CN115028798B - Modified isocyanate resin containing branched structure and preparation method and application thereof - Google Patents
Modified isocyanate resin containing branched structure and preparation method and application thereof Download PDFInfo
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- CN115028798B CN115028798B CN202210739440.3A CN202210739440A CN115028798B CN 115028798 B CN115028798 B CN 115028798B CN 202210739440 A CN202210739440 A CN 202210739440A CN 115028798 B CN115028798 B CN 115028798B
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
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- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- 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
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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- 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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Abstract
The invention discloses a modified isocyanate resin containing a branched structure, a preparation method and application thereof, and relates to the technical field of polyurea coatings, wherein the modified isocyanate resin is prepared from the following raw materials: dipentaerythritol, diisocyanate, polyether polyol, an organic solvent and a catalyst; the components are calculated according to the mass percentage: the sum of the usage amounts of the dipentaerythritol, the diisocyanate and the polyether polyol accounts for 80-95wt% of the total feeding amount; the organic solvent accounts for 5-20wt% of the total feeding amount; the catalyst amount accounts for 0.5-5wt% of the total feeding amount; wherein the total feeding amount of the dipentaerythritol, the diisocyanate, the polyether polyol, the organic solvent and the catalyst is 100wt%. According to the invention, by introducing hexafunctional resin and a large number of flexible groups into isocyanate, the polyurea coating prepared by matching modified isocyanate resin and polyaspartic ester has large crosslinking strength and better flexibility.
Description
Technical Field
The invention relates to the technical field of polyurea coatings, and further relates to a modified isocyanate resin containing a branched structure, and a preparation method and application thereof.
Background
The polyurea technology is called as one of the most promising high technologies and new materials in the 21 st century, is a novel solvent-free and pollution-free green construction technology which is developed and developed for meeting the environmental protection requirement after low (pollution-free) coating technologies such as high-solid coatings, water-based coatings, radiation curing coatings, powder coatings and the like, and is developed rapidly after the technology emerges. The polyurea does not contain catalyst, is quickly cured, can be sprayed and molded on any curved surface, inclined surface and vertical surface, and does not generate the phenomenon of flowing; the coating is insensitive to moisture and humidity during construction, is not influenced by environmental temperature and humidity, is environment-friendly, is compact and continuous, has excellent performance, particularly shows the performances of tensile strength, flexibility, medium resistance, wear resistance and the like, has the flexibility from a soft rubber (Shore A30) to a hard elastomer (Shore D65), and is suitable for the anticorrosion protection of the building industry, the sports field, bridge engineering and industrial facilities.
However, the molecular structure of polyurea contains a large amount of benzene rings and amino groups, and the polyurea coating is easy to oxidize and break bonds under illumination, so that the polyurea coating is aged and discolored, and the phenomenon of pulverization and shedding appears in severe cases. In order to prevent the polyurea coating from aging, a third generation of novel polyurea, namely Polyaspartic Acid Ester (PAE) polyurea is developed, compared with the traditional polyurea, the polyurea coating has the characteristics of convenient construction, no need of special equipment, good wettability to a base material, smooth and flat coating surface, excellent aging resistance and the like, is concerned by coating companies at home and abroad, a large number of polyaspartic acid ester type polyurea products are put into production and application, and related research results are reported in documents. However, polyaspartic acid ester type polyurea products with high strength and high toughness are rare, and the reason for this is that the research on isocyanate component modified resins, especially on isocyanate modified resins containing a multi-branched structure, is relatively rare.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified isocyanate resin containing a branched structure, and a preparation method and application thereof. According to the invention, dipentaerythritol and dihydroxypolyether are chemically grafted to modify isocyanate resin, and hexafunctionality resin and a large number of flexible groups are introduced to isocyanate, so that a polyurea coating prepared by matching the modified isocyanate resin and polyaspartic acid ester has high crosslinking strength, good flexibility and excellent low-temperature resistance.
