CN108424487A - A kind of organic-silicon-modified emulsion water-proof agent of desulfurated plaster and preparation method thereof - Google Patents

Abstract

The invention discloses a kind of organic-silicon-modified emulsion water-proof agent of desulfurated plaster, by 20 25 parts of styrene, 25 30 parts of isobutyl acrylate, 45 parts of function monomer, 35 parts of emulsifier, 68 parts of organosilicon, 46 parts of Ludox, 40 50 parts of deionized water, 0.4 0.7 parts of potassium peroxydisulfate, 0.2 0.5 parts of compositions of 0.4 0.7 parts of sodium bicarbonate and polyvinyl alcohol, with good dispersion, solid content is high, stability is high, good weatherability and the characteristics of the intensity of desulfurated plaster product can be improved under certain condition, simultaneously, the invention also discloses the preparation methods of the organic-silicon-modified emulsion water-proof agent of desulfurated plaster.

Description

A kind of desulfurization gypsum organosilicon modified emulsion waterproofing agent and preparation method thereof

technical field

The invention relates to the technical fields of chemical engineering and materials, in particular to a desulfurized gypsum silicone modified emulsion waterproofing agent and a preparation method thereof.

Background technique

Desulfurization gypsum is an air-hardening material, suitable for wall materials, and has the advantages of wide source of raw materials, low energy consumption for material production, and good process performance. However, desulfurized gypsum products have a fatal weakness of poor water resistance. After absorbing water, the strength loss can reach 75%, and it is easy to warp and deform. Its application is greatly restricted. Therefore, the research of water-resistant desulfurized gypsum has always been a domestic and foreign research topic. subject of much attention. In order to solve the problems of desulfurized gypsum with reduced strength after being exposed to moisture, and poor water resistance such as easy warping and deformation, countries have adopted various methods and measures to study the water resistance of desulfurized gypsum, but the overall can be summarized into three aspects: on the one hand, in desulfurized gypsum The surface is coated or brushed with waterproof materials; on the other hand, finely ground inorganic materials are added to the desulfurized gypsum to improve the water resistance of the desulfurized gypsum; Water resistance.

Publication number: Chinese invention patent application of CN103553415A (disclosure date: February 05, 2014) discloses a cationic emulsified asphalt waterproofing agent for gypsum products. The water resistance problem of gypsum has not been fundamentally solved, and the waterproof effect does not have permanence; the Chinese invention patent application with publication number: CN103242018A (publication date on August 14, 2013) discloses a waterproofing agent for desulfurized gypsum blocks, The method uses stearic acid, polyvinyl alcohol, cement, and borate waterproofing agent to change the hydrophilic surface into a hydrophobic surface, thereby preventing the intrusion of moisture and achieving waterproofing; publication number: Chinese invention patent application of CN102180647A ( Public date (September 14, 2011) discloses a desulfurized building gypsum waterproof building block. The method uses 30%-94% desulfurized building gypsum, 0%-50% calcium silicate slag, and low-alkalinity sulphoaluminate cement 6 %-20%. For the improvement of desulfurized building gypsum blocks, the water resistance of gypsum blocks is greatly improved. Although this method has a certain waterproof effect, it greatly changes the purity of desulfurized gypsum, which is not conducive to the plasticity of desulfurized gypsum products; The Chinese invention patent application with publication number CN106186801A (publication date: December 07, 2016) discloses a preparation method of a composite modified gypsum waterproofing agent, which uses sodium methyl silicate, deionized water, abietic acid polyoxygen Vinyl esters, glycerin, polyvinyl alcohol and potassium persulfate are put into a reaction kettle protected by nitrogen gas to stir and react, and silicon fluoride is used to replace the gas in the reaction kettle to prepare gypsum waterproofing agent. This method requires high equipment conditions and consumes for a long time. At present, domestic water-emulsion type desulfurization gypsum waterproofing agents are mainly paraffin emulsion, rosin emulsion and asphalt modified emulsion. However, this type of waterproofing agent has two disadvantages: first, the amount of addition is relatively large, and the amount added is generally 10% of the amount of gypsum. Second, the storage stability is poor, and the general storage period is no more than 3 months.

Contents of the invention

In order to solve the technical defects in the above-mentioned prior art, the present invention provides a desulfurized gypsum organic silicon modified emulsion waterproofing agent with high conversion rate, convenient synthesis process, economical and environmental protection and its preparation method, which has stable performance and less addition And the preparation process is simple and so on.

