CN109134813A - A kind of carbamide resin synthesis technology - Google Patents

A kind of carbamide resin synthesis technology Download PDF

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Publication number
CN109134813A
CN109134813A CN201810806559.1A CN201810806559A CN109134813A CN 109134813 A CN109134813 A CN 109134813A CN 201810806559 A CN201810806559 A CN 201810806559A CN 109134813 A CN109134813 A CN 109134813A
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component
aminophenyl
ethyl carbonate
added
carbamide
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宋大余
宋健为
郭武忠
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Chengdu Shang Tai Science And Technology Co Ltd
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Chengdu Shang Tai Science And Technology Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/10Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/02Polyureas

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a kind of carbamide resin synthesis technologies, the carbamide paint component A is by 4, 4 '-'-diphenylmethane diisocyanates, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent, ethyl carbonate composition, under certain process control condition, synthesis 4, the performed polymer of 4 '-'-diphenylmethane diisocyanates, B component is by 4, 4 '-bis- sec-butylamine base diphenyl methanes, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), pigment, ethyl carbonate composition, under certain process control condition, it is mixed to form the B component containing chain extender;Under the process control condition of the preparation process of coating, A, B component form polyurea coating after spraying.Carbamide paint of the invention has high stabile against thermal denaturation, tensile strength and high tenacity, chemicals-resistant corrosivity height, excellent electrical insulation capability, it is used as the insulating materials or encapsulating material of electronics, appliance device, also can be widely used to machinery, chemical industry, oil field.

Description

A kind of carbamide resin synthesis technology
Technical field
The invention belongs to the preparations of polymer composite, the especially production field of carbamide resin modified coating.
Background technique
Spray Polyurea Elastomer Technology experienced three polyurethane, polyurethane-urea and polyureas developing stage.In three kinds of systems Middle component A is essentially identical, is aromatic series or aliphatic prepolymer and semi-prepolymer, and difference is B component.Spraying is poly- The B component of urethane is made of terminal hydroxy group resin and terminal hydroxy group chain extender, and contains the catalyst for improving reactivity.
Spraying polyurethane/urea B component is also possible to hold amine resin and amine chainextender group either terminal hydroxy group resin At typically containing the catalyst for improving reactivity.And the B component of spray polyurea must be by Amino End Group resin and end ammonia Base chain extender composition, and any hydroxyl moieties and catalyst are free of, a certain amount of dispersing agent and neutral ash 2BL can be contained.
Since the reactivity of Amino End Group compound and isocyanate component is high, it is not necessarily to any catalyst, it can be in room Temperature or low temperature lower moment complete reaction, thus effectively overcome polyurethane and polyurethane/urea elastomer in the construction process, because The influence of environment temperature and humidity and the fatal defects for foaming, material property being caused sharply to decline.
Polyurea Spraying integrates the plurality of advantages of the anti-corrosion materials such as coating, rubber and plastics, be at present in the world One of state-of-the-art aseptic technic.Its technical advantage is mainly manifested in rapid curing, can be in any curved surface spraying without generating stream Phenomenon is dropped down, gel time is as short as 10s or hereinafter, 10min can reach walking intensity;It is insensitive to temperature, moisture, when construction It is not influenced by environment temperature, humidity.Polyureas can construct under -28 DEG C of low temperature environment, can also be under moist rainy environment Construction;100% solid content, meets environmental requirement, does not have smell in construction and use process, is especially suitable for the storage of improper ventilation The anticorrosive construction of top tank structure and inner wall of the pipe;Primary construction can reach thickness requirement, and overcoming traditional anticorrosive paint must be more The disadvantage of secondary construction;Coating is fine and close, seamless, can tolerate the long-term corrosion of the media such as water, seawater, acid, alkali, salt, oil, chemically-resistant Medium and soil erosion ability are very prominent;High mechanical strength, elongation is good, and shock resistance is good, in temperature alternating and external force Not cracky under percussion;Adhesive force is good, and adhesive force is greater than 10MPa on the steel of sandblasting to Sa2.5 grades, is used for a long time not It falls off;Breakdown voltage resistant up to 20kv/mm or more is good with cathodic protection matching;Without catalyst, resistance to UV aging Can be good, not dusting is used for a long time outdoors, does not crack;It is wide using temperature, it can be used for a long time at -50~+121 DEG C, modification is resistance to High temperature polyureas can be 150 DEG C or less the long-time services the advantages that.