One of the objects of the present invention is to provide a modified isocyanate resin containing a branched structure, wherein the modified isocyanate resin has a structural formula of:
wherein R1 is
Wherein R2 is (C) 2 H 4 O) m (C 3 H 6 O) n (ii) a m and n are any integer of 1 to 10.
Preferably, the modified isocyanate resin is prepared from the following raw materials:
dipentaerythritol, diisocyanate, polyether polyol, an organic solvent and a catalyst;
the components are calculated according to the mass percentage:
the sum of the usage amounts of the dipentaerythritol, the diisocyanate and the polyether glycol accounts for 80-95wt% of the total feeding amount;
the organic solvent accounts for 5-20wt% of the total feeding amount;
the catalyst amount accounts for 0.5-5wt% of the total feeding amount;
wherein the total input amount of the dipentaerythritol, the diisocyanate, the polyether glycol, the organic solvent and the catalyst is 100wt%.
Preferably, the components are calculated according to the mass percentage:
the sum of the usage amounts of the dipentaerythritol, the diisocyanate and the polyether polyol accounts for 82-89wt% of the total feeding amount;
the organic solvent accounts for 10-15wt% of the total feeding amount;
the catalyst amount accounts for 1-3wt% of the total feeding amount;
wherein the total feeding amount of the dipentaerythritol, the diisocyanate, the polyether polyol, the organic solvent and the catalyst is 100wt%.
Preferably, the molar ratio of dipentaerythritol, diisocyanate, and polyether polyol is 1.
The dipentaerythritol is an active monomer containing 6 hydroxyl groups, and has the following structural formula:
the dipentaerythritol can be selected from Shandongtai chemical technology Co., ltd, haomi chemical Co., ltd, guangzhou city, ziboehao chemical Co., ltd.
The structural formula of the diisocyanate is as follows: OCN-R-NCO;
wherein R is
The diisocyanate may be selected from domestic 4,4' -dicyclohexylmethane diisocyanate, isophorone diisocyanate, and the like.
The structural formula of the polyether polyol is as follows: HO-R-OH;
wherein R is (C2H 4O) m (C3H6O) n (ii) a m and n are any integer of 1-10.
The polyether polyol can be at least one selected from domestic polytetrahydrofuran glycol with molecular weight of 800-2000 and propylene glycol polyether.
Preferably, the organic solvent is at least one of an ester solvent, a ketone solvent and a benzene solvent; for example: ethyl acetate, butyl acetate, acetone, butanone, cyclohexanone, cyclopentanone, benzene, toluene, and xylene; preferably xylene, butyl acetate and cyclohexanone, in a ratio of 3:1:1 part by weight of the prepared mixed solvent.
Preferably, the catalyst is at least one of dibutyltin dilaurate and stannous octoate.
Another object of the present invention is to provide a method for preparing a modified isocyanate resin containing a branched structure, the method comprising:
and after the dipentaerythritol is subjected to graft polymerization with diisocyanate, the dipentaerythritol is subjected to graft polymerization with polyether polyol, and finally the dipentaerythritol is subjected to graft polymerization with diisocyanate to obtain the modified isocyanate resin.
The following scheme can be specifically adopted:
and (2) grafting dipentaerythritol and diisocyanate in the presence of an organic solvent and a catalyst, then continuously grafting with polyether polyol, and finally grafting with diisocyanate to synthesize the modified isocyanate resin.
Preferably, the reaction temperature of the dipentaerythritol and diisocyanate graft polymerization is 60-80 ℃, and the reaction time is 4-6 hours; cooling to 40-45 ℃, adding polyether glycol, and reacting for 4-6 hours at 60-80 ℃; cooling to 40-45 ℃, and then adding diisocyanate, wherein the diisocyanate is added twice according to the mass ratio of 1.
The following scheme can be specifically adopted:
mixing dipentaerythritol with an organic solvent to form a liquid, adding a catalyst and diisocyanate to react at the temperature of 60-80 ℃ for 4-6 hours; cooling to 40-45 ℃, adding polyether glycol, reacting at 60-80 ℃ for 4-6 hours, cooling to 40-45 ℃, finally adding diisocyanate, reacting at 60-80 ℃ for 4-6 hours, cooling to 40-45 ℃, discharging to obtain a low-viscosity solution, namely the modified isocyanate resin.
