TW201206990A - Semi-interpenetrating network hydrogel polymer, method for manufacturing the same, and cement composition containing the same - Google Patents

Abstract

A semi-interpenetrating network hydrogel polymer is disclosed, which is represented by the following formula (I): wherein m1, m2, n1, n2, and p each independently are an integer from 10 to 1000, and x and y each independently are an integer from 0 to 3. A method for manufacturing the semi-interpenetrating network hydrogel polymer and a cement composition containing the same are also disclosed.

Description

201206990 VI. Description of the Invention: [Technical Field] The present invention relates to a semi-interpenetrating network 'semi-IPN' type hydrogel polymer, a method for producing the same, and a cement composition using the same, Refers to a semi-interpenetrating network type hydrogel polymer which has good water absorption capacity for pure water or salt water, can reduce moisture loss of cement mortar sample body, and reduces cracks caused by plastic shrinkage, and a method for manufacturing the same and using the same Cement composition. [Prior Art] Concrete is the most widely used civil material for structural construction. The strength of concrete is derived from the hydration product of cement, and the hydration of cement is only sufficient in the environment where water is present. If it is cured in a dry environment, the moisture in the concrete will be volatilized from its surface, so that the hydration of the cement will slow down or even stop with the gradual evaporation of water, which will cause the concrete to shrink and crack. Carry out maintenance exercises to ensure that the concrete has sufficient moisture to ensure the cement hydration, develop sufficient strength 'and avoid dry shrinkage cracks." The properness of curing will affect the degree of hydration and dryness of cement in concrete. Shrinkage cracks, which in turn affect the development of concrete strength, durability and volume stability. If it is not properly maintained, it will not only have an adverse effect on the strength of the concrete, but also tend to produce dry shrinkage cracks, which will make the durability of the concrete structure worse. The maintenance of high performance concrete is more important than ordinary concrete. Because high-performance concrete is added with chemical additives, especially strong plasticizers, the water consumption is lower than that of ordinary concrete, but it still has a good work 201206990, and its hard-solid structure is dense, and the external water is difficult to penetrate. . However, due to the relatively small amount of mixing water of high-performance concrete, if it is not properly maintained, the moisture in the concrete is more likely to be volatilized from its surface, which will affect the hydration of the cement and the development of concrete strength, and produce shrinkage or turtles. Cracking affects the durability of concrete structures. The traditional method of curing concrete structures is the most commonly used method of stagnant water or continuous sprinkling. This method requires periodic watering, watering, or spraying, etc., not only for maintenance and labor, but also for wet and dry , often causing cracks inside the structure. Other conservation methods include cover method, demolition method, and liquid film maintenance method. These methods are all “add-on” curing methods. These methods can be used to achieve the desired maintenance purposes, but these methods require personnel cycles. Sexual watering, watering, or spraying, etc., not only saves labor and costs, and is not suitable for certain working environments or time courses, so it has its shortcomings and inconvenience. In order to improve these shortcomings, in recent years, some studies have turned to the application of "inner-type" curing agents, that is, to find a curing agent with water retention/release properties, and to add self-curing concrete to the self-curing concrete. ), in order to achieve the purpose of self-care, and replace the above-mentioned method of external conservation. The ingredients of the "inner type" curing agent are generally water-soluble resins, water-absorbent resins or hydrogels. Some studies have pointed out that if a water-soluble resin such as polyvinyl alcohol is used in a cementitious material such as cement slurry, cement mortar or concrete, after the water around the water-soluble resin is volatilized, the resin will precipitate and block the capillary pores of the cementitious material, hindering the moisture. The loss, so it can retain more moisture inside the material 'to make the cement hydrate more complete. In contrast, adding 201206990 water-based resin such as sodium polyacrylate or polyacrylate water gel in cementitious materials, because water gel can bind moisture inside, it can play the role of reservoir, when cementitious materials When the water volatilization is lost to the outside, the water inside the water gel will be released and replenished, so that the material can retain more water and higher humidity, so that the cement is more hydrated, and the material is less likely to shrink and crack. It can be seen from the above that compared with the traditional "add-on" curing method, if the "incorporating type" curing method is adopted, the self-curing agent is added to the concrete to self-maintain the material itself, which not only saves manpower, but also saves man-hours. It is not restricted by the working environment or time course, especially to effectively reduce the occurrence of concrete cracks' to improve the durability of concrete, reduce the maintenance of concrete structures, and ensure the service life. When the cement in the concrete encounters water, it will release various ions into the water and react to form hydration products. Therefore, the pore solution in the concrete will contain Na+, K+, Ca2+, OH*, S042 within a few hours. - Waiting for various ionized brines - so the water is added to the concrete as a self-curing agent to act as a reservoir. When the interior of the concrete consumes moisture due to cement hydration reaction, or the water volatilizes from the interior of the concrete to the outside, the water gel can release moisture in a timely manner to keep the interior of the concrete moist and avoid dry shrinkage cracks, so it is used as concrete. The water gel of the curing agent not only has a high water absorption rate in pure water, but also has a high water absorption rate in the brine, so that the function of the reservoir can be exerted. However, the commonly used sodium polyacrylate or polyacrylate water gel can be used as a self-curing agent for concrete, but it has a lot of room for improvement. The original reason is that although sodium polyacrylate or polypropylene 201206990 acid ester Water gel has a high water absorption rate in pure water. Each gram of water gel can absorb hundreds or even thousands of grams. However, the water absorption rate in brine is very low. Generally, water gel can absorb 0.1 M CaCl per gram of water. To ten grams. SUMMARY OF THE INVENTION The present invention relates to a semi-interpenetrating network type hydrocolloid polymer