The present invention solves its technical problem and realizes through the following technical solutions:

A desulfurized gypsum silicone modified emulsion waterproofing agent consists of the following components in parts by weight:

As preferred technical scheme, described styrene is the styrene that adopts 5% sodium hydroxide solution to carry out pretreatment and wash away polymerization inhibitor.

As a preferred technical scheme, the emulsifier is a non-ionic emulsifier nonylphenol polyoxyethylene ether and anionic emulsifier sodium lauryl sulfate composite emulsifier, the nonionic emulsifier nonylphenol polyoxyethylene ether, The ratio of anionic emulsifier sodium lauryl sulfate compound emulsifier is 4:1-2:1.

As a preferred technical solution, the functional monomer is one or more of methyl methacrylate, monobutyl itaconate, N-methylol acrylamide, and glycidyl methacrylate.

As a preferred technical solution, the silicone is one or more of KH-151, KH-550, MPTS, and hydrogen-containing silicone oil 203.

As a preferred technical solution, the silica sol is a dispersion system of colloidal particles of nano-scale amorphous silica in water or an organic solvent, the pH value of the silica sol is 2.0-7.0, and the average particle diameter is 10- 20nm.

The preparation method of the described desulfurized gypsum organosilicon modified emulsion waterproofing agent is characterized in that:

Step 1: take deionized water by weight, and divide into deionized water one, deionized water two and deionized water three, the weight ratio of described deionized water one, deionized water two and deionized water three is 1: 2:1, then carry out high-intensity stirring and mixing with deionized water-and the described composite emulsifier, styrene, isobutyl acrylate, and functional monomers obtained by weight, and the mixing time is 20min to prepare pre-emulsion a stand-by;

Step 2: Dissolve the ammonium persulfate in deionized water 2 in parts by weight, and prepare initiator solution b for use;

Step 3: Add sodium bicarbonate and deionized water into the reaction kettle according to the weight ratio, stir and dissolve, adjust the temperature to 60-70°C, and the reaction time is 30min, and prepare the solution c for use;

Step 4: Divide the pre-emulsion a in the step 1 into pre-emulsion a1 and pre-emulsion a2, divide the initiator solution b in the step 2 into initiator solution b1 and initiator solution b2, take The pre-emulsion a1 and the initiator solution b1 are dropped into the solution c in the step 3, and stirred and mixed, the stirring speed is 350-400r/min, and the temperature is adjusted to rise to 80-85°C to prepare Seed emulsion d for use;

Step 5: Take the organosilicon monomer by weight and mix it into the pre-emulsion a2 in the step 4, and then add it dropwise to the seed emulsion d in the step 4 at the same time as the initiator solution b2 in the step 4 , and stir and mix, the stirring speed is 280-340r/min, and keep warm for 1-2h at the same time, then add the silica sol and stir together for 30min, adjust the temperature to below 40°C, and prepare solution e for use;

Step 6: adjust the pH value of the solution e in the step 5 to 7-8 with ammonia water and filter to obtain the desulfurized gypsum silicone modified emulsion waterproofing agent.

The beneficial technical effect of the present invention is:

(1) Through the combination of nonionic emulsifier and anionic emulsifier, the stability of the modified emulsion is greatly improved, and the emulsion does not break for 1 hour at a speed of 400r/min;

(2) Add functional monomers to introduce functional groups into the polymer chain, thereby greatly improving the weather resistance and freeze-thaw resistance of the modified emulsion;

(3) Adding organosilicon monomers improves the cross-linking degree of the latex film and greatly improves the water resistance, dispersion and adhesion of the modified emulsion;

(4) A layer of hydrophobic film is formed on the desulfurized gypsum crystal, which will not destroy the crystal structure of desulfurized gypsum;

(5) With a dosage of 0.1%, the softening coefficient of the desulfurized gypsum can reach above 0.7, which greatly improves the application range of the desulfurized gypsum.

Detailed ways

The present invention is described in further detail below by specific embodiment, and following embodiment is descriptive only, is not limiting, can not limit protection scope of the present invention with this.

