1233zd is used (having a boiling point of 19° C.) as a physical foaming agent, wherein such a low boiling point can make the material expand more than 5 times (density ≤260 kg/m.sup.3) even in the absence of water and low temperature, thereby effectively fill the cracks and block the outlets. When grouting in the anhydrous environment, the polymer expanding materials obtained in the embodiments 1-4 have material densities of ≤260 kg/m.sup.3, and they are all impermeable and with the expansion rates of ≥5. The expansion ratio of materials used in the anhydrous environment and the infiltration or seepage multi-water environment are all ≤2. During grouting under dry conditions and single-component high-pressure grouting in infiltration or seepage multi-water environment (a grouting pressure is no less than 50 kg), an expansion rate of the material is ≥5 and an expansion rate is ≤2. Furthermore, the material is impermeable. The present invention is suitable for infiltration or seepage watery environment, especially for dam infiltration, piping, and other problems during construction and subsequent operation of water conservancy projects.

(29) Although the embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, and substitutions can be made to these embodiments without departing from the principle and spirit of the present invention. The protection scope of the present invention is defined by the appended claims and their equivalents.