Polyurea Spraying has brilliant physical property and workability, is a kind of novel application techniques.It can be with Substitute traditional polyurethane, epoxy resin, glass reinforced plastic, FBE and polyolefins compound completely or partially, chemical anticorrosion, The industries such as pipeline, building, ship, water conservancy, traffic, machinery, mine be wear-resisting have broad application prospects.
Lining and coating two major classes are generally divided into for chemical metallization storage tank anti-corrosion material.Common lining has rubber lining In, plastic lining and glass reinforced plastic lining etc..Rubber lining generally uses natural rubber or synthetic rubber, can make at normal temperatures and pressures With.The disadvantage is that need scene heating vulcanization, construction technology is sufficiently complex, quality it is difficult to ensure that.Plastic lining is generally prefabricated section Shape material applies the special barbola work of man-hour requirement, and seam crossing easily causes to leak, so as to cause global failure.Glass steel lining In use hand paste technique, smell is big, pollution environment, and multiple tracks is needed to construct, and construction quality is difficult to ensure.
Traditional anticorrosive paint has the advantages that easy for construction, can use in inner wall or outer wall.But these coating systems one As there is hardness have a surplus toughness deficiency, easily crack under thermal stress or percussion, premature cracking may cause storage Liquid leakage, repairing and maintenance cause expense to increase;System contains organic solvent, is harmful to the human body, pollutes environment, solvent volatilization The pin hole of generation will cause the infiltration of corrosive medium;It must be constructed using multiple tracks, the disadvantages of period is long, low efficiency.
Polyureas spraying technology efficiently solves above-mentioned problem, and applying in the inside and outside wall antiseptic project of steel storage tank has Apparent technical advantage, Daqing oil field, Shengli Oil Field, Xinjiang Oilfield, Qilu Petrochemical, Lanzhou Petrochemical, Yueyang petrochemical industry original It is applied successfully in the projects such as oil tank, heavy oil tank, Water Tank and hydrochloric acid tank car.
In addition, SPUA technology can also be used in the chemical storage tank for having thermal requirements, the protective layer as insulating layer.Traditional side Method is galvanized iron sheet to be wrapped up outside polyurethane foam, but existing seam is easy to cause into water, and foam is corroded aging quickly. And anti-corrosion and waterproof can be played a dual role of using SPUA technology, and it is seamless, it is both artistic and practical.
To prevent industrial chemicals from revealing, storage tank cofferdam is had around certain chemical storage tanks.The storage tank cofferdam of early stage is very It is simple and crude, it is usually enclosed and is made by concrete or cob wall, rubble is spread in bottom.Once a large amount of leakages occur for raw material, cofferdam can Interim storage, but the industrial chemicals revealed on a small quantity can penetrate into soil, cause serious pollution to soil.With developed country pair Environmental protection is increasingly paid attention to, it is desirable that storage tank cofferdam must be completely enclosed with soil protection.Plastic lining is once in storage tank cofferdam Using, have the advantages that antiseptic property is good, but complicated construction technique, it is especially non-in complex-shaped, more than pipe fitting place construction It is often difficult.In addition, the plastic lining after construction there are a large amount of seams, leakage is often resulted in, however polyureas can be resistant to water and most Number chemical mediators erosion, and have the characteristics that it is pollution-free, do not trickle, construct it is fast.More importantly polyureas bullet after spraying Property body is seamless, flexibility is good, and elongation is up to 300% or more, the hair cracks on concrete substrate can be connected to one It rises, antiseep excellent.Currently, polyureas widely applied on external concrete storage tank cofferdam Pacific Northwest with And the application of Alaska Sector shows that polyureas can be subjected to harsh weather test.In addition to storage tank cofferdam, similar application neck There are also the protection on the surfaces such as chemical industry trench, power plant gutter and ground impervious barrier in domain.
