CN111635498B - Modified polyurea and application thereof - Google Patents
Modified polyurea and application thereof Download PDFInfo
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- CN111635498B CN111635498B CN202010391885.8A CN202010391885A CN111635498B CN 111635498 B CN111635498 B CN 111635498B CN 202010391885 A CN202010391885 A CN 202010391885A CN 111635498 B CN111635498 B CN 111635498B
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/714—Monoisocyanates or monoisothiocyanates containing nitrogen in addition to isocyanate or isothiocyanate nitrogen
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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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
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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
- 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
- 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
- C09D5/08—Anti-corrosive paints
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Abstract
The invention relates to modified polyurea and application thereof. The modified polyurea is prepared from the following raw materials: monofunctional isocyanates and amino resins containing secondary amino groups; the molar ratio of-NCO in the monofunctional isocyanate to-NH in the secondary amino group-containing amino resin is 1: 1-1: 2; the structural formula of the monofunctional isocyanate is shown as a formula (I), and R represents a hydrocarbon group. The construction time limit can reach 300 minutes, the solid content is high, the VOC emission is low, the construction operation is simple and convenient, the requirement on equipment is low, the low-temperature curing and thick coating construction can be realized, the formed coating has high hardness, good toughness, good adhesion to a substrate, good weather resistance, good chemical corrosion resistance and excellent comprehensive performance, and has wide application prospect.
Description
Technical Field
The invention relates to the field of coatings, in particular to modified polyurea and application thereof.
Background
With the vigorous development of the market of wood furniture, the wood paint has a wide application market correspondingly. In practical applications, in addition to the requirement that a paint film formed by the wood lacquer has excellent performance, the furniture is not easy to spray in places with various sculptures (bulges or grooves), so that the wood lacquer is required to be flexibly applied, and the input cost of coating equipment is required to be low.
Nowadays, solvent-free, low-pollution green coatings such as water-borne coatings, high-solids and radiation-curable coatings, powder coatings, etc. are used in a large number and in a wide range. Among these green coatings, spray polyurea materials are one of the important varieties. The polyurea is a product obtained by reacting an isocyanate component and an amino group-containing resin component, wherein the isocyanate component (a component) may be a monomer, derivative, semi-prepolymer, etc. of aromatic or aliphatic isocyanate; the amino-containing resin component (R component) comprises an amino-terminated compound and an amino-terminated chain extender, and can also comprise other auxiliaries, wherein the chain extender can be aromatic and aliphatic amines.
The polyurea is mainly used for spraying construction, and has the advantages of fast curing, good chemical corrosion resistance, high strength, impermeability, wear resistance, flexibility, impact resistance, good high and low temperature resistance, no seam and the like. In addition, the water-proof and wear-resistant composite material has the advantages of convenient process and environmental protection, has great superiority compared with the traditional water-proof and protection technology, has wide application prospect in anticorrosion, waterproof, wear-resistant and other projects, and can be widely applied to the fields of intercity rail transit, buildings, hydraulic chemical engineering machinery and electricity and the like.
However, there are problems if conventional spray polyurea materials are applied in the field of wood lacquers. For example, the polyurea material has short construction time limit, the gel time is only a few seconds to a few minutes, special equipment is required to be adopted during construction, small-scale flexible application cannot be realized, and the requirement on the cost of wood paint coating equipment is high; in addition, because the curing speed is too fast, the adhesive film has poor wettability to the base material, the adhesive force is influenced, the film coating molding is complex, the appearance is easy to form orange peel and other defects, and the color retention and the ultraviolet resistance are poor.
Disclosure of Invention
Based on the above, there is a need to provide a novel modified polyurea with low activity, slow reaction and long gelling time, which has a construction time limit of 300 minutes, high solid content, low VOC emission, simple and convenient construction operation, low requirement for equipment, low-temperature curing and thick coating construction, and the formed coating has high hardness, good toughness, good adhesion to a substrate, good weather resistance, good chemical corrosion resistance and excellent comprehensive performance.
The technical scheme is as follows:
a modified polyurea is prepared by raw materials comprising:
monofunctional isocyanates and amino resins containing secondary amino groups;
the molar ratio of-NCO in the monofunctional isocyanate to-NH in the secondary amino group-containing amino resin is 1: 1-1: 2;
the structural formula of the monofunctional isocyanate is shown as the formula (I):
r represents a hydrocarbon group.