The structural formula of the graft of dipentaerythritol and diisocyanate is as follows:
wherein R1 is
The structural formula of the graft after the graft is continuously grafted with polyether glycol is as follows:
wherein R1 is
Wherein R2 is (C2H 4O) m (C3H6O) n (ii) a m and n are any integer of 1-10.
Finally, grafting with diisocyanate to synthesize the modified isocyanate resin, wherein the structural formula of the modified isocyanate resin is as follows:
wherein R1 is
Wherein R2 is (C2H 4O) m (C3H6O) n (ii) a m and n are any integer of 1-10.
The general reaction equation of the modified isocyanate resin is as follows:
the invention also aims to provide a flexible weather-resistant coating containing the modified isocyanate resin containing the branched structure, which comprises a component A and a component B;
the component A comprises polyaspartic acid ester resin, pigment and filler, an auxiliary agent and a diluent A;
the component B comprises modified isocyanate resin and a diluent B;
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
20-80 parts of modified isocyanate resin;
10-50 parts of diluent B;
the mass ratio of the component A to the component B is (1-10) to 1;
the diluent A and the diluent B can be the same or different and are respectively and independently selected from one or a combination of ester solvents, ketone solvents or benzene solvents.
Preferably, the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
25-50 parts of modified isocyanate resin;
15-40 parts of diluent B;
the mass ratio of the component A to the component B is (2-7) to 1.
The polyaspartic acid ester resin can be selected from at least one of Shenzhen Feiyang F420, NH 1420 of Bayer company, jun and JH-8142 of Shanghai.
The pigment and filler can be selected from pigments with weather resistance and shielding effects, such as titanium dioxide, carbon black, mica iron oxide, iron oxide red, aluminum powder, organic yellow, scarlet powder, phthalocyanine blue, phthalocyanine green, chromium oxide green and the like; or functional pigment nano silicon dioxide, precipitated barium sulfate, talcum powder, mica powder and other fillers; the skilled person can make the choice according to the actual situation.
The auxiliary agent is conventional in the field, such as: at least one of a defoaming agent, a leveling agent and a wetting dispersant; the defoaming agent can be at least one of BYK-066N defoaming agent, BYK-054 defoaming agent, AFCONA2720 defoaming agent and AFCONA2020 defoaming agent; the flatting agent can be selected from at least one of BYK-322 type flatting agent, BYK-A530 type flatting agent, AFCONA3700 type flatting agent and AFCONA3770 type flatting agent; the wetting dispersant can be at least one selected from BYK-P104S type wetting dispersants, BYK-354 type wetting dispersants and BYK-378 type wetting dispersants.
The diluents a and B are conventional diluents in the art, such as: at least one of ester, ketone or benzene solvents; xylene, cyclohexanone and butyl acetate may be preferred in the present invention as 3:1:1 part by weight of the prepared mixed solvent.
The preparation method of the flexible weather-resistant coating comprises the following steps:
the components are mixed according to the parts by weight to obtain the flexible weather-resistant coating.
The method specifically comprises the following steps:
(1) Uniformly stirring the polyaspartic ester resin, the pigment and filler, the auxiliary agent and the diluent A according to the weight parts, then grinding the mixture to 20-40 mu m by using a sand mill or a three-roll mill, filtering the mixture by using a filter screen, metering and packaging the mixture, and preparing the component A;
(2) And uniformly mixing the modified isocyanate resin and the diluent B according to the weight part to obtain the curing agent, namely the component B.
And uniformly mixing the component A and the component B according to a mass ratio to obtain the flexible weather-resistant coating.
The coating process of the flexible weather-resistant coating can adopt a brush coating or spraying process; the thickness of the coating is controlled between 60 and 200 mu m, and the best use effect can be obtained.
