CN109135526A - A kind of synthesis technology of epoxidized soybean oil modified polyaspartic acid ester polyurea copolymers - Google Patents
A kind of synthesis technology of epoxidized soybean oil modified polyaspartic acid ester polyurea copolymers Download PDFInfo
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- CN109135526A CN109135526A CN201810805776.9A CN201810805776A CN109135526A CN 109135526 A CN109135526 A CN 109135526A CN 201810805776 A CN201810805776 A CN 201810805776A CN 109135526 A CN109135526 A CN 109135526A
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- China
- Prior art keywords
- soybean oil
- epoxidized soybean
- acid ester
- component
- oil modified
- Prior art date
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- 235000012424 soybean oil Nutrition 0.000 title claims abstract description 96
- 239000003549 soybean oil Substances 0.000 title claims abstract description 96
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- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 claims abstract description 33
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 claims abstract description 33
- 239000004970 Chain extender Substances 0.000 claims abstract description 27
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 claims abstract description 27
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C—CHEMISTRY; METALLURGY
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/776—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur phosphorus
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
Landscapes
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a kind of synthesis technologies of epoxidized soybean oil modified polyaspartic acid ester polyurea copolymers, the epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating component A is by 4, 4 '-bis- sec-butylamine base diphenyl methanes, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), diethyl maleate, methylaminobutyric acid sodium composition, under certain process control condition, synthesis 4, the performed polymer of 4 '-'-diphenylmethane diisocyanates, B component is by 4, 4 '-'-diphenylmethane diisocyanates, dispersing agent, 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 epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating after spraying.Epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating 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, petroleum, military project, field of aerospace.
Description
Technical field
The invention belongs to the preparations of polymer composite, the especially life of polyaspartate polyurea resin modified coating
Production field.
Background technique
Spray polyurea resin elasticity body technique experienced polyurethane, polyurethane-urea and polyaspartate polyurea resin three
Developing stage.Component A is essentially identical in three kinds of systems, is aromatic series or aliphatic prepolymer and semi-prepolymer,
Difference is B component.The B component of spraying polyurethane is made of terminal hydroxy group resin and terminal hydroxy group chain extender, and containing for mentioning
The catalyst of high reaction activity.
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 for spraying poly- carbamide resin must be by Amino End Group resin
It is formed with Amino End Group chain extender, and is free of any hydroxyl moieties and catalyst, a certain amount of dispersing agent and neutrality can be contained
Grey 2BL.
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.
Spray polyurea resin technology integrates the plurality of advantages of the anti-corrosion materials such as coating, rubber and plastics, is current state
One of state-of-the-art aseptic technic on border.Its technical advantage is mainly manifested in rapid curing, can be in any curved surface spraying without producing
Raw trickling phenomenon, gel time is as short as 10s or hereinafter, 10min can reach walking intensity;It is insensitive to temperature, moisture, construction
When do not influenced by environment temperature, humidity.Carbamide resin can construct under -28 DEG C of low temperature environment, can also be moist rainy
It constructs under environment;100% solid content, meets environmental requirement, does not have smell in construction and use process, is especially suitable for ventilation not
The anticorrosive construction of good reservoir walls and inner wall of the pipe;Primary construction can reach thickness requirement, overcome traditional anticorrosive paint
The disadvantage that must repeatedly construct;Coating is fine and close, seamless, can tolerate the long-term corrosion of the media such as water, seawater, acid, alkali, salt, oil,
Resistant to chemical media and soil erosion ability are very prominent;High mechanical strength, elongation is good, and shock resistance is good, in temperature alternating
With not cracky under external impacts effect;Adhesive force is good, and adhesive force is greater than 10MPa on the steel of sandblasting to Sa2.5 grades, for a long time
Using not falling off;Breakdown voltage resistant up to 20kv/mm or more is good with cathodic protection matching;Without catalyst, ultraviolet resistance
Ageing properties are good, and 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,
Modified, high temperature resistant carbamide resin can be 150 DEG C or less the long-time services the advantages that.
Spray polyurea resin technology has brilliant physical property and workability, is a kind of novel application techniques.It
Traditional polyurethane, epoxy resin, glass reinforced plastic, FBE and polyolefins compound can be substituted completely or partially, it is anti-in chemical industry
The industries such as corruption, 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, and to body nocuousness, pollution environment is entered, solvent volatilizees
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.
