CN111662536A - Novel graphene modified water-containing vinyl ester resin and preparation method thereof - Google Patents
Novel graphene modified water-containing vinyl ester resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a novel graphene modified aqueous vinyl ester resin and a preparation method thereof. The resin is prepared from the following raw materials in parts by weight: 600 parts of water 200-containing materials, 400 parts of modified vinyl ester resin 800-containing materials, 10-50 parts of hydrophilic agents, 30-100 parts of soft matter transforming agents, 20-60 parts of stabilizing agents and 5-10 parts of functional graphene. Compared with oily vinyl ester resin, the performance of the aqueous vinyl ester resin is obviously improved in alkali resistance, flame retardance, flexibility and temperature resistance, more importantly, the aqueous vinyl ester resin is environment-friendly resin, can be used for desulfurization and denitration, solves the problem of smoke whitening, floors, industrial anticorrosive coatings and the like, and has wide application space.
Description
Technical Field
The invention relates to the technical field of soft substances, in particular to a novel graphene modified water-containing vinyl ester resin and a preparation method thereof.
Background
Soft matter is an emerging discipline emerging in recent years, referred to as "complex fluids" in the united states. In 1991, the concept of soft substances was proposed by the Nobel physics awarding the subject of the main heat susceptance to give a bonus presentation. Soft matter refers to matter intermediate between solid and ideal fluids, generally consisting of macromolecules or groups, such as liquid crystals, polymers, colloids, films, foams, particulate matter, life system matter, and the like, which are ubiquitous in nature, life, everyday life, and production. Many international research institutions are actively developing soft material research, and the soft material content is already available in foreign physical textbooks but not seen in China.
The material is converted into soft material by a new technology, and the soft material has qualitative change, so that the soft material has many properties which the original material does not have at all.
Soft matter has two essential features:
1. very weak external actions have very strong responses.
2. Very small amounts of additives can dramatically change the properties of soft material systems.
Soft materials are said to be "soft" compared to hard materials such as metals, semiconductors, ceramics, etc., because there is no hard structure like a solid. The device can make relatively obvious response and change to relatively weak external influence, such as small change of material composition or structure, such as instant or weak stimulus applied to the material, and the like, namely has the characteristic of weak influence and strong response.
Roughly speaking, soft matter mainly includes two aspects: complexity, variability.
The changeability of the soft substance means that the resistance of the soft substance is weak, the change is usually nonlinear, but the direction and the magnitude of the change of the system can be known.
Hard substance: large stress produces small deformation;
soft matter: the small stress generates large deformation;
the physicist has been prepared with rubber as an example to illustrate the unusual properties of soft materials. Natural rubber is susceptible to oxidation and breakage in air, but becomes a strong and durable material after vulcanization. The sodium indicates that only 1 atom of every 200 carbon atoms of natural rubber reacts with sulfur. Although the chemical action is so weak, it is sufficient to cause a large change in the physical properties of the rubber from liquid to solid, and the change of the gum into rubber proves that some substances change state due to the weak action, which is the unusual characteristic of soft substances-the weak force causes a strong change.
Since the state of the soft matter is between that of a liquid and an ideal solid, molecules in a simple liquid can flow freely, limited only by the container; molecules in an ideal solid move thermally near a fixed position and cannot change sequence, while soft materials have the thermal fluctuation behavior of liquid and the strong binding self-organization property of the solid.
With the increasing awareness of environmental protection, water-based resins using water as a solvent or a dispersion medium are increasingly gaining attention. The water-based resin taking water as a dispersion medium or solvent is not only an environment-friendly material, but also has good construction performance (low viscosity, good permeability, room-temperature curing, nontoxicity, small volatility, environment-friendly property and the like), can be constructed on a wet surface, has low requirements on construction environment, is convenient to clean, is safe to store, transport and use, and has low price, so that the water-based resin becomes the development direction of resin production and application at home and abroad.