(semi_interpenetrating network hydrogel polymer), which is as shown in the following formula (I):

Formula (1)

Wherein 'm〗, m2, ηι, n2, and p are integers from 1〇 to 1〇〇〇, respectively, and y are integers from 〇 to 3, respectively.

X

In the above formula (I), 'ΠΜ, ηι2, ηι, n2, p are more preferably integers from 3〇 to 500; m, m2 'η丨, n2, p are each an integer of 50 to 2〇〇, respectively. ; X and y are preferably 1. When the semi-interpenetrating network type hydrogel polymer of the present invention is placed in an aqueous solution of 01 M CaCl 2 , the semi-interpenetrating network type hydrogel polymer per gram has a water absorption ratio of 10 to 75 g for the CaCl 2 aqueous solution. Further, the present invention relates to a cement composition comprising: a curing agent which is represented by the following formula (I), 7 201206990

Conh2

O C02Na O:

〇2i-c^H〇2-^c\ CONH2 :0 c--C-(b)y C〇2Na j| (?Hi where (I) where 'm丨, m2, n丨, n2, p respectively An integer of 10 to 1000, X and y are each an integer of 0 to 3; and a cementitious material β. The cement composition of the present invention is based on the weight percentage of the cement slurry. The content is in the range of 0.01 to 0.5% by weight, more preferably in the range of 0.05 to 0.40% by weight, most preferably in the range of 0.1 to 0.3% by weight; in the above formula (1), m!, m2, η, η2 Preferably, ρ is an integer of 30 to 500; respectively, mi, m2, rh, η2, and ρ are each an integer of 50 to 200; χ and y are preferably 丨; the curing agent is placed in 〇. i μ CaCl2 aqueous solution. In the middle, the semi-interpenetrating network type hydrogel polymer per gram has a water absorption rate of 10 to 75 grams for the CaClyX solution; the cementitious material may be cement, cement mortar, concrete or a combination thereof, and may include: Acid tricalcium (c3s), dicalcium citrate (ce), tricalcium aluminate (c3A), tetracalcium aluminate (C4AF) or a combination thereof. Further, the cement composition of the present invention may Further, an appropriate amount of a plasticizer is included to increase workability. In addition, the present invention also relates to a method for producing a semi-interpenetrating network type hydrogel polymer, comprising the steps of: (a) polymerizing with aspartic acid monomer; The ring reaction forms polyaspartic acid; (b) the addition of halogen acetate reacts with the polydip 201206990 aspartic acid' to separate the element to form poly(4-formicylmethylamino)-4-oxobutyl (-(4-(carboxylatomethylamino)-4-oxobutanoate), PCM); and (c) adding the acrylamide and the poly(4-formicylmethylamino)-4-oxobutyrate The polymerization is carried out to form a half interpenetrating network type hydrogel polymer, which is represented by the following formula (I):