Polyureas represents the trend of international newest aseptic technic.Many famous pipeline engineering all make in the world at present With polyureas or/in conjunction with polyurethane foam for the oil-gas pipeline that needs to keep the temperature.
With the Popularization And Development of polyureas technology, the superiority of polyureas technology, which has, has obtained the common recognition of people.Soon In the future, polyureas will become together one of the main anti-corrosion material of pipeline outer wall with clinkery epoxy powder, 3PE.
SPUA material is also widely used as the inner wall anti-corrosive of ductile iron pipe, steel pipe and pipe of cement.Reaching 50 years makes With the service life, cast iron pipe or steel pipe inner wall must carry out preservative treatment, and common method was lining cement mortar in the past.Cement mortar Pipe lining with the longest history, but there are stress shrink after it is easy to crack, surface defect (such as pitted skin, sand cave, hollowing) is more; Cement-mortar lining will cause the raising of dissolved matter content, and hardness changes, NH3It is precipitated, water quality is caused to alkalize;Water Unstability also will affect the disadvantages of cement mortar.
As CO in water2Superequilibrium quantity concentration, which reaches 7mg/L, will lead to that mortar is impaired, and sand grains is lost, and influence water quality.SPUA material Material, which is used as cast iron pipe inner wall anti-corrosion material, has adhesive force good, does not crack, corrosion resistance is strong, long service life;Surface is smooth, water The power coefficient of friction resistance is fewer than concrete pipe and steel pipe, can improve emptying effectiveness.Under conditions of identical caliber, the power and energy of pump are saved 20% or more source, substantially reduces operating cost;Non-scaling, water quality will not be stain by the mushroom microorganism in water or oxidation and rusting, The advantages that not generating secondary pollution, being able to maintain permanent carrying capacity and constant clean water quality degree.
A kind of manufacturing method of water-soluble poly carbamide resin, this method are introduced in China Patent No. ZL201110101576.3 The carbamide resin of acquisition is mainly used as the plated film of object.So that part of it carbamide resin is penetrated into inner, is conducive to improve poly- Adherency between carbamide resin and object, the carbamide resin are mainly used as fiber plated film and concrete plated film waterproof etc..It is water-soluble at this In the application process of property polyureas, there are the limitations of application field.
A kind of polyurea resin compound and curing agent, the combination are described in China Patent No. ZL201110403185.7 Object satisfaction does not need to solidify for a long time, and when solidification is not influenced by environmental conditions, and exposure for a long time is not in air for carbamide resin Turn yellow, still, the curing time of the polyurea resin compound is relatively long in fact.
A kind of manufacturing process of nano material carbamide resin is described in China Patent No. ZL201210198415.5, it should Carbamide paint is the carbamide resin synthesized using two component of A, B, while being blended into zinc oxide or the titanium dioxide of 20~50nm As the inorganic modified packing material of carbamide resin, however, in the technical process of the invention, the zinc oxide and titanium dioxide of use Granularity seem and become larger.
It is strong for the shock resistance for further increasing carbamide resin in view of deficiency, the present invention present on the above patented technology Degree, in the process of the present invention, is suitably added inorganic carbon sources packing material, and the purpose is to not reduce carbamide paint using the longevity Under the premise of life, the manufacturing cost of carbamide paint is improved, is conducive to the application field for expanding polyurea modified composite material.
Summary of the invention:
The purpose of the present invention is studying a kind of manufacturing process of carbamide paint, under the premise of not increasing manufacturing cost, fill The characteristics of dividing using synthesis carbamide resin, the performance for improving carbamide paint by reasonably selecting process control condition, raw material is special Sign, reaches the final purpose of optimization performance, while reducing the industrial production cost of carbamide paint.