It should be noted that the styrene in the following examples is pretreated with 5% sodium hydroxide solution to wash away the styrene of the polymerization inhibitor; the emulsifier is nonionic emulsifier nonylphenol polyoxyethylene ether and anion Emulsifier sodium lauryl sulfate composite emulsifier, and the ratio of non-ionic emulsifier nonylphenol polyoxyethylene ether to anionic emulsifier sodium lauryl sulfate composite emulsifier is 4:1-2:1; single function The body is one or more of methyl methacrylate, monobutyl itaconate, N-methylol acrylamide, glycidyl methacrylate; the silicone is KH-151, KH-550, MPTS, One or more of hydrogen-containing silicone oil 203; silica sol is a dispersion system of nano-scale amorphous silica colloidal particles in water or organic solvents, the pH value of the silica sol is 2.0-7.0, and the average particle size The diameter is 10-20nm.

Example 1

A desulfurized gypsum silicone modified emulsion waterproofing agent consists of the following components in parts by weight:

Preparation

Step 1: take deionized water by weight, and divide into deionized water one, deionized water two and deionized water three, the weight ratio of described deionized water one, deionized water two and deionized water three is 1: 2:1, then carry out high-intensity stirring and mixing with deionized water-and the described composite emulsifier, styrene, isobutyl acrylate, and functional monomers obtained by weight, and the mixing time is 20min to prepare pre-emulsion a stand-by;

Step 2: Dissolve the ammonium persulfate in deionized water 2 in parts by weight, and prepare initiator solution b for use;

Step 3: Add sodium bicarbonate and deionized water into the reaction kettle according to the weight ratio, stir and dissolve, adjust the temperature to 60 ° C, and the reaction time is 30 minutes, and prepare the solution c for use;

Step 4: Divide the pre-emulsion a in the step 1 into pre-emulsion a1 and pre-emulsion a2, divide the initiator solution b in the step 2 into initiator solution b1 and initiator solution b2, take The pre-emulsion a1 and the initiator solution b1 are dropped into the solution c in the step 3, and stirred and mixed at a stirring speed of 400r/min, and the temperature is adjusted to 80°C to prepare the seed emulsion d to be prepared. use;

Step 5: Take the organosilicon monomer by weight and mix it into the pre-emulsion a2 in the step 4, and then add it dropwise to the seed emulsion d in the step 4 at the same time as the initiator solution b2 in the step 4 , and stirred and mixed, the stirring speed was 340r/min, and the temperature was kept for 1 hour at the same time, and then the silica sol was added and stirred together for 30 minutes, and the temperature was adjusted to be lower than 40°C, and the solution e was prepared for use;

Step 6: adjust the pH value of the solution e in the step 5 to 8 with ammonia water and filter to obtain the desulfurized gypsum silicone modified emulsion waterproofing agent.

Example 2

A desulfurized gypsum silicone modified emulsion waterproofing agent and a preparation method thereof, the weight ratio of each component is as follows:

Preparation

Step 1: take deionized water by weight, and divide into deionized water one, deionized water two and deionized water three, the weight ratio of described deionized water one, deionized water two and deionized water three is 1: 2:1, then carry out high-intensity stirring and mixing with deionized water-and the described composite emulsifier, styrene, isobutyl acrylate, and functional monomers obtained by weight, and the mixing time is 20min to prepare pre-emulsion a stand-by;

Step 2: Dissolve the ammonium persulfate in deionized water 2 in parts by weight, and prepare initiator solution b for use;

Step 3: Add sodium bicarbonate and deionized water into the reaction kettle according to the weight ratio, stir and dissolve, adjust the temperature to 70°C, and the reaction time is 30 minutes, and prepare the solution c for use;

Step 4: Divide the pre-emulsion a in the step 1 into pre-emulsion a1 and pre-emulsion a2, divide the initiator solution b in the step 2 into initiator solution b1 and initiator solution b2, take The pre-emulsion a1 and the initiator solution b1 are dropped into the solution c in the step 3, and stirred and mixed at a stirring speed of 350r/min, and the temperature is adjusted to 85°C to prepare the seed emulsion d to be use;

Step 5: Take the organosilicon monomer by weight and mix it into the pre-emulsion a2 in the step 4, and then add it dropwise to the seed emulsion d in the step 4 at the same time as the initiator solution b2 in the step 4 , and stirred and mixed, the stirring speed was 280r/min, and the temperature was kept for 2 hours at the same time, and then the silica sol was added and stirred together for 30 minutes, and the temperature was adjusted to be lower than 40°C, and the solution e was prepared for use;

Step 6: adjust the pH value of the solution e in the step 5 to 7 with ammonia water and filter to obtain the desulfurized gypsum silicone modified emulsion waterproofing agent.