Formula (I) wherein mi, m2, ηι, n2, and p are each an integer from 1 〇 to 1 。. In the method for producing a semi-interpenetrating network type hydrogel polymer according to the present invention, in the step (a), the asparagine monomer can be polymerized to form a polyammonium imide, and then the polyammonium imide is further subjected to a ring opening reaction to form polyaspartic acid; the polyaspartic acid may be a-linkage polyaspartate; in step (b), the sulphate acetate and the The reaction molar ratio of polyaspartic acid may be 50-200: 1-5: in step (c), the acrylamide and the poly(4-formicylmethylamino)-4-oxobutanoic acid The reaction molar ratio of the ester) is 100-300: 1-5 » Compared with the common sodium polyacrylate or polyacrylate water gel, the semi-interpenetrating network type hydrogel polymer of the present invention has a better ratio in the brine. High water absorption, so when added to cementitious materials such as cement slurry, cement mortar or concrete, it can obtain better water storage capacity, so that cementitious materials have good water retention of 201206990, thus reducing cracks in materials. Produced, the semi-interpenetrating network type hydrogel polymer of the present invention is a concrete with superior performance. Curing agent 0 [Embodiment] The semi-interpenetrating network type hydrogel polymer of the present invention is obtained by reacting aspartic acid with acid to obtain polysuccinimide (PSI), and then PSI and hydroxide. Sodium reaction to obtain sodium polyaspartate (PAsp), followed by reaction of PAsp with sodium acetate to obtain poly(4-formylguanidino)-4 oxobutyrate (poly(4-(carboxylato)) -methylamino)-4-oxobutanoate), PCM), and finally polymerize PCM with acrylamide to form poly(4-formic acid guanamine)-4-oxobutyric acid S) / polyacrylamide ((poly(4-(carboxylatomethylamino)-4-oxobutanoate)/polyacrylamide), PCPA) ° Hereinafter, embodiments of the present invention will be described by way of specific embodiments, and those skilled in the art can easily disclose the contents disclosed in the present specification. Other advantages and effects of the present invention are understood. The present invention may be embodied or applied in various other specific embodiments, and various modifications and changes may be made without departing from the spirit and scope of the invention. Example 1 Poly(4-methylmercaptomethylamino)-4-oxobutanoate/polyacrylamide (PCPA) Synthesis 201206990 65.5 g of aspartic acid and 48.9 g of phosphoric acid were placed in a four-neck reaction flask, reacted in a 200 ° C oil bath for 4.5 hours, and extracted with decyl alcohol to obtain 55.7. A yellow viscous solid polysuccinimide (PSI). 20 g of polyacetamide and 15 g of sodium hydroxide were dissolved in 100 ml of water, and the reaction was stirred for 2 hours in an ice bath, and the pH of the solution was adjusted to 9-10 by using 12 hydrazine hydrochloric acid, followed by methanol. After extraction, the solvent was removed in an oven at 25 ° C for 24 hours to obtain 17.3 g of sodium polyspartate (PAsp). 57 g of sodium polyaspartate and 65.5 g of sodium bromoacetate were dissolved in 150 ml of aqueous ethanol solution (ethanol: water = 3:7), placed in a four-necked reaction flask, and treated with sodium hydroxide. The pH of the solution was adjusted to 9-10, the reaction was carried out at 78 ° C for 6 hours, and the reaction was stirred at room temperature for 1 day, and then extracted with acetone to obtain 96.8 g of poly(4-formicylmethylamino)-4-oxo. Poly(4-(carboxylato-methylamino)-4-oxobutanoate), PCM). 20 g of poly(4-formylmethylamino)·4-oxobutyrate) and 20 g of acrylamide were dissolved in 200 ml of deionized water and placed in a four-necked reactor. The reaction temperature is slowly raised to 75 ° C, and then an appropriate amount of ammonium persulfate as a starter and N,N-methylene diacrylamide as a crosslinking agent are added dropwise (Ν, Ν- Methylenebisacrylamide), continue to react for 20 minutes until the solution becomes colloidal. Purify with methanol, soak the product in deionized water, change water once every other day to remove unreacted monomer, and remove it at 55 ° after 3 days. After 24 hours in the C oven, 19.4 g of white solid semi-interpenetrating network (semi-IPN) water gel was obtained. 