Carbamide resin spraying technology efficiently solves above-mentioned problem, applies in the inside and outside wall antiseptic project of steel storage tank
With apparent technical advantage, in Daqing oil field, Shengli Oil Field, Xinjiang Oilfield, Qilu Petrochemical, Lanzhou Petrochemical, Yueyang petrochemical industry
The projects such as petroleum tank, heavy oil tank, Water Tank and hydrochloric acid tank car on be applied successfully.
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 has a large amount of seams, often result in leakage, however carbamide resin can be resistant to water with
The erosion of most of chemical mediators, and have the characteristics that it is pollution-free, do not trickle, construct it is fast.More importantly gathering after spraying
Carbamide resin elastomer is seamless, flexibility is good, and elongation is up to 300% or more, can be by the hair cracks on concrete substrate
It links together, antiseep excellent.Currently, carbamide resin is widely applied on external concrete storage tank cofferdam too
The application of flat madder the north and Alaska Sector shows that carbamide resin can be subjected to harsh weather test.Except storage tank cofferdam with
Outside, there are also the protection on the surfaces such as chemical industry trench, power plant gutter and ground impervious barrier for similar application field.
Carbamide resin represents the trend of international newest aseptic technic.Many famous pipeline engineering in the world at present
All employ carbamide resin or/in conjunction with polyurethane foam for the oil-gas pipeline that needs to keep the temperature.
With the Popularization And Development of carbamide resin technology, the superiority of carbamide resin technology have common recognition.
In the near future, carbamide resin 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, the party are introduced in China Patent No. ZL201110101576.3
The carbamide resin that method obtains is mainly used as the plated film of object.Penetrate into part of it polyaspartate polyurea resin in object
Portion is conducive to improve the adherency between carbamide resin and object, which is mainly used as fiber plated film and concrete plated film
Waterproof etc..In the application process of the water-soluble poly carbamide resin, 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 resin coating is the carbamide resin synthesized using two component of A, B, while being blended into the zinc oxide or titanium white of 20~50nm
Powder makees the inorganic modified packing material of carbamide resin, however, in the technical process of the invention, the zinc oxide and titanium white of use
The granularity of powder, which seems, to become larger.
A kind of non-polyurea waterproof coating material and its preparation, user are described in China Patent No. ZL201410843526.6
Method and carbamide resin;Use polyaspartate polyurea resin for base-material in the patent, joined dust-proof base, pigment filler material with
And dispersing agent and the substances such as defoaming agent and levelling agent, the carbamide resin is that the modification of polyaspartate polyurea resin is multiple in fact
Condensation material, shortcoming are that the reaction time excess enthalpy of polyaspartate polyurea resin is too long, are unfavorable for mass production exploitation.
In view of deficiency present on the above patented technology, the present invention is modified poly- asparagus fern to further increase epoxidized soybean oil
The impact strength of propylhomoserin ester carbamide resin is suitably added diisocyanate base phenyl phosphonic acid esters and four in the process of the present invention
Xylene diisocyanate, the purpose is to not reduce epoxidized soybean oil modified polyaspartic acid ester carbamide resin
Under the premise of coating characteristic and service life, reduce epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating manufacture at
This, is conducive to the application field for expanding epoxidized soybean oil modified polyaspartic acid ester carbamide resin modified composite material.
Summary of the invention:
The purpose of the present invention is study a kind of manufacture work of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Skill makes full use of synthesizing epoxy soybean oil modified polyaspartic acid ester carbamide resin under the premise of not increasing manufacturing cost
Feature is applied by reasonably selecting process control condition, raw material to improve epoxidized soybean oil modified polyaspartic acid ester carbamide resin
The performance characteristic of material reaches the final purpose of optimization performance, to realize epoxidized soybean oil modified polyaspartic acid ester carbamide resin
The industrial production of coating.