In one embodiment, the starting materials for preparing the monofunctional isocyanate include: toluene diisocyanate, aliphatic monohydric alcohol and auxiliary agent;
the molar ratio of-NCO in the toluene diisocyanate to-OH in the aliphatic monohydric alcohol is 2: 1-2.5: 1.
in one embodiment, the toluene diisocyanate is selected from at least one of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
In one embodiment, the aliphatic monohydric alcohol is selected from at least one of n-hexanol, n-octanol, isooctanol, 2-dodecanol, and 2-hexadecanol.
In one embodiment, the method of preparing the monofunctional isocyanate comprises the steps of:
and mixing the toluene diisocyanate, the auxiliary agent and the aliphatic unit alcohol, reacting, and stopping the reaction when the-NCO content in the system is less than 15%.
In one embodiment, the reaction temperature is 40-60 ℃, and the reaction time is 6-10 h.
In one embodiment, the secondary amino group-containing amino resin is selected from polyaspartic acid ester resins.
In one embodiment, the secondary amino group-containing amino resin is selected from the group consisting of F420 polyaspartate resin, F520 polyaspartate resin, or F530 polyaspartate resin.
In one embodiment, the adjuvant comprises an antioxidant;
the addition amount of the antioxidant accounts for 0.05-0.15% of the total mass of the raw materials for preparing the monofunctional isocyanate.
In one embodiment, the antioxidant is 2, 6-di-tert-butyl-p-methylphenol.
In one embodiment, the adjuvant further comprises a solvent;
the solvent is at least one selected from ester solvents, ether solvents and aromatic hydrocarbon solvents.
In one embodiment, the amount of the solvent added is 2 to 10% by mass based on the total mass of the raw materials for preparing the monofunctional isocyanate.
In one embodiment, the solvent is selected from at least one of ethyl acetate, butyl acetate, toluene, and xylene.
The invention also provides application of the modified polyurea in preparation of wood lacquer.
The technical scheme is as follows:
the raw materials for preparing the wood lacquer comprise the modified polyurea.
Compared with the prior art, the invention has the following beneficial effects:
the modified polyurea provided by the invention has the preparation raw materials comprising monofunctional isocyanate and amino resin containing a secondary amino group in a specific molar ratio. The modified polyurea is obtained by reacting-NCO in monofunctional isocyanate with-NH in amino resin containing secondary amino to generate carbamido. Because the monofunctional isocyanate only has one-NCO functional group, the viscosity is gradually increased when the monofunctional isocyanate is reacted with amino resin containing a secondary amino group, the phenomenon of violent increase of molecular weight is avoided, and the construction time limit is favorably prolonged. Meanwhile, because the amino component in the amino resin is a secondary amino group instead of a primary amino group, the reaction speed of the amino resin and isocyanate is reduced, the gel time of the modified polyurea is prolonged, the construction time limit is increased and can reach 300 minutes, the requirement on equipment is relatively low, the existing wood lacquer spraying equipment can be adopted for spraying, and the construction operation is simpler and more convenient.
In addition, the modified polyurea also has the advantages of high solid content and low VOC emission, and accords with the environmental protection production concept. Meanwhile, the problems of complex coating forming, performance reduction and poor adhesion caused by excessively high polyurea reaction speed in the past are solved. When the modified polyurea is used in wood lacquer, the formed coating has high hardness, good toughness, good adhesive force, good weather resistance and chemical corrosion resistance, excellent comprehensive performance and wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
Interpretation of terms:
(1) toluene diisocyanate: abbreviated as TDI, and has a molecular weight of 174.15. There are two isomers of 2, 4-isomer (2, 4-toluene diisocyanate) and 2, 6-isomer (2, 6-toluene diisocyanate), as shown in formula (II-1) and formula (II-2). There are three specifications of products in industry, depending on the content of the two isomers: the TDI-65 contains 2,4-TDI 65% and 2,6-TDI 35%; ② TDI-80 containing 2,4-TDI 80% and 2,6-TDI 20%; ③ TDI-100, containing 100 percent of 2, 4-TDI.
(2) Functionality: in a particular reaction, the number of reactive chemical functional groups, for example, propylene glycol, has a functionality of 2. The present invention is directed specifically to the functional group of-NCO.
(3) Construction time limit: particularly refers to the time when the viscosity of the mixed material is increased to the viscosity which can not meet the construction requirement when the timing is started after the two-component coating is mixed.