201206990 Polymer: poly(4-formicylmethylamino)-4- O.oly(4-(carboxylato-methylamino)-4-oxobutanoate)/poly-§_crylamide, PCPA). The spectrum of 111 is shown in Figure 1. Wavenumber 3438.2 (; 111-丨 is the absorption peak of 1^-11, 2969.4 cm·1 is the absorption peak of CH' 172〇丨cm-i is c=〇 The absorption peak, 1578.4 cm 1 is the absorption peak of -NH 2 , and 丨 173 3 cm.i is the absorption peak of c 。. Test Example 1 Two water gels were tested for the water absorption rate of the aqueous solution. One of them was the pcpA of the first embodiment. Water gel, another kind of polyacrylate water gel (code 386A, from Taiwan Plastics Co., Ltd.) as a comparative example 1. Take an appropriate amount of the first example and the first example of the water gel, placed in a tea bag dip Ionized water or Oi M CaCl2 brine, etc. After soaking for a certain period of time, take out the weight to obtain the weight of the water gel that absorbs the water, and the water gel can absorb the water before and after the water gel absorbs water. _ The two kinds of water gel in deionization The water absorption in water and 0.1 M CaCl2 brine is shown in Figure 2. 'The water absorption of the water gel increases first with the increase of the soaking time, and then gradually becomes flat. The maximum value is the saturated water absorption rate. · The saturated water absorption of the water gel of Comparative Example 1 in deionized water and 〇1 MCaCl2 brine It is 27,.9 g; each gram of the water gel in deionized water and (MMCaa2 brine, the saturated water absorption rate is similar and correct. The results show that the example - the water gel in deionized water and ... (four) cents The water absorption rate in the brine is higher than that of the water gel of Comparative Example 1, because the water gel structure of the first embodiment has a functional group of a cation (·.Ν+) and an anion (_c〇〇.), so that it can be adsorbed more. More water. Test Example 2 Water release rate test of cement slurry pore solution 12 201206990 Mixing cement slurry with water-cement ratio (W/C)=0.485, pumping the pore solution of cement in the air. Then take appropriate amount of Comparative Example 1 (386A water gel) and Example 1 (PCPA water gel), respectively, after saturated in deionized water, and then placed in the pore solution of cement glory in the water-cement ratio = 0.485 After soaking for different time, take out the weight of the water gel. When the water gel is immersed in the pore solution, the water inside the water gel will be released to the outside because of the difference in ion concentration inside and outside the water gel. Weight (wl) and water after soaking in a pore solution The relative weight difference of the weight of the glue (w2) is the water desorption ratio, ie: water release rate = (wl-w2) / wl χ 100% water release of the two water gels in the pore solution of the cement slurry The rate is shown in Fig. 3. It can be seen from Fig. 3 that after the water gel is placed in the pore solution, the water will be released quickly due to the poor penetration of the ion concentration in the water gel and the solution, and then reach a fixed value. The saturated water has 271 grams of water per gram of water in the comparative example. After being placed in the pore solution for 2 hours, the water gel will release water, from the initial water containing 271 grams of water per gram of water gel, down to gram of water per gram. It contained 51.4 g, that is, the water release rate of Comparative Example 1 water gel reached 81%. In contrast, the water release behavior of Example 1 after the water gel was placed in the pore solution was quite different from that of the first example. Each gram of water-absorbing gel that absorbs saturated water contains 426 grams of water. After being placed in the pore solution for 2 hours, the water gel releases less water, from the initial water containing 426 grams of water per gram of water gel, down to each The water gel contains 295 grams, that is, the water release rate of the water gel of the first embodiment is only 31%, and then the water gel changes from the water release state to the water absorption state, because the water gel of the first embodiment is in the pore solution for a period of time. A change has occurred in the functional group, that is, some of the guanamine groups (-CONH2) in the water-gel structure 13 201206990 are converted into a carboxylic acid group (-coo·), so that the water gel exhibits a phenomenon of first releasing water and then absorbing water. The results show that, compared with the water gel of the first example, the water gel of the first embodiment is added to the cement material such as cement slurry, cement mortar or concrete, and can bind more water inside, and can play the role of a reservoir. 