The purpose of the present invention is be realized in that
A kind of synthesis technology of epoxidized soybean oil modified polyaspartic acid ester polyurea copolymers, the epoxidized soybean oil are modified poly-
Aspartate carbamide resin coating component A is by diamino dimethyl sulfenyl chlorobenzene, -5 (6) aminobenzene of 2- (4- aminophenyl)
Base benzimidazole, diethyl maleate, methylaminobutyric acid sodium, epoxidized soybean oil composition, under certain process control condition, synthesis
The performed polymer of epoxidized soybean oil modified polyaspartic acid ester, B component are by 4,4 '-'-diphenylmethane diisocyanates, dispersing agent, group
At being mixed to form the B component containing chain extender under certain process control condition;In the technology controlling and process of the preparation process of coating
Under the conditions of, A, B component form epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating after spraying.Its concrete technology
It is as follows:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 300~500rpm, reaction kettle is warming up to 48~66 DEG C, 50~80min it
Interior, being added with the molar ratio of aminated compounds is the diethyl maleate of 0.40~0.60:1.0~1.006, and temperature is controlled at 60 DEG C
Hereinafter, controlling temperature after adding at 68~88 DEG C, after reacting 9~14h, 2~3%wt calcium chloride being added, immediately with 66~88
The epoxidized soybean oil of 0.1~0.3mol/mol diethyl maleate is added in drop/min rate, and temperature rises to 123~138 DEG C, after
After 9.0~15.0h of continuous reaction, add methylaminobutyric acid sodium, the reaction was continued 0.5~0.8h, immediately -0.088~-
Under conditions of 0.096MPa, temperature are 163~188 DEG C, 3.5~4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to
Room temperature, component A performed polymer needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino two
Methylsulfany chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be 0.68~
0.86:0.12~0.24:0.02~0.08.
Under the protection of nitrogen, be added into reaction kettle with the molar ratio of diethyl maleate be 0.99~1.0:1.03~
The 4 of 1.08,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene diisocyanate
The mixture of ester heats mixture, temperature is made to rise to 48~66 DEG C under conditions of control stirring rate is 200~300rpm,
33~38min is kept the temperature, with the mixture of B component is cooled to room temperature, it is poly- to obtain epoxidized soybean oil modified polyaspartic acid ester
Chain extender B component needed for carbamide resin coating;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters
Molar ratio with tetramethylxylylene diisocyanate is 0.68~0.81:0.08~0.13:0.06~0.24.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time is 180~900s.
In the process of the present invention, in order to improve the rigidity of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
And wearability is suitably added 2- (4- aminobenzene in the component of synthesizing epoxy soybean oil modified polyaspartic acid ester carbamide resin
Base) -5 (6) aminophenyl benzimidazoles, the purpose is to make full use of -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl)
Molecular structure in, containing there are two the rigid structure of phenyl ring and an imidazole ring, by testing repeatedly, discovery be added it is a certain amount of
- 5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl) after, epoxidized soybean oil modified polyaspartic acid ester carbamide resin
The rigidity and wearability of coating are able to a degree of raising, in order to adapt to epoxidized soybean oil modified polyaspartic acid ester polyureas tree
The application of rouge coating, the amount that 2- (4- aminophenyl) -5 (6) aminophenyl benzimidazole is added are relatively large.It is opposite by being added
After the monomer of -5 (6) aminophenyl benzimidazole of a large amount of 2- (4- aminophenyl), the modified poly- asparagus fern ammonia of discovery epoxidized soybean oil
The impact strength of acid esters carbamide resin coating is greatly improved, and is tested the modified poly- asparagus fern ammonia of discovery epoxidized soybean oil repeatedly
The impact strength of acid esters carbamide resin coating is related with the rigid structure of its phenyl ring and imidazole ring, while suitably increasing 2-
After the dosage of the monomer of (4- aminophenyl) -5 (6) aminophenyl benzimidazole, impact strength increase is fairly obvious, but
It is, when -5 (6) aminophenyl benzimidazole monomer dosage of 2- (4- aminophenyl) increases to 0.28mol/mol diamino dimethyl
When sulfenyl chlorobenzene, the increase of obtained epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating impact strength at double,
But other characteristics of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating are sacrificed, such formula is outdated
's.
When -5 (6) aminophenyl benzimidazole monomer dosage of 2- (4- aminophenyl) is reduced to 0.03mol/mol diamino
When dimethyl sulfenyl chlorobenzene, obtained epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating impact strength is at double
It reduces, such formula is also out of season.
In addition the present invention is control appropriate using the purpose of 2- (4- aminophenyl) -5 (6) aminophenyl benzimidazole monomer
The reaction rate of polyaspartate processed, while reducing interior the answering of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Power, and then the adhesive force of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating is improved, be conducive to improve epoxy soybean
The service life of oily modified polyaspartic acid ester carbamide resin coating.