The water-based resin has the following remarkable characteristics: good wetting property to inorganic pigments, fillers and glass fibers, good mechanical property, good processing property, flame retardance, low shrinkage and the like.
Disclosure of Invention
The aqueous vinyl ester resin of the present invention is prepared by a soft material preparation technique, wherein water is first prepared into a soft material, and then the soft material is crosslinked with the resin to form the novel aqueous resin. The aqueous vinyl ester resins of the present invention are distinguished from any aqueous resins in that the water in the aqueous resin product does not evaporate to form a film, but must evaporate after the aqueous resin has formed a film. Firstly, the fundamental difference between the water-based resin and the water-based resin is that the water-based resin such as the water-based epoxy resin and the water-based acrylic resin has to be volatilized after the water-based resin and the water-based resin are made into products, but the water-based vinyl ester resin researched by the patent of the invention skillfully fuses the water and the resin together, so that the originally added water is kept but is not volatilized in the prepared coating, daub, glass fiber reinforced plastic and foaming body, which is the essential difference between the water-based resin and the water-based resin. The implementation of the technology has to be out of the conventional thinking and realized by adopting the soft matter preparation technology.
The greatest innovation of the technology is that water is used for replacing partial resin, the technology is essentially different from water-based resin, and the implementation of the technology is best proved by the implementation of soft substance technology. The use of softened water in combination with a resin to form an aqueous resin having the characteristics of a resin which enhances the heat resistance, alkali resistance, flexibility and fire resistance of the neat resin is an object of the present invention.
The first aspect of the invention provides a novel graphene modified hydrous vinyl ester resin, which is prepared from the following raw materials in parts by weight:
600 parts of water, 800 parts of modified vinyl ester resin, 10-50 parts of hydrophilic agent, 30-100 parts of soft matter transforming agent, 20-60 parts of stabilizing agent and 5-10 parts of functional graphene;
the functional graphene is prepared from the following raw materials: 3-15 parts of graphene, 0.1-0.5 part of coupling agent or cross-linking agent, 200 parts of carrier, 0.03-0.3 part of anti-flocculating agent and 0.1-0.5 part of anti-precipitating agent.
In some embodiments of the invention, the water is purified water meeting GB17323-1998 or drinking water meeting GB 5749-2006.
Water is a very important component, and some mineral ions in water are too high to affect the mechanical and chemical properties of the finally obtained resin, especially the alkali resistance.
In some embodiments of the invention, the modified vinyl ester resin is a hydroxyl modified vinyl ester resin, preferably xinco-221, and more preferably xinco-221 having an acid number of 8 to 15.
The adopted modified vinyl ester resin is different from common similar products, but is the hydroxylated modified vinyl ester resin, and the mechanical property is not ideal in the combination of the unmodified vinyl ester resin and water.
In some embodiments of the invention, the hydrophilic agent is a nonionic surfactant, preferably one or more of a sorbitan fatty acid ester, a fatty alcohol polyoxypropylene ether, and a dispersion solubilizer S, KBK-305305.
The function of the hydrophilic agent is to further enable the modified vinyl ester resin to have stronger hydrophilic function and promote the combination of the vinyl ester resin and water. In research, the mixture of the fatty alcohol polyoxypropylene ether and the sorbitan fatty acid ester has very good effect, is better than the single sorbitan fatty acid ester, the fatty alcohol polyoxypropylene ether and the dispersion solubilizer S, KBK-305305, particularly takes the combination with the weight ratio of 1:2 as the best effect, and obviously influences the flexibility of the finally obtained resin.
In some embodiments of the present invention, the soft matter conversion agent is a nonionic surfactant, preferably one or more of sorbitan glycerides and polyoxyethylene ethers.
The soft matter transforming agent endows water with lipophilic function and water loss function. When the temperature resistance of the finally obtained resin is inspected, the sorbitan glyceride soft substance conversion agent is obviously superior to polyoxyethylene ether. The xinco-608 used in the examples is a 1:1 weight ratio combination of glyceryl sorbitan monostearate and glyceryl sorbitan monooleate.