(4) Amine: is an organic compound in which a hydrogen atom of ammonia is substituted with a hydrocarbon group. Compounds formed by substituting one, two or three hydrogen atoms in an ammonia molecule with a hydrocarbyl group are referred to as primary, secondary and tertiary amines, respectively. The general formulas are respectively: RNH2(Primary amine), R2NH (secondary amine), R3N (tertiary amine).
(5) Polyaspartate polyurea: (Polyaerodynamic esters, abbreviated as PAEs), a novel aliphatic polyurea, which is mainly prepared by reacting aliphatic isocyanate with Polyaspartic ester and an auxiliary agent.
(6) Wood lacquer: which is a coating used in the field of woodware.
(7) HDI: hexamethylene diisocyanate or 1, 6-hexamethylene diisocyanate.
The polyurea is mainly used for spraying construction, and has the advantages of fast curing, good chemical corrosion resistance, high strength, impermeability, wear resistance, flexibility, impact resistance, good high and low temperature resistance, no seam and the like. In addition, the water-proof and wear-resistant composite material has the advantages of convenient process and environmental protection, has great superiority compared with the traditional water-proof and protection technology, has wide application prospect in anticorrosion, waterproof, wear-resistant and other projects, and can be widely applied to the fields of intercity rail transit, buildings, hydraulic chemical engineering machinery and electricity and the like.
However, there are problems if conventional spray polyurea materials are applied in the field of wood lacquers. For example, the polyurea material has short construction time limit, the gel time is only a few seconds to a few minutes, special equipment is required to be adopted during construction, small-scale flexible application cannot be realized, and the requirement on the cost of wood paint coating equipment is high; in addition, because the curing speed is too fast, the adhesive film has poor wettability to the base material, the adhesive force is influenced, the film coating molding is complex, the appearance is easy to form orange peel and other defects, and the color retention and the ultraviolet resistance are poor.
The invention provides a novel modified polyurea with low activity, slow reaction and long gelling time.
The technical scheme is as follows:
a modified polyurea is prepared by raw materials comprising:
monofunctional isocyanates and amino resins containing secondary amino groups;
the molar ratio of-NCO in the monofunctional isocyanate to-NH in the secondary amino group-containing amino resin is 1: 1-1: 2;
the structural formula of the monofunctional isocyanate is shown as the formula (I):
r represents a hydrocarbon group.
In one embodiment, the starting materials for preparing the monofunctional isocyanate include: toluene diisocyanate, aliphatic monohydric alcohol and auxiliary agent;
the molar ratio of-NCO in the toluene diisocyanate to-OH in the aliphatic monohydric alcohol is 2: 1-2.5: 1.
the modified polyurea provided by the invention has the preparation raw materials comprising monofunctional isocyanate and amino resin containing a secondary amino group in a specific molar ratio. The modified polyurea is obtained by reacting-NCO in monofunctional isocyanate with-NH in amino resin containing secondary amino to generate carbamido. Because the monofunctional isocyanate only has one-NCO functional group, the viscosity is gradually increased when the monofunctional isocyanate is reacted with amino resin containing a secondary amino group, the phenomenon of violent increase of molecular weight is avoided, and the construction time limit is favorably prolonged. Meanwhile, because the amino component in the amino resin is a secondary amino group instead of a primary amino group, the reaction speed of the amino resin and isocyanate is reduced, the gel time of the modified polyurea is prolonged, the construction time limit is increased and can reach 300 minutes, the requirement on equipment is relatively low, the existing wood lacquer spraying equipment can be adopted for spraying, and the construction operation is simpler and more convenient.
In addition, the modified polyurea also has the advantages of high solid content and low VOC emission, and accords with the environmental protection production concept. Meanwhile, the problems of complex coating forming, performance reduction and poor adhesion caused by excessively high polyurea reaction speed in the past are solved. When the modified polyurea is used in wood lacquer, the formed coating has high hardness, good toughness, good adhesive force, good weather resistance and chemical corrosion resistance, excellent comprehensive performance and wide application prospect.
In one embodiment, the starting materials for preparing the monofunctional isocyanate include: toluene diisocyanate, aliphatic monohydric alcohol and auxiliary agent; the molar ratio of-NCO in the toluene diisocyanate to-OH in the aliphatic monohydric alcohol is 2: 1-2.5: 1. the monofunctional isocyanic acid has the characteristics of high solid content, low viscosity and low free TDI content.