The flexible weather-resistant coating has the following excellent comprehensive properties:
flexibility (mm): 1;
pull-off adhesion (MPa): more than 8.00;
impact strength (kg. Cm): 50;
water resistance (23. + -. 2 ℃): the paint film does not wrinkle, bubble or fall off after 180 days;
abrasion resistance (500g, 500r weight loss/g): 0.06-0.12;
resistance to alternating damp-heat salt fog, (salt fog (35 ℃ X4 h) + damp-heat (50 ℃ X7 d)): the paint film does not crack, bubble or fall off in 4 periods;
resistance to artificial weathering (UVB): changing color for 2000h, grade 0, powdering grade 1, cracking grade 0;
seawater scouring resistance (seawater flow rate is 12m/s, continuous scouring for 200h + soaking for 200h, 1 period): the paint film does not crack, bubble or fall off in 3 periods;
salt spray resistance: no bubbling, no falling off and no color change after 3000 hours.
The flexible weather-resistant coating can be cured at normal temperature; the coating can be applied to the protective coatings of construction facilities such as sewage treatment pools, swimming pools, water parks, dam banks, bridge piers, stadium stands, roofs, balconies, terraces, high-speed railway beds and the like, outdoor chemical equipment plants, offshore oil exploration drilling platforms, ship fenders and the like which need long-term weather resistance and wear resistance, and can also be applied to instruments and equipment used at low temperature, and the lowest temperature can reach-65 ℃.
Detailed Description
While the present invention will be described in conjunction with specific embodiments thereof, it is to be understood that the following embodiments are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.
The starting materials used in the examples are all commercial products.
The organic solvents in the examples were: xylene, butyl acetate and cyclohexanone are mixed according to the proportion of 3:1:1 part by weight of a preparation;
diluents a and B in the examples are: xylene, butyl acetate and cyclohexanone are mixed according to the proportion of 3:1:1 part by weight.
Example 1
Preparation of modified isocyanate resin containing branched structure:
after 2.63 parts by weight (0.01 mole) of dipentaerythritol (Shandongteng Tai) and 13 parts by weight of an organic solvent were mixed to obtain a liquid, 2 parts by weight of dibutyltin dilaurate and 16.3 parts by weight (0.06 mole) of 4,4' -dicyclohexylmethane diisocyanate were added. Reacting for 4 hours at 60 ℃, cooling to 40 ℃, then adding 49.77 parts by weight (0.06 mol) of propylene glycol polyether with the molecular weight of 800, reacting for 4 hours at 60 ℃, cooling to 40 ℃, finally adding 16.3 parts by weight (0.06 mol) of 4,4' -dicyclohexylmethane diisocyanate, reacting for 4 hours at 60 ℃, cooling to 40 ℃, discharging to obtain a low-viscosity solution, namely the modified isocyanate resin containing the branched structure. Measured by infrared absorption spectrum at 3400-3500cm -1 The peak of hydroxyl disappears, and 1730-1750cm -1 、1700-1710cm -1 1640-169900 cm -1 The characteristic absorption peak of ester bond appears, and meanwhile, the concentration of the product is 2260-2280cm -1 The characteristic absorption peak of NCO group of (1) does not disappear and is 1060-1250cm -1 And an absorption peak of irregular vibration characteristics of ether bonds appears, which proves that a corresponding modified isocyanate resin target product containing a branched structure is obtained through a synthetic reaction.