In some embodiments of the present invention, the stabilizer is selected from one or more of a cellulose-based thickener, a polyacrylic-based thickener, a polyoxyethylene-based thickener, preferably one or more of polyvinyl alcohol, carboxyl paste starch, and hydroxy cellulose.
The stabilizer serves to enhance the storage stability of the finally obtained resin (aqueous vinyl ester resin) and can be a thickening agent or an anti-settling agent.
In some embodiments of the present invention, the functional graphene is prepared from graphene by the following steps:
s1, mixing graphene, a cross-linking agent or a coupling agent and a carrier;
s2, grinding to obtain a graphene polymer primary polymer;
s3, adding an anti-flocculant and an anti-settling agent into the graphene polymer primary polymer, and grinding to obtain the functional graphene;
preferably, the crosslinking or coupling agent is one or more of titanate, vulcanizing agent bis 25 and dicumyl peroxide DCP;
preferably, the carrier comprises an epoxy resin or a carrier plasticizer dibutyl ester;
preferably, the deflocculant is one or more of polyacrylamide, Efka LP-9009 and BEVLOID 6721;
preferably, the anti-precipitation agent is one or more of solvent type anti-precipitation agents 202P, 6900-20X and 4400-20X;
preferably, 0.03-0.10 part of anti-flocculant and 0.1-0.8 part of anti-precipitant are added into the graphene polymer primary polymer, and the functional graphene is obtained by grinding.
The second aspect of the present invention provides the method for producing the resin of the first aspect, comprising the steps of:
s11, mixing a hydrophilic agent with the modified vinyl ester resin, heating, and performing dispersion treatment to obtain A;
s12, mixing the soft matter transforming agent with water, and softening to obtain B;
s13, preparing functional graphene;
s14, dropwise adding the B into the A, adding the functional graphene and the stabilizer, and performing dispersion treatment;
in some embodiments of the present invention, the step S11 of controlling the parts by weight of the hydrophilic agent and the modified vinyl ester resin comprises the following steps:
step A1, constructing sample data according to the following formula:
wherein X represents a sample data matrix formed by n recordings of the hydrophilizing agent and the modified vinyl ester resin in different parts by weight, wherein the matrix has n rows and 2 columns, the first column of the matrix X represents the part by weight of the hydrophilizing agent added in each of the n recordings, and X represents the weight of the hydrophilizing agent added in each of the n recordings11Represents the part by weight of the hydrophilic agent in the first recording, the second column of the matrix X represents the part by weight of the modified vinyl ester resin added each time in n recordings, X21Represents parts by weight of the modified vinyl ester resin in the first recording;
step A2, calculating the information loss amount in the matrix A according to the following formula:
wherein, JiRepresenting the information loss of the ith column of the matrix X, i.e. the information loss of the ith material, n representing the total number of rows of the matrix X, XijA value representing the ith column and the jth row of the matrix X, and t representing the temperature at the time of reaction, i being 1,2, j being 1,2, 3.
And a step A3 of controlling the parts by weight of the hydrophilizing agent and the modified vinyl ester resin based on the information loss amount obtained in the step A2, wherein the parts by weight of the hydrophilizing agent is decreased when the information loss amount of the hydrophilizing agent obtained is excessively large, and the parts by weight of the vinyl ester resin is decreased when the information loss amount of the vinyl ester resin obtained is excessively large.
The information loss amount of each material can be obtained by the technology, the larger the information loss of the material is, the larger the obtained value is, so when the obtained information loss amount of the hydrophilic agent is too large, the weight part of the hydrophilic agent is reduced, when the obtained information loss amount of the vinyl ester resin is too large, the weight part of the vinyl ester resin is reduced, the accuracy and precision of laboratory data amount are improved, unnecessary waste caused by experiments is avoided, and the method has a strong mathematical theoretical basis.