In the process of the present invention, in order to improve the anti-flammability of epoxidized soybean oil modified polyaspartic acid ester polyurea coating
Can, in the monomer of diisocyanate, diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate is added
Monomer, it is therefore an objective to appropriate to increase diisocyanate base Phenylphosphine under the premise of not increasing aspartic acid ester carbamide resin curing time
On the one hand the dosage of acid esters and tetramethylxylylene diisocyanate is conducive to improve the modified poly- asparagus fern ammonia of epoxidized soybean oil
The anti-flammability of acid esters polyurea coating, still further aspect do not extend the solidification of epoxidized soybean oil modified polyaspartic acid ester polyurea coating
Time, while will not also reduce each performance indicator of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating.
Since polyaspartate polyurea is the relatively slow aliphatic polyurea of a kind of novel low activity, reaction rate,
Amino group in its raw material has been secondary amine rather than primary amine, reduce with isocyanates reaction speed, gel time can
Adjustment is in a few minutes between dozens of minutes;It compares with tradition carbamide resin synthesis, constructing operation is more simple and convenient, to equipment
Requirement not high, coating performance etc. relatively also greatly improve, and solve polyureas reaction speed it is too fast caused by coating
Molding relative difficulty, the reduced performance for making polyurea coating and adhesive force are deteriorated.
Polyaspartate polyurea have the characteristic comparable with common carbamide resin coating, have low-temperature curable,
And curing rate is very fast, hardness is high, good toughness, it can thick coating construction, durability of coating energy good, resistance toization good to substrate adhesive force
The advantages that product have corroded.
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 modified poly- asparagus fern ammonia of epoxidized soybean oil
The stomata that acid esters carbamide resin coating forming process generates, to shorten the painting of epoxidized soybean oil modified polyaspartic acid ester carbamide resin
The service life of layer.
The present invention is in order to improve the stability of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating ingredients, in B
In component, appropriate as needed that certain methylaminobutyric acid sodium is added, it is steady in spraying process that purpose improves A, B component
Qualitative, purpose controls the degree of polymerization of polyaspartate, to control the soybean oil modified polyaspartate polyurea resin of epoxy
Coating causes the phenomenon that coating is uneven because reaction rate is too fast, is on the one hand conducive to construct in this way, and it is big in addition to improve epoxy
The quality of soya-bean oil modified polyaspartic acid ester carbamide resin coating.
Certainly the aesthetics of the invention in order to increase epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating, according to
The color of coated article part, can selection appropriate add a certain amount of organic or inorganic pigment, the purpose is to improve coated article
While the aesthetic measure of part, the simulation quality of coated article part can also be improved.
Discoloration occurs in order to reduce epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating because of ultraviolet irradiation, it can
To be properly added antioxidant in B component.
Meanwhile according to the application of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating, can also add certain
Defoaming agent, to improve the compactness of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating.
The defoaming agent and pigment that can be added in the present invention are in order to according to ring not within claim of the invention
The actual needs of the soybean oil modified polyaspartate polyurea resinous coat of oxygen is properly added.
Process description of the invention:
In the manufacturing process of epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating of the present invention, in certain technique control
Under the conditions of system, into reaction kettle be added diamino dimethyl sulfenyl chlorobenzene when, -5 (6) aminophenyl benzo of 2- (4- aminophenyl)
Imidazoles, diethyl maleate, methylaminobutyric acid sodium synthesize the component A containing polyaspartate performed polymer, pre-polymerization by reaction
Body becomes a kind of solids, is convenient for construction application after the substance processing of deaeration or removing volatilization.
Under the protection of nitrogen, under certain process control condition, the 4 of certain mole, 4 '-hexichol are added into reaction kettle
The mixture of methane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate, control
Certain stirring rate heats mixture, and temperature is made to rise to 48~66 DEG C, keeps the temperature 33~38min, with i.e. by the mixed of B component
It closes object to be cooled to room temperature, chain extender B component needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating.
It is modified poly- to form epoxidized soybean oil by spraying for the epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Aspartate carbamide resin coating.
The beneficial effects of the present invention are:
Epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating of the invention has high stabile against thermal denaturation, tension strong
Degree and high tenacity, chemicals-resistant corrosivity height, excellent electrical insulation capability, are used as electronics, the insulating materials of appliance device or envelope
Package material also can be widely used to machinery, chemical industry, petroleum, military project, field of aerospace.