Example 2
Preparation of modified isocyanate resin containing branched structure:
after 2.53 parts by weight (0.01 mole) of dipentaerythritol (blooms, guangzhou) and 10 parts by weight of an organic solvent were mixed to prepare a liquid, 1 part by weight of stannous octoate and 13.29 parts by weight (0.06 mole) of isophorone diisocyanate were added. Reacting at 70 deg.C for 5 hr, cooling to 45 deg.C, adding 59.88 weight parts of polytetrahydrofuran diol with molecular weight of 1000 (0.06 mol), reacting at 70 deg.C for 5 hr, cooling to 45 deg.C, and adding 13.29 weight parts (0.06 mol) of isopropanolReacting phorone diisocyanate at 70 ℃ for 5 hours, cooling to 45 ℃, and discharging to obtain a low-viscosity solution, namely the modified isocyanate resin containing the branched structure. Measured by infrared absorption spectrum at 3400-3500cm -1 The peak of hydroxyl group disappears, and 1730-1750cm -1 、1700-1710cm -1 1640-169900 cm -1 The characteristic absorption peak of ester bond appears, and meanwhile, the concentration of the product is 2260-2280cm -1 The characteristic absorption peak of NCO group of (1) does not disappear and is 1060-1250cm -1 And an absorption peak with irregular vibration characteristics of ether bond appears, and the corresponding target product of the modified isocyanate resin containing the branched structure is obtained through the synthetic reaction.
Example 3
Preparation of modified isocyanate resin containing branched structure:
after mixing 1.35 parts by weight (0.0053 mol) of dipentaerythritol (catalpanhao) with 15 parts by weight of an organic solvent to give a liquid, 3 parts by weight of dibutyltin dilaurate and 8.37 parts by weight (0.032 mol) of 4,4' -dicyclohexylmethane diisocyanate were added. Reacting at 80 ℃ for 6 hours, cooling to 45 ℃, then adding 63.9 parts by weight of propylene glycol polyether with molecular weight of 2000 (0.032 mol), reacting at 80 ℃ for 6 hours, cooling to 45 ℃, finally adding 8.37 parts by weight (0.032 mol) of 4,4' -dicyclohexylmethane diisocyanate, reacting at 80 ℃ for 6 hours, cooling to 45 ℃, discharging to obtain a low-viscosity solution, namely the modified isocyanate resin containing a branched structure. Measured by infrared absorption spectrum at 3400-3500cm -1 The peak of hydroxyl disappears, and 1730-1750cm -1 、1700-1710cm -1 And 1640-169900 cm -1 The characteristic absorption peak of ester bond appears, and meanwhile, the concentration of the product is 2260-2280cm -1 The characteristic absorption peak of NCO group of (1) does not disappear and is 1060-1250cm -1 And an absorption peak of irregular vibration characteristics of ether bonds appears, which proves that a corresponding modified isocyanate resin target product containing a branched structure is obtained through a synthetic reaction.
Example 4
Preparation of flexible weather-resistant paint:
100 parts of polyaspartic acid ester resin (Shenzhen Feiyang F420) is weighed, put into a stainless steel tank and stirred by a high-speed stirrer, 0.2 part of defoamer BYK066N, 0.3 part of flatting agent BYK322 and 0.5 part of wetting dispersant BYK-P104S are added, after even stirring, 15 parts of carbon black, 5 parts of titanium pigment, 3 parts of talcum powder and 2 parts of nano-silica are added, after even stirring, 60 parts of diluent A are evenly stirred, and then ground to standard fineness by a sand mill or a three-roll grinder, and filtered and packaged to be a coating A component.
50 parts by weight of the modified isocyanate resin prepared in example 1 and 40 parts by weight of the diluent B were weighed and stirred uniformly to obtain a coating B component.
When in use, the component A and the component B are mixed according to the weight ratio of 2:1, mixing and spraying to form a film.
Example 5
Preparation of flexible weather-resistant paint:
100 parts of polyaspartic acid ester resin (NH 1420 of Bayer company) is weighed, put into a stainless steel tank and stirred by a high-speed stirrer, 15 parts of aluminum powder, 5 parts of organic yellow, 3 parts of phthalocyanine blue, 15 parts of mica powder, 2 parts of nano-silica and 70 parts of diluent A are added after uniform stirring, the mixture is ground to a standard fineness by a sand mill or a three-roll mill, and the mixture is filtered and packaged into a coating A component.
25 parts by weight of the modified isocyanate resin prepared in example 3 and 17.4 parts by weight of the diluent B were weighed and stirred uniformly to obtain a coating B component.