Example 3

A desulfurized gypsum silicone modified emulsion waterproofing agent and a preparation method thereof, the weight ratio of each component is as follows:

Preparation

Step 1: take deionized water by weight, and divide into deionized water one, deionized water two and deionized water three, the weight ratio of described deionized water one, deionized water two and deionized water three is 1: 2:1, then carry out high-intensity stirring and mixing with deionized water-and the described composite emulsifier, styrene, isobutyl acrylate, and functional monomers obtained by weight, and the mixing time is 20min to prepare pre-emulsion a stand-by;

Step 2: Dissolve the ammonium persulfate in deionized water 2 in parts by weight, and prepare initiator solution b for use;

Step 3: Add sodium bicarbonate and deionized water into the reaction kettle according to the weight ratio, stir and dissolve, adjust the temperature to 60 ° C, and the reaction time is 30 minutes, and prepare the solution c for use;

Step 4: Divide the pre-emulsion a in the step 1 into pre-emulsion a1 and pre-emulsion a2, divide the initiator solution b in the step 2 into initiator solution b1 and initiator solution b2, take The pre-emulsion a1 and the initiator solution b1 are dropped into the solution c in the step 3, and stirred and mixed at a stirring speed of 350r/min, and the temperature is adjusted to 80°C to prepare the seed emulsion d to be prepared. use;

Step 5: Take the organosilicon monomer by weight and mix it into the pre-emulsion a2 in the step 4, and then add it dropwise to the seed emulsion d in the step 4 at the same time as the initiator solution b2 in the step 4 , and stirred and mixed, the stirring speed was 280r/min, and the temperature was kept for 1h at the same time, and then the silica sol was added and stirred together for 30min, and the temperature was adjusted to be lower than 40°C, and the solution e was prepared for use;

Step 6: adjust the pH value of the solution e in the step 5 to 7 with ammonia water and filter to obtain the desulfurized gypsum silicone modified emulsion waterproofing agent.

Example 4

A desulfurized gypsum silicone modified emulsion waterproofing agent and a preparation method thereof, the weight ratio of each component is as follows:

Preparation

Step 1: take deionized water by weight, and divide into deionized water one, deionized water two and deionized water three, the weight ratio of described deionized water one, deionized water two and deionized water three is 1: 2:1, then carry out high-intensity stirring and mixing with deionized water-and the described composite emulsifier, styrene, isobutyl acrylate, and functional monomers obtained by weight, and the mixing time is 20min to prepare pre-emulsion a stand-by;

Step 2: Dissolve the ammonium persulfate in deionized water 2 in parts by weight, and prepare initiator solution b for use;

Step 3: Add sodium bicarbonate and deionized water into the reaction kettle according to the weight ratio, stir and dissolve, adjust the temperature to 70°C, and the reaction time is 30 minutes, and prepare the solution c for use;

Step 4: Divide the pre-emulsion a in the step 1 into pre-emulsion a1 and pre-emulsion a2, divide the initiator solution b in the step 2 into initiator solution b1 and initiator solution b2, take The pre-emulsion a1 and the initiator solution b1 are dropped into the solution c in the step 3, and stirred and mixed at a stirring speed of 400r/min, and the temperature is adjusted to 85°C to prepare the seed emulsion d to be prepared. use;

Step 5: Take the organosilicon monomer by weight and mix it into the pre-emulsion a2 in the step 4, and then add it dropwise to the seed emulsion d in the step 4 at the same time as the initiator solution b2 in the step 4 , and stirred and mixed, the stirring speed was 340r/min, and the temperature was kept for 2 hours at the same time, and then the silica sol was added and stirred together for 30 minutes, and the temperature was adjusted to be lower than 40°C, and the solution e was prepared for use;

Step 6: adjust the pH value of the solution e in the step 5 to 8 with ammonia water and filter to obtain the desulfurized gypsum silicone modified emulsion waterproofing agent.

According to the material ratio in Example 1-4, accurately measure each component, and the prepared desulfurized gypsum waterproofing agent is stirred in NJ-160A slurry mixer for 2 minutes, according to GB/T 17669.4-1999 standard and GB/T 17669.3 -1999 Standard Experimental Method to test the physical and mechanical properties of desulfurized gypsum, the test results are shown in Table 1 and Table 2.