〃When the moisture in the cementitious material is lost, the water inside the water gel can be released and replenished, so that the cement material can retain more water and higher humidity, and the cementitious material is less likely to shrink. crack. Test Example: Water-Soluble Agent for Cement Mortar Tests: The cement mortar with water-cement ratio (W/C) = 0.485 is added, and 0-0.2% (% by weight relative to cement) is added. Example 1 The amount of water gel was prepared into a 5x5x5 cm3 sample. At room temperature, the weight of the mortar sample is weighed at regular intervals to obtain the weight loss of the sample relative to the initial sample at a certain time. This is the weight of the moisture loss in the test vessel. Table 1 is the composition ratio of the cement mortar (W/C=0.485) to which the first embodiment is added, and the cement used is from the Portland cement type I Portland cement, and the fine sand used is Ottawa standard sand ( Ottawa sand), cement / sand = 1/2.75 (weight ratio), add appropriate amount of plasticizer (A30, from Qixin company), so that the new sand is controlled to a certain degree of fluidity. The fluidity test of the cement mortar test body is based on CNS 3655. After the mixed cement mortar is poured into the mold, it is shaken up and down 25 times in 15 seconds on the flow table, and the mortar diameter is measured 4 times, and the average is taken. value. 201206990 Table 1 Cement (g) Sand (g) Example 1 Water gel (g) Water (g) Strong plasticizer (g) Diffusion diameter (cm) Application comparison example 750 2062 0 363.8 0.61 21.2 Application example one 0.75 0.79 21.2 Application Example 2 1.50 0.96 20.9 Figure 4 is the moisture weight loss of the mortar sample to which the different water-gel dosages were added. The results show that the weight loss of the test piece rises as the standing time increases, and then tends to a constant value. Application Example 1 (addition of 0 75 g (water gel/cement = 0.1 ° / ❶) Example 1 water gel) and application example 2 (add 15 g (water gel / cement = 0.2%) Example 1 water gel) mortar The moisture loss of the sample was lower than that of the mortar sample of Comparative Example 1 (No Example 1 water gel). After 28 days of storage, the moisture weight loss of the mortar sample of Comparative Example 1 was 14 32 g. The moisture weight loss of the mortar samples of Application Example 1 and Application Example 2 was 13.72 g and 13.22 g, respectively, which were 95.8 ° / 〇 and 92.3% of the moisture weight loss of the mortar sample of Comparative Example 1 respectively. Therefore, the water gel of the embodiment of the present invention can reduce the loss of moisture in the cement mortar. Test Example 4: Effect of water-based glue agent on the compressive strength of cement mortar test piece. Mix the cement mortar with water-cement ratio (W/C) = 0.485 as in Test Example 3. The composition ratio is shown in Table 1 above. Example 1 The range of water gel dose is in the range of 0-0.2% (% by weight relative to cement). The test piece was made into 5χ5χ5 cm3 and placed in a constant temperature and humidity chamber at 25 °C '60% humidity. According to CNS 1232, the compressive test machine was used to test the compressive pressure of the sand test body for 3, 7 and 28 days. Intensity, the average of three test tests. 15 201206990 Figure 5 shows the compressive strength of the cement mortar sample of Example 1 in different proportions. The results show that the compressive strength of the test piece first rises first with the increase of curing time, and then tends to a fixed value. The compressive strength of the mortar sample of Application Example 1 and Application Example 2 (adding Example 1 water gel) is higher than that of the mortar sample of Comparative Example 1 (without adding water gel), and Application Example 2 (addition of 1.5 g (water) Glue/cement = 0.2%) The compressive strength of the mortar sample of Example 1 is higher than that of the mortar sample of the application example (0.75 g (water gel/cement = 0.1%) Example 1 water gel). After 28 days of standing, the compressive strength of the mortar sample of Comparative Example 1 was 31.9 MPa. The compressive strengths of the mortar samples of Application Example 1 and Application Example 2 were 32.8 MPa and 34.2 MPa, respectively. Therefore, the water gel of the novel embodiment of the present invention can increase the compressive strength of the cement mortar. The test example five water glue agent Dong to the cement mortar test body shrinkage film