The purpose of the present invention is be realized in that
A kind of carbamide resin synthesis technology, the carbamide paint component A are living by 4,4 '-'-diphenylmethane diisocyanates, height Property polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent, ethyl carbonate composition, in certain process control condition Under, the performed polymer of 4,4 '-'-diphenylmethane diisocyanates is synthesized, B component is by 4,4 '-bis- sec-butylamine base diphenyl methanes, 2- (4- aminophenyl) -5 (6) aminophenyl benzimidazole, pigment, ethyl carbonate composition, under certain process control condition, mixing Form the B component containing chain extender;Under the process control condition of the preparation process of coating, A, B component are formed after spraying Polyurea coating.Itself the specific process is as follows:
1, it is added in a kettle and accounts for twice of component A total weight of ethyl carbonate, high activity polypropylene oxide-ethylene oxide Ethoxylated polyhydric alcohol, sorbitan fatty acid ester dispersing agent are high first with closed reactor after air 10min in nitrogen displacement bottle 4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity under vigorous stirring by speed stirring premix 18~26min of bottom material In the system of polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol and ethyl carbonate.Reaction temperature is 66~88 DEG C, is continued after adding anti- It answers 4.5~6.0h and then chlorobenzoyl chloride is added, the reaction was continued 0.6~1.0h, immediately in -0.088~-0.096MPa, temperature Under conditions of 123~136 DEG C, 3.5~4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains polyureas Component A performed polymer needed for coating;Wherein, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol accounts for the 33 of component A total weight ~38%wt, sorbitan fatty acid ester are 0.3~0.6%wt, and 4,4 '-'-diphenylmethane diisocyanates are 62~67%; Chlorobenzoyl chloride is 0.3~0.6%wt;Dispersing agent hydroxyethyl ethylenediamine triacetate is 3~6%wt.
2, under the protection of nitrogen, it is added twice of B component total weight of ethyl carbonate into reaction kettle, it is added 0.3~ The sorbitan fatty acid ester of 0.6%wt adds and 4,4 '-diphenylmethane diisocyanates under conditions of being stirred continuously The molar ratio of ester is -5 (6) aminophenyl benzo miaow of 4,4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) of 1:1 The mixture of azoles heats mixture, temperature is made to rise to 68~86 DEG C under conditions of control stirring rate is 200~300rpm, Flow back 38~48min, with the mixture of B component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Its In the molar ratio of -5 (6) aminophenyl benzimidazole of 4,4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) be 0.68~0.86:0.32~0.14.
3, the chain extender B component obtained by component A performed polymer needed for the carbamide paint 1) obtained and 2), by spraying Afterwards, setting time is 3~8s.
In the process of the present invention, in order to improve the rigidity and wearability of carbamide resin coating, in synthesis carbamide resin In component, it is suitably added -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), the purpose is to make full use of 2- (4- amino Phenyl) -5 (6) aminophenyl benzimidazoles molecular structure in, containing there are two the rigid structure of phenyl ring and an imidazole ring, warp It crosses and tests repeatedly, discovery is after being added a certain amount of -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), carbamide resin The rigidity and wearability of coating are able to a degree of raising, and in order to adapt to the application of carbamide resin coating, 2- (4- amino is added Phenyl) -5 (6) aminophenyl benzimidazoles amount it is relatively large.By the way that -5 (6) of relatively great amount of 2- (4- aminophenyl) are added After the monomer of aminophenyl benzimidazole, it is found that the impact strength of polyurea coating is greatly improved, tested discovery repeatedly The impact strength of carbamide resin coating is related with the rigid structure of its phenyl ring and imidazole ring, while suitably increasing 2- (4- Aminophenyl) -5 (6) aminophenyl benzimidazoles monomer dosage after, impact strength increase it is fairly obvious, still, when - 5 (6) aminophenyl benzimidazole monomer dosage of 2- (4- aminophenyl) increases to 0.38mol/mol 4,4 '-bis- sec-butylamine bases When diphenyl methane, the increase of obtained carbamide resin coating impact strength at double but sacrifices its of carbamide resin coating His characteristic, such formula is out of season.
When -5 (6) aminophenyl benzimidazole monomer dosage of 2- (4- aminophenyl) is reduced to 0.03mol/mol 4,4 ' - When double sec-butylamine base diphenyl methanes, the reduction of obtained carbamide resin coating impact strength at double, it is such formula be also It is out of season.