Table 1. Various performance tests of the desulfurized gypsum silicone modified emulsion waterproofing agent of Examples 1-4

Table 2 Tests of Examples 1-4 Desulfurized Gypsum Organosilicon Modified Emulsion Waterproofing Agent Used in Desulfurized Gypsum (Amount of 0.1%)

The results in Table 2 show that compared with not adding the desulfurized gypsum waterproofing agent, the desulfurized gypsum waterproofing agent of the present invention has a significant improvement in the performance of desulfurized gypsum.

The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (7)

1. a kind of organic-silicon-modified emulsion water-proof agent of desulfurated plaster, it is characterised in that：It is made of following parts by weight of component：

。

2. the organic-silicon-modified emulsion water-proof agent of desulfurated plaster according to claim 1, it is characterised in that：The styrene is The styrene of polymerization inhibitor is pre-processed and is washed away using 5% sodium hydroxide solution.

3. the organic-silicon-modified emulsion water-proof agent of desulfurated plaster according to claim 1 or 2, it is characterised in that：The emulsification Agent be nonionic emulsifier nonylphenol polyoxyethylene ether and anion emulsifier lauryl sodium sulfate compound emulsifying agent, it is described non- Ionic emulsifying agent nonylphenol polyoxyethylene ether, the ratio of anion emulsifier lauryl sodium sulfate compound emulsifying agent are 4:1-2: 1。

4. the organic-silicon-modified emulsion water-proof agent of desulfurated plaster according to claim 1 or 2, it is characterised in that：The function Monomer is one in methyl methacrylate, monobutyl itaconate, N hydroxymethyl acrylamide, glycidyl methacrylate Kind is several.

5. the organic-silicon-modified emulsion water-proof agent of desulfurated plaster according to claim 1 or 2, it is characterised in that：It is described organic Silicon is one or more of KH-151, KH-550, MPTS, containing hydrogen silicone oil 203.

6. the organic-silicon-modified emulsion water-proof agent of desulfurated plaster according to claim 1 or 2, it is characterised in that：The silicon is molten Glue is dispersion of the colloidal particle of nano level amorphous silica in water or organic solvent, the PH of the Ludox Value is 2.0-7.0, average grain diameter 10-20nm.

7. the preparation method of the organic-silicon-modified emulsion water-proof agent of desulfurated plaster according to claim 1, it is characterised in that：

Step 1：Ionized water is removed by weight, and is divided into deionized water one, deionized water two and deionized water three, it is described to go The weight ratio of ionized water one, deionized water two and deionized water three is 1:2:1, then take deionized water one and by weight The compound emulsifying agent, styrene, isobutyl acrylate, the function monomer obtained carries out high intensity and is stirred, and incorporation time is It is for use that pre-emulsion a is prepared in 20min；

Step 2：The ammonium persulfate is taken to be dissolved in deionized water two by weight, it is for use that allotment obtains initiator solution b；

Step 3：It takes sodium bicarbonate and deionized water three to be added in reaction kettle by weight, and stirring and dissolving, adjusts temperature liter Up to 60-70 DEG C, it is for use that solution c is prepared in reaction time 30min；

Step 4：It is pre-emulsion a1 and pre-emulsion a2 by a points of pre-emulsion in the step 1, it will be in the step 2 Initiator solution b points be initiator solution b1 and initiator solution b2, take the pre-emulsion a1 and the initiator solution B1 is instilled in the solution c in the step 3, and is stirred, mixing speed 350-400r/min, is adjusted temperature and is increased to 80-85 DEG C, it is for use that seed emulsion d is prepared；

Step 5：Take by weight in the pre-emulsion a2 that organic silicon monomer is mixed into the step 4, then with the step 4 In initiator solution b2 be added dropwise simultaneously into the seed emulsion d in the step 4, and be stirred, mixing speed 280- 340r/min, while insulation reaction 1-2h are added the Ludox and stir 30min together later, adjust temperature and are reduced to 40 DEG C Hereinafter, obtained solution e is for use；

Step 6：The pH value of the solution e in the step 5 is reconciled with ammonium hydroxide to 7-8 and is filtered, and the desulfurated plaster, which is made, to be had Machine Si modification emulsion water-proof agent.