mixing test, such as test case three water-cement ratio (W / C) = 0.485 cement mortar into the mold, the composition ratio such as the above Table 1 It is shown that the amount of the water gel of Example 1 is in the range of 0-0.2% (% by weight relative to the cement). Pour the cement mortar into the mold and tamper it with a spatula. Place it in a constant temperature and humidity chamber (temperature: 25±2°C, humidity: 90±5°C) and remove the mold for 1 day. The X 2 X 1.7 cm3 sample was placed in a constant temperature and humidity chamber (temperature: 25 ± 2 ° C, humidity: 60 5%). Based on the first day, the dry shrinkage of the mortar sample was measured for the next day. Fig. 6 is the effect of the water-gel dosage of the first embodiment on the dry shrinkage of the cement mortar. The results show that the dry shrinkage of the test body first rises with the increase of the standing time, and then tends to be gentle. Application example 1 (add 〇·75 g (7jc glue/cement = 〇. 1%) Example 1 water gel) and application example 2 (add 1.5 g (water gel/cement = 0.2%) real 201206990 The dry shrinkage of the mortar sample was lower than that of the mortar sample of Comparative Example 1 (No Example 1 water gel was added). After 28 days, the dry shrinkage of the mortar of Comparative Example 1 was 0.236 mm, and the dry shrinkage of the mortar samples of Application Example 1 and Application Example 2 were 0.208 mm and 0.189 mm, respectively. The mortar sample has 88% and 80% shrinkage. Therefore, the novel embodiment of the present invention, the water-based glue can reduce the dry shrinkage of the cement mortar sample. The effect of the six-water gel dosage on the internal humidity of the cement mortar test mixture is mixed with the water-cement ratio of the test example (W/ The cement sand of C) = 0.485 is filled into the mold's composition ratio as shown in Table 1, wherein the amount of the water gel of Example 1 is in the range of 0-0.2% (% by weight relative to the cement). Pour the cement mortar into the mold and tamper it with a spatula. Place it in a constant temperature and humidity chamber (temperature: 25±2°C, humidity: 90±5%) and remove the mold for 1 day to obtain 32 X. 2 X 1.7 cm3 of the test piece' was placed in a constant temperature and humidity chamber (temperature: 25 ± 2 ° C, humidity: 60 ± 5%). Based on the first day, the humidity of the mortar sample at different times was measured by humidity. Figure 7 shows the effect of the water gel dose on the internal humidity of the cement mortar sample. The results show that the internal humidity of the sample is first fixed (100%), and the humidity begins to decrease with time after a certain time. Application Example 1 (addition of 0.75 g (water gel/cement = 0.1%) Example 1 water gel) and application example 2 (add 1 · 5 g (water gel / cement = 0.2%) Example 1 water gel) mortar test The internal humidity of the body decreased after 9 days and 12 days, respectively, and the humidity began to increase with time. The humidity of the mortar sample of Comparative Example 1 (with no addition of Example 1) began to increase with time after 8 days. decline. After 28 days, the internal humidity of the mortar sample of Comparative Example 1 was 64.7%, and the internal humidity of the application of Example 1 and Application Sand 2 201206990 was 66.8% and 68.7%, respectively. The internal humidity of the mortar sample was 3.2% and 6.2%. Therefore, the new embodiment of the present invention, the water gel, can increase the internal humidity of the cement mortar, thereby reducing the amount of dry shrinkage of the cement mortar. Test Example 7 Crack test of cement pulp Take a certain amount of cement, water, and cement of Comparative Example 1 (3 86Α水胜) or Example 1 (PCPA water gel) to obtain water-cement ratio (W/C)=0.3 The composition ratio of the slurry, as shown in Table 2, in which the water gel dose is 0-0.4% (% by weight relative to the cement). Pour the mixed cement slurry into a ring-shaped mold. The inner and outer rings of the mold are 15 cm and 30 cm in diameter respectively. There are some ribs on the outer ring and the inner surface of the outer ring to promote the cement slurry test. The body produces cracks with a height of 2.5 cm. An air funnel was placed 8 cm above the cement slurry test at a wind speed of 4.5 m/s. It was placed on the experimental table at room temperature. After one day, the number of cracks on the surface of the cement slurry was observed and recorded. The crack index (CI) is calculated using the formula below:

Cl = (IL1 +EL2)/2 where Ll = width at the beginning of each crack and L2 = width at the end of each crack. Table 2 Cement (g) Water (g) Comparative Example 1 Water gel (g) Example Water gel (g) Water gel / cement (wt%) Crack index (mm) Application comparison example 2100 630 0 0 0 0.43 Application example 3 0 2.1 0.1 0 Application Example 4 0 4.2 0.2 0 Application Comparison Example 3 2.1 0 0.1 0.34 Application Comparison Example 4 8.4 0 0.4 0.07 201206990 Cement material such as cement slurry, cement mortar or concrete after pouring, if the surface of the material is moisture When the volatilization rate is higher than the external or self-replenishing speed, it will shrink and crack. Generally, the higher the cement content in the material and the lower the water content, the more likely cracks are generated. Figure 8 shows the cracks produced on the surface of the ring cement slurry test specimens under certain conditions (wind speed of 4.5 m/s, room temperature) after one day. It can be observed that the addition of water glue is added to the cement slurry to reduce the crack occurrence. The CI value of the cement slurry of Comparative Example 2 (without adding water glue, Figure 8 (a)) is 0.43 mm, and the comparative example 3 is applied (adding 0.1% comparison) In the first example, the cement slurry of Figure 8(d)) has a CI value of 0.34 mm, while the CI value of the cement slurry used in Comparative Example 4 (adding 0.4% Comparative Example 1, Figure 8 (e)) is reduced to 0.07 mm. This result shows that the addition of the comparative example one water gel in the cement slurry can reduce the crack generation of the cement slurry, and the more the water glue is added, the better the effect. On the other hand, the application of the third example (adding 0.1% of the first water gel, Figure 8 (b)) or the application of the fourth example (adding 0.2% of the first water gel, Figure 8 (c)) of the cement slurry CI value trend At zero, it was confirmed that the addition of the first embodiment (pcpa water gel) was more effective in reducing the crack generation of the cement slurry than the addition of the first comparative example (386A water gel) in the cement slurry. This is because the first embodiment has better water absorption and water retention rate in the pore solution or the saline solution in the cement slurry than in the first embodiment, and can play the role of a reservoir, and tightly binds the water to the cement. In the material. When the moisture in the cementitious material is volatilized, the water inside the first embodiment has more water to be released and replenished, so that the material can retain more water and the moisture is less likely to shrink and crack. Therefore, the embodiment of the present invention is a concrete self-curing agent with superior performance. 201206990 The above test results show that the water gel of the first embodiment of the present invention has good water absorption capacity for pure water or salt water; when the moisture inside the cementitious material such as cement slurry, cement mortar or concrete is due to When the cement is consumed by the reaction, or is volatilized and lost to the outside of the material, the water in the water gel of the first embodiment is slowly released from the inside to be replenished. In addition, the addition of the first embodiment of the present invention to the cement mortar can reduce the water weight loss of the cement sand damaged test body and has the water retention effect, and can also increase the compressive strength of the cement sand test Zhao, and more importantly. The invention can reduce the crack caused by the shrinkage of the material and improve the durability of the material. Therefore, the semi-interpenetrating network type water-gel polymer of the invention is a concrete self-curing agent with superior performance. In summary, the semi-interpenetrating network type hydrogel polymer of the present invention has good water absorption capacity for pure water or brine, and can be used as a new self-curing agent for concrete, and at the same time can reduce the moisture weight loss of the cement mortar sample. It has a water retention effect and can reduce cracks caused by plastic shrinkage and improve durability. This may alleviate or even replace the traditional "additional" method to facilitate labor saving; if compared with the commonly used polyacrylate water gel, the semi-interpenetrating network type hydrogel polymer of the present invention has higher water absorption capacity in brine. The semi-interpenetrating network type hydrogel polymer of the present invention is a novel concrete self-curing agent with superior performance. The above-described embodiments are merely examples for the convenience of the description, and the scope of the claims is intended to be limited by the scope of the claims. 20 201206990 BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an IR spectrum diagram of PCPA in the first embodiment of the present invention. Fig. 2 is a graph showing the water absorption rate of the water gel in Comparative Example 1 and Example 1 in the test example 1 of the present invention. Fig. 3 is a graph showing the water release rate of the water gel in the cement slurry pore solution of Comparative Example 1 and Example 1 in Test Example 2 of the present invention. Figure 4 is a graph showing the water weight loss of the cement mortar sample of Example 1 in Test Example 3 of the present invention. Fig. 5 is a graph showing the compressive strength of the cement mortar sample of the first embodiment of the test example 4 of the present invention. Fig. 6 is a graph showing the amount of the water gel of the first embodiment of the test example 5 of the present invention on the dry shrinkage of the cement mortar. Fig. 7 is a graph showing the internal rubber humidity of the cement sand sample in the first example of the test example 6 of the present invention. Figure 8 is a test result of the crack of the test sample VII_cement slurry of the present invention, wherein (a) is the application of the second comparative example (no water gel is added), (b) is the application example three (adding the first example water gel), (c) is Application Example 4 (adding 〇2% Example 1 water gel) '(d) is Application Comparative Example 3 (adding 〇丨% Comparative Example 1), and (e) is Application Comparison Example 4 (adding 0.4%) Comparative Example 1). [Main component symbol description] None 0 21