In some embodiments of the present invention, the dispersion treatment in S11 is to utilize a high speed disperser 300-.
In the step S11, low-speed dispersion is performed first, and then medium-speed dispersion is performed. The time required for dispersion can be greatly reduced, and the dispersion time is saved by at least 10min compared with the constant low speed (300 and 500 revolutions/min) and the constant medium speed (2000 and 3000 revolutions/min).
In some embodiments of the present invention, the softening treatment in S12 is performed by using a high speed disperser 3000-.
In some embodiments of the present invention, the dispersing process in S14 is to disperse for 30-50min at 1000-3000 rpm of the high speed disperser, and then increase the speed to 8000-10000 rpm for 1-3 h.
In the step A14, medium-speed and high-speed dispersion is adopted, and compared with medium-speed (1000-.
The invention has the beneficial effects that:
compared with oily vinyl ester resin, the performance of the aqueous vinyl ester resin is obviously improved in alkali resistance, flame retardance, flexibility and temperature resistance, and more importantly, the aqueous vinyl ester resin is environment-friendly resin, can be used for desulfurization and denitration, solves the problem of smoke whitening, floors, industrial anticorrosive coatings and the like, and has wide application space.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
Before the present embodiments are further described, it is to be understood that the scope of the invention is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
In the following examples and comparative examples, parallel tests of the same operation were conducted unless otherwise specified. The stirring was carried out in a high speed disperser model ESJ-500, available from shanghai jele electromechanical devices, ltd. The grinding was carried out in a grinder, model EDW-1 nano-sand grinder, available from shanghai jele electromechanical devices limited company. The modified vinyl ester resin is xinco-221 type modified vinyl ester resin which is purchased from Qitai Xin Ke nanometer new material science and technology development limited company. The fatty alcohol polyoxypropylene ether S-60 is purchased from Heisen chemical Limited. The specific surface area of the graphene oxide is more than or equal to 50m2(ii) in terms of/g. The dispersion solubilizer S is purchased from Jiangsu Haian petrochemical plants. The type 201 titanate coupling agent is available from Nanjing Temeng chemical Co. The water is purified water meeting GB17323-1998 or drinking water meeting GB 5749-2006. The vulcanizing agent bis 25 and the DCP are purchased from Dongguan eucalyptus silica gel science and technology Co., Ltd; the polyacrylamide, Efka LP-9009, BEVLOID6721 are available from Efka corporation; said 202P, 6900-20X, 4400-20X were purchased from DE modest.
The specific implementation example is as follows:
example 1
Taking 400g of xinco-221 modified vinyl ester resin with the acid value of 15, adding 10g of fatty alcohol polyoxypropylene ether and 5g of dispersing solubilizer S, heating to 35 ℃ under the stirring of 300 revolutions/min, dispersing for 30min under 300 revolutions/min, and accelerating to 2000 revolutions/min for dispersing for 40 min;
b, taking 600g of water, adding xinco-60830 g of soft matter transforming agent, and dispersing for 1h at 3000 r/min;
c, preparing functional graphene: uniformly mixing 3 parts by weight of graphene oxide, 0.1 part by weight of titanate coupling agent and 100 parts by weight of carrier epoxy resin E51100; adding the mixture into a grinder, and grinding for 4h at 2000r/min to obtain a graphene polymer primary polymer; adding 0.03 weight part of anti-flocculant polyacrylamide and 0.1 weight part of anti-precipitant, namely a humble 202P into the graphene polymer primary polymer, and then grinding for 1h by a grinder 2500r/min to obtain functional graphene;
and D, sequentially adding the product obtained in the step A into a high-speed dispersion machine, dripping the product obtained in the step B at 1000 revolutions per minute, finishing dripping for 60 minutes, adding 5g of the product obtained in the step C and 20g of polyvinyl alcohol serving as a stabilizer, accelerating to 8000 revolutions per minute, and dispersing for 1 hour to obtain a finished product.