In one embodiment, the toluene diisocyanate is selected from at least one of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
In one preferred embodiment, the toluene diisocyanate is selected from TDI-65, TDI-80 or TDI-100.
In a more preferred embodiment, the toluene diisocyanate of the present invention is TDI-100. The reaction formula of TDI-100 and monoalcohol is shown as formula (III):
in one embodiment, the monohydric alcohol is selected from at least one of n-hexanol, n-octanol, isooctanol, 2-dodecanol, and 2-hexadecanol.
In one embodiment, the method of preparing the monofunctional isocyanate comprises the steps of:
and mixing the toluene diisocyanate, the auxiliary agent and the aliphatic unit alcohol, reacting, and stopping the reaction when the-NCO content in the system is less than 15%.
In one embodiment, the reaction temperature is 40-60 ℃, and the reaction time is 6-10 h.
In one embodiment, the adjuvant comprises an antioxidant;
the addition amount of the antioxidant accounts for 0.05-0.15% of the total mass of the raw materials for preparing the monofunctional isocyanate.
In one embodiment, the antioxidant is 2, 6-di-tert-butyl-p-methylphenol, also known as 2, 6-di-tert-butyl-4-methylphenol, or 3,5-3, 5-di-tert-butyl-4-hydroxytoluene, hereinafter abbreviated as BHT-264.
In one embodiment, the adjuvant further comprises a solvent;
the solvent is at least one selected from ester solvents, ether solvents and aromatic hydrocarbon solvents.
In one embodiment, the amount of the solvent added is 2 to 10% by mass based on the total mass of the raw materials for preparing the monofunctional isocyanate.
In one embodiment, the solvent is selected from at least one of ethyl acetate, butyl acetate, toluene, and xylene.
In one preferable embodiment, the solvent is butyl acetate, and the addition amount of the butyl acetate accounts for 2 to 10 mass percent of the total mass of the raw materials for preparing the monofunctional isocyanate.
Preferably, the formulation and preparation method of the monofunctional isocyanate described in the present invention are as follows:
1mol of TDI (toluene diisocyanate) and 1mol of monohydric alcohol, and also contains 2 to 10 percent of butyl acetate and 0.05 to 0.15 percent of 2, 6-di-tert-butyl-p-methylphenol in percentage by mass of the total mass of the raw materials for preparing the monofunctional isocyanate.
And mixing toluene diisocyanate, butyl acetate and aliphatic monohydric alcohol at the temperature of 40-60 ℃, and reacting for 6-10 hours. And detecting NCO% by a hydrochloric acid chemical titration method in the reaction process, cooling and packaging when the NCO% reaches theoretical NCO%, and finally obtaining a TDI modified monofunctional isocyanate product.
Wherein, the aliphatic unit alcohol can be fed step by step or added into the mixture of toluene diisocyanate and butyl acetate drop by drop.
In one embodiment, the secondary amino group-containing amino resin is selected from polyaspartic acid ester resins. The amino component is a secondary amine rather than a primary amine, reducing the reaction rate with isocyanate and extending the gel time to hundreds of minutes.
Taking the monofunctional isocyanate formed by TDI-100 and monoalcohol as an example, the reaction formula of the monofunctional isocyanate and polyaspartate resin to form modified polyurea is shown as formula (IV):
wherein R is1Is a hydrocarbyl group, the most commonly used being ethyl: CH (CH)3CH2-
Wherein R is2、R3The most commonly used are 4,4 ' diaminocyclohexylmethane and residues of 3,3 ' -dimethyl-4, 4 ' -diaminocyclohexylmethane in which the active hydrogen undergoes Michael addition to the double bond.
In one embodiment, the secondary amino group-containing amino resin is selected from the group consisting of F420 polyaspartate resin, F520 polyaspartate resin, or F530 polyaspartate resin.
The invention also provides application of the modified polyurea in preparation of wood lacquer.
The technical scheme is as follows:
the raw materials for preparing the wood lacquer comprise the modified polyurea.
The following are specific examples.
The amino resin containing a secondary amino group used in examples 1 to 6 and comparative examples 1 to 2 was F520 polyaspartic acid ester resin (solid content: 97%, viscosity at 25 ℃ 1000 mpa.s) from shenzhen heiyang corporation, china.
The remaining raw materials used in examples 1 to 6 and comparative example were all commercially available products unless otherwise specified.
Example 1
The embodiment provides modified polyurea and application thereof.