When in use, the A and B components are mixed according to the weight ratio of 5:1, mixing and spraying to form a film.
Example 6
Preparation of flexible weather-resistant coating:
100 parts of polyaspartic acid ester resin (Jun and Shanghai JH-8142) are weighed, put into a stainless steel tank and stirred by a high-speed stirrer, added with 2720.2 parts of defoaming agent AFCONA, 700.6 parts of flatting agent AFCONA, and 1.2 parts of wetting dispersant BYK-378, stirred uniformly, added with 30 parts of mica iron oxide, 20 parts of iron oxide red, 3 parts of precipitated barium sulfate, 25 parts of mica powder, 2 parts of nano-silica, and 75 parts of diluent A, stirred uniformly, ground by a sand mill or a three-roll grinder to standard fineness, and filtered and packaged to be the component A of the coating.
28 parts by weight of the modified isocyanate resin prepared in example 3 and 15 parts by weight of the diluent B were weighed and stirred uniformly to obtain a coating B component.
When in use, the A and B components are mixed according to the weight ratio of 7:1, mixing and spraying to form a film.
Example 7
Preparation of flexible weather-resistant coating:
weighing 100 parts of polyaspartic acid ester resin (Shenzhen Feiyang F420), putting into a stainless steel tank, stirring by a high-speed stirrer, adding 0.8 part of defoaming agent AFCONA2020, 0.6 part of flatting agent BYK-A530 and 0.6 part of wetting dispersant BYK-P104S, uniformly stirring, adding 15 parts of titanium dioxide, 5 parts of phthalocyanine green, 3 parts of chromium oxide green, 35 parts of mica powder, 2 parts of nano-silica and 78 parts of diluent A, uniformly stirring, grinding to a standard fineness by a sand mill or a three-roll mill, filtering and packaging to obtain the coating A component.
32 parts by weight of the modified isocyanate resin prepared in example 2 and 28 parts by weight of the diluent B were weighed and stirred uniformly to obtain a coating B component.
When in use, the A and B components are mixed according to the weight ratio of 4:1, mixing and spraying to form a film.
The coatings obtained in examples 4 to 7 were sprayed to form films, and the properties of the obtained films were tested, wherein the flexibility was determined by reference to the GB/T1731 paint film flexibility test method; the pull-open method adhesion is tested according to the GB/T5210 colored paint and varnish pull-open method adhesion test; the impact strength is measured according to a GB/T1732 paint film impact resistance measurement method; the water resistance is determined according to the determination of GB/T9274 colored paint and varnish to resist liquid medium; the wear resistance is measured according to a rotary rubber grinding wheel method for measuring the wear resistance of GB/T1768 colored paint and varnish; the alternating-humidity-heat-resistant salt fog is tested according to the CB 1146.13 ship equipment environment test method: and (3) measuring by alternating salt spray, wherein the test conditions are as follows: salt spray (35 ℃ X4 h) + moist heat (50 ℃ X7 d); the artificial weathering resistance (UVB) is determined according to the rating method of the ageing of the coatings of the plastic, paint and rubber materials for GB/T14522 mechanical industrial products by a fluorescent ultraviolet lamp GB/T1766 color paint and varnish; the seawater scouring resistance is measured according to a GB/T7789 dynamic test method for antifouling performance of marine antifouling paint, and the test conditions are as follows: the flow rate of the seawater is 12m/s, the washing is continuously carried out for 200h + the soaking is carried out for 200h, and the period is 1; the salt spray resistance is determined according to the determination of the neutral salt spray resistance of GB/T1771 colored paint and varnish. The test results are given in table 1 below:
TABLE 1
Claims (10)
1. A modified isocyanate resin containing a branched structure is characterized in that the structural formula of the modified isocyanate resin containing the branched structure is as follows:
in the formula R 1 Is composed of
Or
；
In the formula R 2 Is (C) 2 H 4 O) m (C 3 H 6 O) n (ii) a m and n are any integer of 1-10.