In addition the present invention is control appropriate using the purpose of 2- (4- aminophenyl) -5 (6) aminophenyl benzimidazole monomer Make 4,4 '-'-diphenylmethane diisocyanate performed polymers and 4,4 '-bis- sec-butylamine base diphenyl methanes reaction rate, simultaneously The internal stress of polyurea coating is reduced, and then improves the adhesive force of polyurea coating, be conducive to raising carbamide resin coating uses the longevity Life.
In the process of the present invention, it in order to improve the flexibility of carbamide resin coating, is added in the structure of polyurea coating Certain high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol containing epoxy construction, the purpose is to apply improving polyureas The flexibility of layer.
In the process of the present invention, it either during the pre-polymerization of component A or in the forming process of B component, is intended to Deaeration is carried out to component materials or removes the processing of volatile substances, the purpose is to reduce the generation of polyurea coating forming process Stomata, to shorten the service life of polyurea coating.
In the process of the present invention, quickly due to 4,4 '-'-diphenylmethane diisocyanates and aminated compounds reaction rate, In order to reduce the reaction rate of MDI and aminated compounds, MDI compound is subjected to a degree of modification, is converted it into MDI tripolymer compound, and 4 are made full use of, 4 '-'-diphenylmethane diisocyanates (MDI) can occur three under catalytic action Poly- reaction, is limited by reaction condition, usually mainly obtains tripolymer, pentamer, heptamer etc. containing isocyanurate ring Mixture.But in order to synthesis process again through may more than obtain 4,4 '-'-diphenylmethane diisocyanate tripolymer compounds, When reaction carries out to a certain extent, addition chlorobenzoyl chloride makes 4,4 '-'-diphenylmethane diisocyanates terminate reaction, due to HDI tri- Aggressiveness belongs to aliphatic compound, the characteristics of according to carbamide resin coating, is free of this kind of oxidizable group of phenyl ring, therefore have There is good anti-yellowing property.Meanwhile the stable structure of the isocyanurate ring of HDI trimer, not legibility at high temperature, therefore It has many advantages, such as that thermal stability is good, wearability is good, good corrosion resistance.
The present invention fits in two active principles of A, B as needed in order to improve the mobility of carbamide resin figure layer component When the certain ethyl carbonate of addition, purpose improves the mobility of A, B component in spraying process, reduces polyurea coating because instead It answers rate too fast, causes the phenomenon that coating is uneven, be on the one hand conducive to construct in this way, in addition improve the matter of polyurea coating Amount.
Certainly the present invention appropriate can select to increase the aesthetics of polyurea coating according to the color of coated article part A certain amount of organic or inorganic pigment is added, the purpose is to can also improve while improving the aesthetic measure of coated article part The simulation quality of coated article part.
Discoloration occurs because of ultraviolet irradiation in order to reduce polyurea coating, antioxidant can be properly added in B component.
Meanwhile according to the application of polyurea coating, certain fire retardant can also be added, or is added centainly in its component Defoaming agent, to improve the anti-flammability and compactness of polyurea coating.
The defoaming agent and pigment that can be added in the present invention are in order to according to poly- not within claim of the invention The actual needs of urea coating is properly added.
Process description of the invention:
In the manufacturing process of carbamide paint of the present invention, under certain process control condition, 4,4 '-two are added into reaction kettle Phenylmethane diisocyanate, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent are closed by reaction At containing 4,4 '-'-diphenylmethane diisocyanates and high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol performed polymer A group Point, performed polymer becomes a kind of solids, is convenient for construction application after the substance processing of deaeration or removing volatilization.
Under certain process control condition, a certain amount of ethyl carbonate is added into reaction kettle, in the condition being sufficiently stirred Under, dispersing agent, which is dissolved in ethyl carbonate solvent, adds 4,4 '-bis- sec-butylamine base diphenyl methanes, 2- (4- aminophenyl) -5 (6) aminophenyl benzimidazole, so that these mixture of substances are uniform, forms the B group containing chain extender by being sufficiently stirred Point.
The carbamide paint forms polyurea coating by spraying.