(1) Preparation of monofunctional isocyanates 1
174.16g (1 mol) of T-100, 130.22g (1 mol) of isooctanol, 34g of butyl acetate and 2g of BHT-264 are put into a reaction kettle, nitrogen is introduced, the temperature is raised to 40-42 ℃, the reaction is carried out for 6 hours, when the NCO percent is 12.3 percent, the temperature is reduced to room temperature, and the mixture is filtered and packaged to obtain the monofunctional isocyanate 1, and the performance results are shown in Table 1.
(2) Preparation of modified polyurea 1
Monofunctional isocyanate 1 was reacted with F520 polyaspartate resin at-NCO: -NH in a molar ratio of 1: 1, and uniformly stirring to obtain the modified polyurea 1, wherein the performance results are shown in a table 2.
Example 2
The embodiment provides modified polyurea and application thereof.
(1) Preparation of monofunctional isocyanates 2
174.16g (1 mol) of T-80, 16g of butyl acetate and 3g of BHT-264 are put into a reaction kettle, nitrogen is introduced, the temperature is raised to 58-60 ℃, 130.22g (1 mol) of isooctanol is dripped into the reaction kettle for 2 hours, after the dripping is finished, the reaction is carried out for 4 hours at the temperature of 58-60 ℃, when the NCO percent is 13.0 percent, the temperature is reduced to room temperature, and the mixture is filtered and packaged to obtain the monofunctional isocyanate 2, wherein the performance results are shown in Table 1.
(2) Preparation of modified polyurea 2
Monofunctional isocyanate 2 was reacted with F520 polyaspartate resin at-NCO: -NH in a molar ratio of 1: 1, mixing and uniformly stirring to obtain the modified polyurea 2, wherein the performance results are shown in a table 2.
Example 3
The embodiment provides modified polyurea and application thereof.
(1) Preparation of monofunctional isocyanates 3
174.16g (1 mol) of T-100, 130.22g (1 mol) of n-octanol, 34g of butyl acetate and 2g of BHT-264 are put into a reaction kettle, nitrogen is introduced, the temperature is raised to 40-42 ℃, the reaction is carried out for 6 hours, when the NCO percent is 12.3 percent, the temperature is reduced to room temperature, and the mixture is filtered and packaged to obtain the monofunctional isocyanate 3, wherein the performance results are shown in Table 1.
(2) Preparation of modified polyurea 3
Monofunctional isocyanate 3 was reacted with F520 polyaspartate resin at-NCO: -NH in a molar ratio of 1: 1, mixing and uniformly stirring to obtain the modified polyurea 3, and the performance results are shown in a table 2.
Example 4
The embodiment provides modified polyurea and application thereof.
(1) Preparation of monofunctional isocyanates 4
174.16g (1 mol) of T-100, 102.17g (1 mol) of n-hexanol, 25g of butyl acetate and 3g of BHT-264 are put into a reaction kettle, nitrogen is introduced, the temperature is raised to 55-57 ℃, the reaction is carried out for 6 hours, when the NCO% is 13.8%, the temperature is reduced to room temperature, and the mixture is filtered and packaged to obtain the monofunctional isocyanate 4, wherein the performance results are shown in Table 1.
(2) Preparation of modified polyurea 4
Monofunctional isocyanate 4 was reacted with F520 polyaspartate resin at-NCO: -NH in a molar ratio of 1: 1, and uniformly stirring to obtain the modified polyurea 4, wherein the performance results are shown in a table 2.
Example 5
The embodiment provides modified polyurea and application thereof.
(1) Preparation of monofunctional isocyanates 5
174.16g (1 mol) of T-65, 186.33g (1 mol) of 2-dodecanol, 30g of butyl acetate and 3g of BHT-264 are put into a reaction kettle, nitrogen is introduced, the temperature is raised to 58-60 ℃, the reaction is carried out for 6 hours, when the NCO percent is 10.7 percent, the temperature is reduced to room temperature, and the mixture is filtered and packaged to obtain the monofunctional isocyanate 5, wherein the performance results are shown in Table 1.
(2) Preparation of modified polyurea 5
Monofunctional isocyanate 5 was reacted with F520 polyaspartate resin at-NCO: -NH in a molar ratio of 1: 1, and uniformly stirring to obtain the modified polyurea 5, wherein the performance results are shown in a table 2.
Example 6
The embodiment provides modified polyurea and application thereof.