Detailed description of the invention:
Fig. 1 is epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating performance mark sheet of the invention.
Specific embodiment
Technique of the invention is described in further detail below with reference to embodiment.
Embodiment 1:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 300~500rpm, reaction kettle is warming up to 48 DEG C, within 50min, be added with
The molar ratio of aminated compounds be 0.40:1.0 diethyl maleate, temperature control 60 DEG C hereinafter, adding after, control temperature exist
68 DEG C, after reacting 14h, 2%wt calcium chloride is added, 0.1mol/mol diethyl maleate is added with 66 drops/min rate immediately
Epoxidized soybean oil, temperature rises to 123 DEG C, after the reaction was continued 15.0h, adds methylaminobutyric acid sodium, the reaction was continued 0.5h, with
I.e. under conditions of -0.088MPa, temperature are 188 DEG C, 3.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature,
Component A performed polymer needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino dimethyl
Sulfenyl chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be 0.68:0.24:
0.08。
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 0.99:1.03 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 200rpm, so that temperature is risen to 48 DEG C, keeps the temperature 38min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.81:0.13:0.06.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time 180s.
Embodiment 2:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 500rpm, reaction kettle is warming up to 66 DEG C, within 80min, is added and amine
Close object molar ratio be 0.60:1.006 diethyl maleate, temperature control 60 DEG C hereinafter, adding after, control temperature 88
DEG C, after reacting 9h, 3%wt calcium chloride is added, 0.3mol/mol diethyl maleate is added with 88 drops/min rate immediately
Epoxidized soybean oil, temperature rise to 38 DEG C, after the reaction was continued 9.0h, add methylaminobutyric acid sodium, the reaction was continued 0.8h, immediately
Under conditions of -0.096MPa, temperature are 163 DEG C, 4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains
To component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino dimethyl disulfide
Base chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be 0.86:0.12:
0.02。
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 1.0:1.08 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 300rpm, so that temperature is risen to 66 DEG C, keeps the temperature 38min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.68:0.08:0.24.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time is 180~900s.
Embodiment 3:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 300~500rpm, reaction kettle is warming up to 54 DEG C, within 63min, be added with
The molar ratio of aminated compounds be 0.52:1.004 diethyl maleate, temperature control 60 DEG C hereinafter, adding after, control temperature
At 77 DEG C, after reacting 13h, 2.4%wt calcium chloride is added, 0.15mol/mol maleic acid is added with 76 drops/min rate immediately
The epoxidized soybean oil of diethylester, temperature rise to 131 DEG C, after the reaction was continued 11h, add methylaminobutyric acid sodium, the reaction was continued
0.6h vacuumizes 4.0h immediately under conditions of -0.093MPa, temperature are 175 DEG C, removes small molecule and residual monomer, cooling
To room temperature, component A performed polymer needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino
Dimethyl sulfenyl chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be
0.74:0.18:0.08。
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 0.99:1.08 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 235rpm, so that temperature is risen to 55 DEG C, keeps the temperature 35min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.76:0.09:0.15.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time 436s.
Comparative example 1:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 300rpm, reaction kettle is warming up to 48 DEG C, within 80min, is added and amine
Close object molar ratio be 0.40:1.0 diethyl maleate, temperature control 60 DEG C hereinafter, adding after, control temperature at 68 DEG C,
After reacting 14h, 2%wt calcium chloride is added, the ring of 0.1mol/mol diethyl maleate is added with 66 drops/min rate immediately
Oxygen soybean oil, temperature rise to 123 DEG C, after the reaction was continued 15.0h, immediately under conditions of -0.088MPa, temperature are 163 DEG C, take out
Vacuum 4.5h removes small molecule and residual monomer, is cooled to room temperature, obtains epoxidized soybean oil modified polyaspartic acid ester polyureas tree
Component A performed polymer needed for grease coating material;Wherein diamino dimethyl sulfenyl chlorobenzene, -5 (6) aminophenyl of 2- (4- aminophenyl)
Benzimidazole molar ratio is 0.68:0.32.
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 0.99:1.03 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 200rpm, so that temperature is risen to 48 DEG C, keeps the temperature 38min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.81:0.13:0.06.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time 18s.