Example 2
A, taking 600g of xinco-221 modified vinyl ester resin with an acid value of 10, adding 5g of dispersing solubilizer S and KBK-30530530 g, heating to 40 ℃ under stirring at 300 revolutions per minute, dispersing for 40min at 400 revolutions per minute, and accelerating to 2500 revolutions per minute for dispersing for 50 min;
b, taking 400g of water, adding xinco-60830 g of soft matter transforming agent, and dispersing for 2 hours at 4000 revolutions/min;
c, preparing functional graphene: mixing 10 parts of physical graphene, 250.20 parts of cross-linking agent and 51150 parts of carrier epoxy resin uniformly; adding the mixture into a grinder, and grinding for 3h at 2000r/min to obtain a graphene polymer primary polymer; adding an anti-flocculant Efka LP-90090.10 weight part and an anti-precipitant 6900-20X 0.4 weight part into the graphene polymer primary polymer, and grinding for 2.5h by a grinder 2000r/min to obtain functional graphene for later use.
And D, sequentially adding the product obtained in the step A into a dispersion machine, dripping the product obtained in the step B at 1000 revolutions per minute, finishing dripping for 60 minutes, adding 8g of the product obtained in the step C and 40g of carboxyl pasty starch serving as a stabilizer, accelerating to 9000 revolutions per minute, and dispersing for 2 hours to obtain a finished product.
Example 3
A, taking 800g of xinco-221 modified vinyl ester resin with an acid value of 8, adding KBK-30530550 g, heating to 50 ℃ under stirring at 300 revolutions per minute, dispersing for 50min at 500 revolutions per minute, and increasing the speed to 3000 revolutions per minute for 60 min;
b, taking 200g of water, adding xinco-608100 g of soft matter transforming agent, and dispersing for 2 hours at 5000 r/min;
c, preparing functional graphene: mixing 15 parts by weight of physical method graphene, 0.50 part by weight of cross-linking agent DCP and 200 parts by weight of carrier plasticizer dibutyl ester uniformly; adding the mixture into a grinder, and grinding for 5h at 2000r/min to obtain a graphene polymer primary polymer; adding an anti-flocculant BEVLOID 67210.30 weight part and an anti-precipitant 4400-20X 0.5 weight part into the graphene polymer primary polymer, and grinding for 2 hours at 1500r/min by a grinder to obtain functional graphene for later use;
and D, sequentially adding the product obtained in the step A into a dispersion machine, dripping the product obtained in the step B at 1000 revolutions per minute, finishing dripping for 60 minutes, adding 10g of the product obtained in the step C and 60g of stabilizer hydroxymethyl cellulose, increasing the speed to 10000 revolutions per minute, and dispersing for 3 hours to obtain a finished product.
Comparative example 1
The difference from example 1 is that step B is omitted and the product obtained in step B is not added dropwise in step C.
Examples of the experiments
The products of examples and comparative examples were subjected to property tests in a conventional manner, and the results are shown in Table 1.
TABLE 1 comparison of product Properties
| 20％NaOH | Flame retardancy/UL 94 Standard | Flexibility/mm | Temperature resistance/. degree.C | |
| Example 1 | Slightly whitening in 30 days | V-2 | 1 | 320 |
| Example 2 | 60d without whitening | V-0 | 1 | 330 |
| Example 3 | 25d has local whitening | V-1 | 2 | 300 |
| Comparative example 1 | 7d surface whitening and hand sticking | HB | 3 | 280 |
As shown in Table 1, the performance of the prepared aqueous vinyl ester resin is obviously improved compared with that of oily vinyl ester resin in alkali resistance, flame retardance, flexibility and temperature resistance, more importantly, the prepared aqueous vinyl ester resin is environment-friendly resin, can be used for desulfurization and denitration, and can solve the problems of smoke whitening, terrace, industrial anticorrosive coatings and the like, particularly, the aqueous vinyl ester resin can meet the requirement of ammonia corrosion resistance when being used for denitration because the original vinyl ester resin is not resistant to ammonia corrosion, and has wide application space.