(1) Preparation of monofunctional isocyanates 6
174.16g (1 mol) of T-100, 242.44g (1 mol) of 2-hexadecanol, 36g of butyl acetate and 4g of BHT-264 are put into a reaction kettle, nitrogen is introduced, the temperature is raised to 58-60 ℃, the reaction is carried out for 6 hours, when the NCO percent is 9.2 percent, the temperature is reduced to room temperature, and the mixture is filtered and packaged to obtain the monofunctional isocyanate 6, wherein the performance results are shown in Table 1.
(2) Preparation of modified polyurea 6
Monofunctional isocyanate 6 was reacted with F520 polyaspartate resin at-NCO: -NH in a molar ratio of 1: 1, and uniformly stirring to obtain the modified polyurea 6, wherein the performance results are shown in a table 2.
Comparative example 1
The present comparative example provides a modified polyurea and its use.
(1) L-75 from Jia Bao Li paint Co., Ltd was used as the isocyanate component in this comparative example, L-75 was an isocyanate prepolymer obtained by reacting TDI and trimethylolpropane, the solid content was 75%, and the viscosity was 1500mPa.S/25 ℃.
(2) Mixing L-75 with F520 polyaspartic acid ester resin at the ratio of-NCO: -NH in a molar ratio of 1: 1, adding butyl acetate solvent for dilution, and uniformly stirring to obtain a solution capable of being sprayed in a construction state, thereby obtaining the modified polyurea 7, wherein the performance results are shown in a table 2.
Comparative example 2
The present comparative example provides a modified polyurea and its use.
(1) N3390 manufactured by Corcisco was used as the isocyanate component of this comparative example, and N3390 was HDI trimer, 90% in solid content, and 700mPa. S/25 ℃.
(2) N3390 was reacted with F520 polyaspartate resin at the ratio of-NCO: -NH in a molar ratio of 1: 1, adding butyl acetate solvent for dilution, and uniformly stirring to obtain a solution capable of being sprayed in a construction state, thereby obtaining the modified polyurea 8, wherein the performance results are shown in a table 2.
Test example 1
The monofunctional isocyanates of examples 1-6, L-75 of comparative example 1 and N3390 of comparative example 2 were tested for performance using the following criteria or methods:
appearance: GB/T14074.1.
Color number (Fe-Co): GB/T1722.
③ solid portion (%): GB/T2793.
Viscosity (mPa. S/25 ℃ C.): GB/T2794; botiffei DV-1 rotational viscometer.
-NCO content: GB 12009.4A method for determining the-NCO content of polymethylene polyphenyl isocyanate.
The test results are shown in table 1:
TABLE 1
Test example 2
The modified polyureas of examples 1-6 and comparative examples 1-2 were tested for performance, and the testing method was as follows:
solid content: GB/T2793.
② the solid content of the mixed liquid: GB/T2793.
③ viscosity of the mixed solution (S/25 ℃): including initial viscosity and doubled viscosity, GB/T1723 & 1993 paint viscometry
Construction time limit: custom, in minutes, the time it took for the initial viscosity to double was recorded.
The test results are shown in table 2:
TABLE 2
As can be seen from Table 2, the solid content of the modified polyureas of examples 1 to 6 was more than 70%, and the working life was 300 minutes, while the working lives of the modified polyureas of comparative examples 1 and 2 were shorter.
Test example 3
The coating properties in examples 1 to 6 and comparative examples 1 to 2 were tested.
Firstly, preparing paint: diluting to spraying state, (12-14S/coating-4 cups), spraying on 30CM 20CM wood veneer, and testing its dryness, hardness, adhesion, VOC content and water resistance under construction state, wherein the test environment temperature is 25 + -2 deg.C and humidity is 50% + -10%.
The evaluation method is as follows:
(1) the paint film dryness test is carried out according to the GB 1728 paint film and putty drying time measuring method standard.
(2) Paint film hardness test the test is carried out according to the GB 6739 color paint and varnish pencil method for determining the paint film hardness standard.
(3) The adhesion test was carried out according to the standard of the marking test for paint films of GB/T9286 paints and varnishes.
(4) VOC was measured according to the standard for determining the Volatile Organic Compound (VOC) content of coatings containing reactive diluents in GB/T34682.
(5) Water resistance the test was carried out according to the water resistance specification GB/T4893.1.