This example compares with example 1, is added without methylaminobutyric acid sodium in a kettle, is found that while that setting time is basic
It is identical, but obtained epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating surface exists centainly roughly
Side.
Embodiment 4:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 430rpm, reaction kettle is warming up to 61 DEG C, within 73min, is added and amine
Close object molar ratio be 0.5:1.0 diethyl maleate, temperature control 60 DEG C hereinafter, adding after, control temperature at 83 DEG C, instead
After answering 13h, 2.6%wt calcium chloride is added, the ring of 0.21mol/mol diethyl maleate is added with 76 drops/min rate immediately
Oxygen soybean oil, temperature rise to 131 DEG C, after the reaction was continued 13.0h, add methylaminobutyric acid sodium, the reaction was continued 0.7h, immediately
Under conditions of -0.094MPa, temperature are 181 DEG C, 3.9h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains
To component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino dimethyl disulfide
Base chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be 0.81:0.16:
0.03。
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 1.0:1.03 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 270rpm, so that temperature is risen to 65 DEG C, keeps the temperature 38min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.76:0.11:0.13.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time 561s.
Embodiment 5:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 300~500rpm, reaction kettle is warming up to 66 DEG C, within 50min, be added with
The molar ratio of aminated compounds be 0.60:1.0 diethyl maleate, temperature control 60 DEG C hereinafter, adding after, control temperature exist
88 DEG C, after reacting 14h, 3%wt calcium chloride is added, 0.3mol/mol diethyl maleate is added with 88 drops/min rate immediately
Epoxidized soybean oil, temperature rises to 138 DEG C, after the reaction was continued 15.0h, adds methylaminobutyric acid sodium, the reaction was continued 0.8h, with
I.e. under conditions of -0.096MPa, temperature are 188 DEG C, 4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature,
Component A performed polymer needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino dimethyl
Sulfenyl chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be 0.86:
0.124:0.02。
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 1.0:1.03 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 300rpm, so that temperature is risen to 66 DEG C, keeps the temperature 38min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.68:0.13:0.19.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time 674s.
Embodiment 6:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene, -5 (6) ammonia of 2- (4- aminophenyl) are added into reaction kettle
Base phenylbenzimidazol, under the stirring condition of 500rpm, reaction kettle is warming up to 48 DEG C, within 50min, is added and amine
Close object molar ratio be 0.40:1.006 diethyl maleate, temperature control 60 DEG C hereinafter, adding after, control temperature 68
DEG C, after reacting 9h, 2%wt calcium chloride is added, 0.1mol/mol diethyl maleate is added with 66 drops/min rate immediately
Epoxidized soybean oil, temperature rise to 123 DEG C, after the reaction was continued 9.0h, add methylaminobutyric acid sodium, the reaction was continued 0.5h, immediately
Under conditions of -0.088MPa, temperature are 163 DEG C, 3.5h is vacuumized, small molecule and residual monomer is removed, is cooled to room temperature, obtains
To component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino dimethyl disulfide
Base chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be 0.68:0.24:
0.08。
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 0.99:1.08 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 300rpm, so that temperature is risen to 48 DEG C, keeps the temperature 33min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.81:0.13:0.06.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time 784s.
Comparative example 2:
Under nitrogen protection, diamino dimethyl sulfenyl chlorobenzene is added into reaction kettle, under the stirring condition of 500rpm,
Reaction kettle is warming up to 66 DEG C, and within 50min, being added with the molar ratio of aminated compounds is 0.60:1.006 maleic acid diethyl
Ester, temperature control 60 DEG C hereinafter, adding after, control temperature at 88 DEG C, react 9h after, be added 3%wt calcium chloride, immediately with 88
The epoxidized soybean oil of 0.3mol/mol diethyl maleate is added in drop/min rate, and temperature rises to 138 DEG C, the reaction was continued 9.0h
Afterwards, methylaminobutyric acid sodium is added, the reaction was continued, and 0.8h is vacuumized immediately under conditions of -0.096MPa, temperature are 188 DEG C
4.5h removes small molecule and residual monomer, is cooled to room temperature, obtains the painting of epoxidized soybean oil modified polyaspartic acid ester carbamide resin
Component A performed polymer needed for material;Wherein diamino dimethyl sulfenyl chlorobenzene, methylaminobutyric acid sodium molar ratio be 0.92:0.08.