The beneficial effects of the present invention are:
Carbamide paint of the invention has high stabile against thermal denaturation, tensile strength and high tenacity, chemicals-resistant corrosivity high, excellent Different electrical insulation capability is used as the insulating materials or encapsulating material of electronics, appliance device, also can be widely used to machinery, chemical industry, Petroleum, military project, field of aerospace.
Detailed description of the invention:
Fig. 1 is 1 polyurea coating performance characteristic table of comparative example of the invention.
Fig. 2 is 2 polyurea coating performance characteristic table of comparative example of the invention.
Specific embodiment
Technique of the invention is described in further detail below with reference to embodiment.
Embodiment 1:
Addition accounts for twice of component A total weight of ethyl carbonate, 33%wt high activity polypropylene oxide-oxidation in a kettle Ethylene ethoxylated polyhydric alcohol, 0.3%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 3% Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 18min, in high degree of agitation It is lower by 67%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol In the system of ethyl carbonate.Reaction temperature is 66 DEG C, the reaction was continued 6.0h and then 0.3%wt benzoyl is added after adding Chlorine, the reaction was continued 0.6h vacuumize 3.5h immediately under conditions of -0.088MPa, temperature are 136 DEG C, remove small molecule and residual Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.3%wt's Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 200rpm, and temperature is made to rise to 86 DEG C, and flow back 38min, with i.e. by B The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.68:0.32.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 8s.
Embodiment 2:
Addition accounts for twice of component A total weight of ethyl carbonate, 38%wt high activity polypropylene oxide-oxidation in a kettle Ethylene ethoxylated polyhydric alcohol, 0.6%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 6% Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 26min, in high degree of agitation It is lower by 62%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol In the system of ethyl carbonate.Reaction temperature is 88 DEG C, the reaction was continued 4.5h and then 0.6%wt benzoyl is added after adding Chlorine, the reaction was continued 1.0h vacuumize 4.5h immediately under conditions of -0.096MPa, temperature are 123 DEG C, remove small molecule and residual Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.6%wt's Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 300rpm, and temperature is made to rise to 68 DEG C, and flow back 48min, with i.e. by B The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.86:0.14.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 3s.
Embodiment 3:
Addition accounts for twice of component A total weight of ethyl carbonate, 34%wt high activity polypropylene oxide-oxidation in a kettle Ethylene ethoxylated polyhydric alcohol, 0.4%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 4% Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 21min, in high degree of agitation It is lower by 66%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol In the system of ethyl carbonate.Reaction temperature is 72 DEG C, the reaction was continued 5.3h and then 0.4%wt benzoyl is added after adding Chlorine, the reaction was continued 0.8h vacuumize 4.1h immediately under conditions of -0.090MPa, temperature are 126 DEG C, remove small molecule and residual Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.4%wt's Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 220pm, and temperature is made to rise to 71 DEG C, and flow back 41min, with i.e. by B The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.73:0.27.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 4s.
Comparative example 1:
33%wt high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, 0.3%wt dehydration mountain are added in a kettle Pears alcohol fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate is 3%wt, first with air in nitrogen displacement bottle Closed reactor after 10min, high-speed stirred premixes bottom material 18min, under vigorous stirring by 67%wt4,4 '-diphenyl-methanes two Isocyanates is gradually added drop-wise in the system of high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol and ethyl carbonate.Reaction temperature Degree is 86 DEG C, the reaction was continued 4.5h and then 0.3%wt chlorobenzoyl chloride is added after adding, the reaction was continued 0.6h, immediately- Under conditions of 0.088MPa, temperature are 136 DEG C, 4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains A component performed polymer needed for carbamide paint.
Under the protection of nitrogen, the sorbitan fatty acid ester of 0.3%wt is added into reaction kettle, what is be stirred continuously Under the conditions of, add 4, the 4 '-bis- sec-butylamine base diphenylmethyls for being 1:1 with the molar ratio of 4,4 '-'-diphenylmethane diisocyanates The mixture of -5 (6) aminophenyl benzimidazole of alkane and 2- (4- aminophenyl), the condition that control stirring rate is 200rpm Under, mixture is heated, temperature is made to rise to 86 DEG C, flow back 38min, with the mixture of B component is cooled to room temperature, is gathered Chain extender B component needed for urea coating;Wherein -5 (6) ammonia of 4,4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) The molar ratio of base phenylbenzimidazol is 0.68:0.32.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 3s.