Claims (1)

201206990 VII. Patent application scope: ^—A kind of semi-interpenetrating network type water-gel polymer, which is not as follows (1) Wherein ' mi, m2, nt, n2, p are integers from 10 to 1000, respectively, and X and y are integers from 〇 to 3, respectively. 2. The semi-interpenetrating network type hydrocolloid polymer as described in claim 1, wherein m丨, m2, m, n2, and p are each an integer of from 30 to 500. 3. The semi-interpenetrating network type hydrocolloid polymer as described in claim 1 which has a water absorption of 10 to 75 grams per gram in an aqueous solution of 〇·1 M CaCl 2 . 4. The semi-interpenetrating network type hydrogel polymer according to claim 1, wherein X and y are each 1. 5. A cement composition comprising: a curing agent, which is represented by the following formula (1), 22 201206990 COW Formula (1) wherein mi, m2, n2, and p are integers of 10 to 1000, respectively, and x and y are integers of 0 to 3, respectively; and a cementitious material. 6. The cement composition of claim 5, wherein the curing agent is present in an amount ranging from 〇.〇1 to 0.5% by weight based on the weight percent of the cement aggregate. 7. The cement composition according to claim 5, wherein m丨, m2, η丨, n2, and p of the formula (I) are each an integer of from 30 to 500. 8. The cement composition of claim 5, wherein the curing agent has a water absorption of from 10 to 75 grams per gram in a 0.1 M CaCl 2 aqueous solution. 9. The cement composition of claim 5, wherein the cementitious material is cement slurry, cement mortar, concrete or a combination thereof. 1. The cement composition according to claim 5, wherein the cementitious material comprises: tricalcium citrate (CsS), dicalcium citrate (c2S), tricalcium citrate (CsA), aluminum Tetracalcium ferrite (c4AF) or a combination thereof. 11. The cement composition according to claim 5, wherein X and y are respectively 1. 23 201206990 12. A method for producing a semi-interpenetrating network type hydrogel polymer, comprising the steps of: (a) polymerizing a ring opening reaction with aspartic acid monomer to form polyaspartic acid; (b) adding a letter The acetate is reacted with the polyaspartic acid to remove the halogen to form poly(4-formicylmethylamino)-4-oxobutyrate) (2ply(4-(carboxylatooiethyl mino)-4- Oxo seven utanoate, PCM); and (c) adding the acrylamide and the poly(4.methylcarbamate) 4-oxobutyrate to polymerize to form a half interpenetrating network type hydrogel polymerization The substance is as shown in the following formula (I): Wherein mi, m2, η丨, η2, and ρ are integers of 1〇 to 1〇〇〇, respectively. 13. The method for producing a semi-interpenetrating network type hydrogel polymer according to claim 12, wherein in the step (a), the asparagine monopolymer is first polymerized to form a polysuccinimide. Thereafter, the polysuccinimide is subjected to a ring opening reaction to form polyaspartic acid. 14. The method for producing a semi-interpenetrating network type hydrogel polymer according to claim 12, wherein the polyaspartic acid is an α-linkage polyaspartate. The method for producing a semi-interpenetrating network type hydrogel polymer according to claim 12, wherein in the step (b), the reaction of the (tetra) acetate with the polyaspartic acid is not The ear ratio is 5G2GQ: 15. 16. The method for producing a semi-interpenetrating network type hydrogel polymer according to claim 12, wherein in the step (4), the acrylamide and the poly(4-phthalic acid methylamino group) The reaction molar ratio of _4-oxobutyrate is 100-300: 1_5. 17. The method for producing a semi-interpenetrating network type water-based gel polymer according to claim 12, wherein the formula (1) is an integer of 30 to 500, respectively. 18. The method for producing a semi-interpenetrating network type hydrogel polymer according to claim 12, wherein the semi-interpenetrating network type hydrogel polymer has from 1 to 75 per gram in a 0.1 M CaCh aqueous solution. The water absorption rate of grams. Eight, round (see next page): 25