Under the protection of nitrogen, 4,4 '-with the molar ratio of diethyl maleate for 1.0:1.08 are added into reaction kettle
The mixture of '-diphenylmethane diisocyanate and diisocyanate base phenyl phosphonic acid esters and tetramethylxylylene diisocyanate,
Stirring rate is controlled to heat mixture under conditions of 300rpm, so that temperature is risen to 66 DEG C, keeps the temperature 33min, with i.e. by B group
The mixture divided is cooled to room temperature, chain extender B needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating
Component;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene two are different
The molar ratio of cyanate is 0.68:0.08:0.24.
By component A performed polymer needed for epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating derived above and
Obtained chain extender B component, after spraying, setting time 900s.
This example compares with example 2, finds the setting time of epoxidized soybean oil modified polyaspartic acid ester carbamide resin
It is identical, but the tensile strength of the modified poly- asparagus fern acid esters polyureas of epoxidized soybean oil reduces.
Claims (1)
1. a kind of synthesis technology of epoxidized soybean oil modified polyaspartic acid ester polyurea copolymers, which is characterized in that the epoxy is big
Soya-bean oil modified polyaspartic acid ester carbamide resin coating component A is by diamino dimethyl sulfenyl chlorobenzene, 2- (4- aminophenyl)-
5 (6) aminophenyl benzimidazoles, diethyl maleate, methylaminobutyric acid sodium, epoxidized soybean oil composition, in certain technology controlling and process
Under the conditions of, the performed polymer of synthesizing epoxy soybean oil modified polyaspartic acid ester, B component is by 4,4 '-diphenylmethane diisocyanates
Ester, dispersing agent, composition are mixed to form the B component containing chain extender under certain process control condition;In the preparation of coating
Under the process control condition of journey, A, B component form epoxidized soybean oil modified polyaspartic acid ester carbamide resin after spraying and apply
Layer.Itself the specific process is as follows:
1) diamino dimethyl sulfenyl chlorobenzene, -5 (6) amino of 2- (4- aminophenyl) under nitrogen protection, are added into reaction kettle
Phenylbenzimidazol, under the stirring condition of 300~500rpm, reaction kettle is warming up to 48~66 DEG C, within 50~80min,
Being added with the molar ratio of aminated compounds is the diethyl maleate of 0.40~0.60:1.0~1.006, temperature control 60 DEG C with
Under, after adding, control temperature at 68~88 DEG C, react 9~14h after, be added 2~3%wt calcium chloride, immediately with 66~88 drop/
The epoxidized soybean oil of 0.1~0.3mol/mol diethyl maleate is added in the rate of min, and temperature rises to 123~138 DEG C, continues
After reacting 9.0~15.0h, add methylaminobutyric acid sodium, the reaction was continued 0.5~0.8h, immediately -0.088~-
Under conditions of 0.096MPa, temperature are 163~188 DEG C, 3.5~4.5h is vacuumized, small molecule and residual monomer is removed, is cooled to
Room temperature, component A performed polymer needed for obtaining epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating;Wherein diamino two
Methylsulfany chlorobenzene, -5 (6) aminophenyl benzimidazole of 2- (4- aminophenyl), methylaminobutyric acid sodium molar ratio be 0.68~
0.86:0.12~0.24:0.02~0.08;
2) under the protection of nitrogen, be added into reaction kettle with the molar ratio of diethyl maleate be 0.99~1.0:1.03~
The 4 of 1.08,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters and tetramethylxylene diisocyanate
The mixture of ester heats mixture, temperature is made to rise to 48~66 DEG C under conditions of control stirring rate is 200~300rpm,
33~38min is kept the temperature, with the mixture of B component is cooled to room temperature, it is poly- to obtain epoxidized soybean oil modified polyaspartic acid ester
Chain extender B component needed for carbamide resin coating;Wherein 4,4 '-'-diphenylmethane diisocyanates and diisocyanate base phenyl phosphonic acid esters
Molar ratio with tetramethylxylylene diisocyanate is 0.68~0.81:0.08~0.13:0.06~0.24;
3) component A performed polymer needed for the epoxidized soybean oil modified polyaspartic acid ester carbamide resin coating for obtaining step 1) and
2) the chain extender B component obtained, after spraying, setting time is 180~900s.
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