This example compares with example 1, is added without ethyl carbonate in a kettle, is found that while the basic phase of setting time Together, but there is certain rough place in obtained polyurea coating surface.
Embodiment 4:
Addition accounts for twice of component A total weight of ethyl carbonate, 35%wt high activity polypropylene oxide-oxidation in a kettle Ethylene ethoxylated polyhydric alcohol, 0.5%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 5% Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 23min, in high degree of agitation It is lower by 65%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol In the system of ethyl carbonate.Reaction temperature is 81 DEG C, the reaction was continued 5.8h and then 0.5%wt benzoyl is added after adding Chlorine, the reaction was continued 0.8h vacuumize 4.5h immediately under conditions of -0.093MPa, temperature are 135 DEG C, remove small molecule and residual Remaining monomer, is cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.5%wt's Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 246rpm, and temperature is made to rise to 81 DEG C, and flow back 44min, with i.e. by B The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.81:0.19.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 6s.
Embodiment 5:
Addition accounts for twice of component A total weight of ethyl carbonate, 36%wt high activity polypropylene oxide-oxidation in a kettle Ethylene ethoxylated polyhydric alcohol, 0.3%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 3.8%wt, first with closed reactor after 10 min of air in nitrogen displacement bottle, high-speed stirred premixes bottom material 26min, in fierceness By 64%wt4 under stirring, it is more that 4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ether In the system of the pure and mild ethyl carbonate of member.Reaction temperature is 88 DEG C, the reaction was continued 6.0h and then 0.4%wt benzene is added after adding Formyl chloride, the reaction was continued, and 1.0h vacuumizes 4.5h, removes small point immediately under conditions of -0.096 MPa, temperature are 136 DEG C Son and residual monomer, are cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.3%wt's Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 300rpm, and temperature is made to rise to 86 DEG C, and flow back 48min, with i.e. by B The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.84:0.16.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 5s.
Embodiment 6:
Addition accounts for twice of component A total weight of ethyl carbonate, 37%wt high activity polypropylene oxide-oxidation in a kettle Ethylene ethoxylated polyhydric alcohol, 0.6%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 4.8%wt, first with closed reactor after 10 min of air in nitrogen displacement bottle, high-speed stirred premixes bottom material 18min, in fierceness By 63%wt4 under stirring, it is more that 4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ether In the system of the pure and mild ethyl carbonate of member.Reaction temperature is 66 DEG C, the reaction was continued 4.5h and then 0.6%wt benzene is added after adding Formyl chloride, the reaction was continued, and 0.6h vacuumizes 3.5h, removes small point immediately under conditions of -0.088MPa, temperature are 123 DEG C Son and residual monomer, are cooled to room temperature, component A performed polymer needed for obtaining carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.6%wt's Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 200rpm, and temperature is made to rise to 68 DEG C, and flow back 38min, with i.e. by B The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.78:0.22.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 7s.
Comparative example 2:
Addition accounts for twice of component A total weight of ethyl carbonate, 38%wt high activity polypropylene oxide-oxidation in a kettle Ethylene ethoxylated polyhydric alcohol, 0.6%wt sorbitan fatty acid ester dispersing agent, dispersing agent hydroxyethyl ethylenediamine triacetate are 6% Wt, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirred premixes bottom material 26min, in high degree of agitation It is lower by 62%wt4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol In the system of ethyl carbonate.Reaction temperature is 88 DEG C, after adding after the reaction was continued 6.0h, immediately -0.088~- Under conditions of 0.096MPa, temperature are 123 DEG C, 4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains A component performed polymer needed for carbamide paint.