The test results are shown in table 3:
TABLE 3
| Item | Watch (min) | Nut stem (h) | Adhesion force | Hardness of | VOC g/L | Water resistance |
| Example 1 | 15 | 2.0 | 1 | H | 270 | No abnormality |
| Example 2 | 14 | 1.5 | 1 | H | 240 | No abnormality |
| Example 3 | 14 | 1.5 | 1 | H | 270 | No abnormality |
| Example 4 | 8 | 1.0 | 1 | H | 280 | No abnormality |
| Example 5 | 9 | 1.0 | 1 | H | 270 | No abnormality |
| Example 6 | 13 | 1.2 | 1 | H | 270 | No abnormality |
| Comparative example 1 | 1 | 0.5 | 3 | 2H | 400 | No abnormality |
| Comparative example 2 | 15 | 3.0 | 1 | H | 260 | No abnormality |
As can be seen from Table 3, the dry, hardness, adhesion, water resistance and other indexes of the coating formed in the embodiments 1-6 reach the standard of GB/T23997 solvent type wood lacquer coating, and the coating has excellent comprehensive performance and wide application prospect. As can be seen from the comparison example 1, the construction time limit of the modified common TDI-based adduct curing agent which is not adopted in the invention can not meet the construction requirements when the modified common TDI-based adduct curing agent is used for polyurea modification. In comparison with comparative example 2, when HDI modified trimer solid solution agent modified polyurea was used, the construction time limit was prolonged due to the low reactivity of HDI, but the requirement of coating wood coatings could not be satisfied, and HDI modified trimer was expensive and could not be normally applied to the field of wood coatings for reasons well known in the industry. The above experimental results fully show that the modified polyurea suitable for the wood lacquer can be prepared according to the technical scheme of the invention.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (14)
1. A modified polyurea characterized in that the raw materials for preparing the modified polyurea comprise:
monofunctional isocyanates and amino resins containing secondary amino groups;
the molar ratio of-NCO in the monofunctional isocyanate to-NH in the secondary amino group-containing amino resin is 1: 1-1: 2;
the structural formula of the monofunctional isocyanate is shown as the formula (I):
r represents a hydrocarbon group.
2. The modified polyurea of claim 1, wherein the starting materials for preparing the monofunctional isocyanate comprise: toluene diisocyanate, aliphatic monohydric alcohol and auxiliary agent;
the molar ratio of-NCO in the toluene diisocyanate to-OH in the aliphatic monohydric alcohol is (2: 1) - (2.5: 1).
3. The modified polyurea of claim 2, wherein the toluene diisocyanate is selected from at least one of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate.
4. The modified polyurea of claim 2, wherein the aliphatic unit alcohol is selected from at least one of n-hexanol, n-octanol, isooctanol, 2-dodecanol, and 2-hexadecanol.
5. The modified polyurea according to claim 2, wherein the monofunctional isocyanate is prepared by a method comprising the steps of:
and mixing the toluene diisocyanate, the auxiliary agent and the aliphatic unit alcohol, reacting, and stopping the reaction when the-NCO content in the system is less than 15%.
6. The modified polyurea according to claim 5, wherein the reaction temperature is 40 ℃ to 60 ℃ and the reaction time is 6h to 10 h.
7. The modified polyurea of any one of claims 1 to 6, wherein the amino resin containing secondary amino groups is selected from polyaspartic ester resins.
8. The modified polyurea of claim 7, wherein the amino resin containing a secondary amino group is selected from the group consisting of F420 polyaspartate resin, F520 polyaspartate resin, and F530 polyaspartate resin.
9. The modified polyurea of any one of claims 2 to 6, wherein the auxiliary agent comprises an antioxidant;
the addition amount of the antioxidant accounts for 0.05-0.15% of the total mass of the raw materials for preparing the monofunctional isocyanate.
10. The modified polyurea of claim 9, wherein the antioxidant is 2, 6-di-tert-butyl-p-methylphenol.
11. The modified polyurea of any one of claims 2 to 6, wherein the adjuvant further comprises a solvent;
the solvent is at least one selected from ester solvents, ether solvents and aromatic hydrocarbon solvents.
12. The modified polyurea according to claim 11, wherein the solvent is added in an amount of 2 to 10 mass% based on the total mass of the raw materials for preparing the monofunctional isocyanate.
13. The modified polyurea of claim 11, wherein the solvent is selected from at least one of ethyl acetate, butyl acetate, toluene, and xylene.
14. A wood lacquer characterized in that the raw materials for preparing the wood lacquer comprise the modified polyurea of any one of claims 1 to 13.
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