While the preferred embodiments and examples of the present invention have been described in detail, the present invention is not limited to the embodiments and examples, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. The novel graphene modified aqueous vinyl ester resin is prepared from the following raw materials in parts by weight:
600 parts of water, 800 parts of modified vinyl ester resin, 10-50 parts of hydrophilic agent, 30-100 parts of soft matter transforming agent, 20-60 parts of stabilizing agent and 5-10 parts of functional graphene;
the functional graphene is prepared from the following raw materials: 3-15 parts of graphene, 0.1-0.5 part of coupling agent or cross-linking agent, 200 parts of carrier, 0.03-0.3 part of anti-flocculating agent and 0.1-0.5 part of anti-precipitating agent.
2. Resin according to claim 1, characterized in that the water is purified water satisfying GB17323-1998 or drinking water for life satisfying GB 5749-2006.
3. Resin according to claim 1 or 2, wherein the modified vinyl ester resin is a hydroxy modified vinyl ester resin, preferably xinco-221, more preferably xinco-221 with an acid number of 8-15.
4. The resin according to any one of claims 1 to 3, wherein the hydrophilic agent is a non-ionic surfactant, preferably one or more of sorbitan fatty acid ester, fatty alcohol polyoxypropylene ether, and dispersion solubilizer S, KBK-305305.
5. The resin according to any one of claims 1 to 4, wherein the soft matter conversion agent is a nonionic surfactant, preferably one or more of glyceryl sorbitan esters and polyoxyethylene ethers.
6. The resin according to any one of claims 1 to 5, wherein the stabilizer is one or more selected from the group consisting of a cellulose-based thickener, a polyacrylic-based thickener, and a polyoxyethylene-based thickener, preferably one or more selected from the group consisting of polyvinyl alcohol, carboxyl starch paste, and hydroxycellulose.
7. The resin according to any one of claims 1 to 6, wherein the functional graphene is prepared from graphene by the following steps:
s1, mixing graphene, a cross-linking agent or a coupling agent and a carrier;
s2, grinding to obtain a graphene polymer primary polymer;
s3, adding an anti-flocculant and an anti-settling agent into the graphene polymer primary polymer, and grinding to obtain the functional graphene;
preferably, the crosslinking or coupling agent is one or more of titanate, vulcanizing agent bis 25 and dicumyl peroxide DCP;
preferably, the carrier comprises an epoxy resin or a carrier plasticizer dibutyl ester;
preferably, the deflocculant is one or more of polyacrylamide, Efka LP-9009 and BEVLOID 6721;
preferably, the anti-precipitation agent is one or more of solvent type anti-precipitation agents 202P, 6900-20X and 4400-20X;
preferably, 0.03-0.10 part of anti-flocculant and 0.1-0.8 part of anti-precipitant are added into the graphene polymer primary polymer, and the functional graphene is obtained by grinding.
8. A method of preparing the resin of any of claims 1-7, comprising the steps of:
s11, mixing a hydrophilic agent with the modified vinyl ester resin, heating, and performing dispersion treatment to obtain A;
s12, mixing the soft matter transforming agent with water, and softening to obtain B;
s13, preparing functional graphene;
s14, dropwise adding the B into the A, adding the functional graphene and the stabilizer, and performing dispersion treatment;
preferably, the heating is to 30-50 ℃.
9. The method as claimed in claim 8, wherein the dispersion treatment in S11 is performed by using a high speed disperser 300-3000 rpm for 30-50min, and then increasing the speed to 2000-3000 rpm for 40-60 min.
10. The method as claimed in claim 8 or 9, wherein the softening treatment in S12 is performed by using a high speed disperser 3000-;
and/or the dispersion treatment in the S14 is to disperse for 30-50min by using the rotating speed of a high-speed dispersion machine of 1000-3000 r/min, and then increase the speed to 8000-10000 r/min and disperse for 1-3 h.
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