Under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, is added 0.6%wt's Sorbitan fatty acid ester adds and mole of 4,4 '-'-diphenylmethane diisocyanates under conditions of being stirred continuously Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 300rpm, and temperature is made to rise to 68 DEG C, and flow back 48min, with i.e. by B The mixture of component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-bis- sec-butylamine base hexichol The molar ratio of -5 (6) aminophenyl benzimidazole of methylmethane and 2- (4- aminophenyl) is 0.86:0.14.
Component A performed polymer needed for carbamide paint derived above and 2 are contained into chain extender B component, after spraying, coagulated Gu the time is 18s.
This example compares with example 2, it is found that the setting time of polyureas is opposite and extend, tracing it to its cause is in MDI performed polymer Synthesis process in, since reaction rate is too fast, the degree of polymerization of MDI performed polymer is caused to increase.

Claims (1)

1. a kind of carbamide resin synthesis technology, which is characterized in that the carbamide paint component A is by 4,4 '-diphenyl-methane, two isocyanide Acid esters, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol, chlorobenzoyl chloride, dispersing agent, ethyl carbonate composition, in certain work Under skill control condition, the performed polymer of 4,4 '-'-diphenylmethane diisocyanates is synthesized, B component is by 4,4 '-bis- sec-butylamine base hexichol Methylmethane, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), pigment, ethyl carbonate composition, in certain technology controlling and process item Under part, it is mixed to form the B component containing chain extender;Under the process control condition of the preparation process of coating, A, B component are by spray Polyurea coating is formed after painting;Itself the specific process is as follows:
1) in a kettle be added account for twice of component A total weight ethyl carbonate, high activity polypropylene oxide-ethylene oxide ether it is more First alcohol, sorbitan fatty acid ester dispersing agent, first with closed reactor after air 10min in nitrogen displacement bottle, high-speed stirring Premix 18~26min of bottom material is mixed, 4,4 '-'-diphenylmethane diisocyanates are gradually added drop-wise to high activity polyoxy under vigorous stirring In the system for changing propylene-ethylene oxide ethoxylated polyhydric alcohol and ethyl carbonate.Reaction temperature is 66~88 DEG C, and the reaction was continued after adding 4.5~6.0h and then chlorobenzoyl chloride is added, the reaction was continued 0.6~1.0h is in -0.088~-0.096MPa, temperature immediately Under conditions of 123~136 DEG C, 3.5~4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains polyureas painting Component A performed polymer needed for material;Wherein, high activity polypropylene oxide-ethylene oxide ethoxylated polyhydric alcohol account for component A total weight 33~ 38%wt, sorbitan fatty acid ester are 0.3~0.6%wt, and 4,4 '-'-diphenylmethane diisocyanates are 62~67%;Point Powder chlorobenzoyl chloride is 0.3~0.6%wt;Dispersing agent hydroxyethyl ethylenediamine triacetate is 3~6%wt;
2) under the protection of nitrogen, twice of B component total weight of ethyl carbonate is added into reaction kettle, 0.3~0.6%wt is added Sorbitan fatty acid ester, under conditions of being stirred continuously, add with mole of 4,4 '-'-diphenylmethane diisocyanates Than 4 for 1:1, the mixing of -5 (6) aminophenyl benzimidazole of 4 '-bis- sec-butylamine base diphenyl methanes and 2- (4- aminophenyl) Object heats mixture under conditions of control stirring rate is 200~300rpm, and temperature is made to rise to 68~86 DEG C, and reflux 38~ 48min, with the mixture of B component is cooled to room temperature, chain extender B component needed for obtaining carbamide paint;Wherein 4,4 '-is bis- The molar ratio of -5 (6) aminophenyl benzimidazole of sec-butylamine base diphenyl methane and 2- (4- aminophenyl) is 0.68~0.86: 0.32~0.14;
3) the chain extender B component obtained by component A performed polymer needed for carbamide paint that step 1) obtains and 2), by spraying Afterwards, setting time is 3~8s.
CN201810806559.1A 2018-07-20 2018-07-20 A kind of carbamide resin synthesis technology Pending CN109134813A (en)

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CN113480840A (en) * 2021-07-09 2021-10-08 成都上泰科技有限公司 Method for manufacturing high-performance polyurea composite material containing reinforced fiber cloth
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