2. The modified isocyanate resin containing a branched structure according to claim 1, wherein the modified isocyanate resin containing a branched structure is prepared from raw materials comprising:
dipentaerythritol, diisocyanate, polyether polyol, an organic solvent and a catalyst;
the components are calculated according to the mass percentage:
the sum of the usage amounts of the dipentaerythritol, the diisocyanate and the polyether polyol accounts for 80-95wt% of the total feeding amount;
the organic solvent accounts for 5-20wt% of the total feeding amount;
the catalyst amount accounts for 0.5-5wt% of the total feeding amount;
wherein the total feeding amount of the dipentaerythritol, the diisocyanate, the polyether polyol, the organic solvent and the catalyst is 100wt%.
3. The modified isocyanate resin containing a branched structure according to claim 2, wherein:
the components are calculated according to the mass percentage:
the sum of the usage amount of the dipentaerythritol, the diisocyanate and the polyether polyol accounts for 82-89wt% of the total feeding amount;
the organic solvent accounts for 10-15wt% of the total feeding amount;
the catalyst amount accounts for 1-3wt% of the total feeding amount;
wherein the total feeding amount of the dipentaerythritol, the diisocyanate, the polyether polyol, the organic solvent and the catalyst is 100wt%.
4. The modified isocyanate resin having a branched structure according to claim 2, wherein: the molar ratio of dipentaerythritol, diisocyanate, and polyether polyol is 1.
5. The modified isocyanate resin having a branched structure according to claim 2, wherein: the organic solvent is at least one of ester solvent, ketone solvent and benzene solvent.
6. The modified isocyanate resin containing a branched structure according to claim 2, wherein: the catalyst is at least one of dibutyltin dilaurate and stannous octoate.
7. A process for producing a modified isocyanate resin containing a branched structure according to any one of claims 1 to 6, which comprises:
and after the dipentaerythritol is subjected to graft polymerization with diisocyanate, carrying out graft polymerization with polyether polyol, and finally carrying out graft polymerization with diisocyanate to obtain the modified isocyanate resin.
8. The method of producing a modified isocyanate resin having a branched structure according to claim 7, wherein:
the reaction temperature of the dipentaerythritol and diisocyanate graft polymerization is 60-80 ℃, and the reaction time is 4-6 hours; cooling to 40-45 ℃, adding polyether glycol, and reacting for 4-6 hours at 60-80 ℃; cooling to 40-45 ℃, and then adding diisocyanate, wherein the diisocyanate is added twice according to the mass ratio of 1.
9. A flexible weather-resistant coating material comprising the modified isocyanate resin having a branched structure according to any one of claims 1 to 6, characterized in that: the flexible weather-resistant coating comprises a component A and a component B;
the component A comprises polyaspartic acid ester resin, pigment and filler, an auxiliary agent and a diluent A;
the component B comprises the modified isocyanate resin containing the branched structure and a diluent B;
the component A comprises the following components in parts by weight:
100 parts by weight of polyaspartic ester resin;
20-100 parts of pigment and filler;
0.5-5 parts of an auxiliary agent;
50-90 parts of diluent A;
the component B comprises the following components in parts by weight:
20-80 parts by weight of modified isocyanate resin containing a branched structure;
10-50 parts of diluent B;
the mass ratio of the component A to the component B is (1-10) to 1;
the diluent A and the diluent B can be the same or different and are respectively and independently selected from one or a combination of ester solvents, ketone solvents or benzene solvents.
10. The flexible weather-resistant coating material containing a modified isocyanate resin having a branched structure according to claim 9, characterized in that:
the component A comprises the following components in parts by weight:
100 parts by weight of polyaspartic acid ester resin;
25-80 parts of pigment and filler;
1-3 parts of an auxiliary agent;
60-80 parts of diluent A;
the component B comprises the following components in parts by weight:
25-50 parts by weight of modified isocyanate resin containing a branched structure;
15-40 parts of diluent B;
the mass ratio of the component A to the component B is (2-7) to 1.
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