CN117209700A - Modified polyisocyanate composition, preparation method thereof and varnish - Google Patents
Modified polyisocyanate composition, preparation method thereof and varnish Download PDFInfo
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- CN117209700A CN117209700A CN202311157051.0A CN202311157051A CN117209700A CN 117209700 A CN117209700 A CN 117209700A CN 202311157051 A CN202311157051 A CN 202311157051A CN 117209700 A CN117209700 A CN 117209700A
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- polyisocyanate composition
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- hexamethylene diisocyanate
- pentamethylene diisocyanate
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- 239000000203 mixture Substances 0.000 title claims abstract description 69
- 239000005056 polyisocyanate Substances 0.000 title claims abstract description 57
- 229920001228 polyisocyanate Polymers 0.000 title claims abstract description 57
- 239000002966 varnish Substances 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 6
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 claims abstract description 55
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims abstract description 52
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012948 isocyanate Substances 0.000 claims abstract description 18
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000003054 catalyst Substances 0.000 claims description 26
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 14
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- 238000004821 distillation Methods 0.000 claims description 9
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- 239000003795 chemical substances by application Substances 0.000 claims description 7
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- 238000004519 manufacturing process Methods 0.000 claims description 4
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- -1 aromatic isocyanate Chemical class 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
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- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a modified polyisocyanate composition, a process for its preparation and a varnish. The modified polyisocyanate composition has the following characteristics: the polyisocyanate composition comprises isocyanurate formed by trimerization reaction of pentamethylene diisocyanate and 1, 6-hexamethylene diisocyanate, and the composition simultaneously comprises three structural isocyanurate mononucleosomes, and the mass ratio of the three mononucleosomes meets a certain relationship based on the total mass of the isocyanate composition. The modified polyisocyanate composition prepared by the invention greatly improves the quick-drying property and chemical resistance of the existing product, has a certain improvement on the adhesive force of a metal base, and is particularly suitable for the fields with certain requirements on the construction period and chemical resistance, such as the fields of automotive factory paints and repair paints.
Description
Technical Field
The invention belongs to the field of high polymer materials, in particular to the field of isocyanate, and more particularly relates to a modified polyisocyanate composition and polyurethane varnish.
Background
The coating film prepared from the aromatic isocyanate series has higher reactivity in the curing process, but with the prolonged use time, the product is easy to generate yellowing phenomena with different degrees, so that the coating film is mainly used in occasions with non-strict requirements on appearance. The aliphatic isocyanate series products have more excellent yellowing resistance, and the products are more applied to the field with higher requirements on weather resistance. For example, in the original paint or repair paint of automobiles, the widely used 1, 6-hexamethylene diisocyanate composition has excellent weather resistance, but the construction process requires longer drying time due to lower reaction activity, thus greatly influencing the construction efficiency and progress.
In recent years, quick-drying type varnish has been attracting more and more attention in the automobile refinish paint market, and patent CN102153691a provides a method for improving the drying speed by optimizing the solvent composition and introducing a modified cellulose acetate butyrate and isophorone diisocyanate curing agent, but the scheme has higher cost and the actual drying of the product is not obviously improved. The patent CN101812261a uses 80% of 1, 6-hexamethylene diisocyanate trimer and 20% of isophorone diisocyanate or quick-drying 1, 6-hexamethylene diisocyanate trimer as an isocyanate curing agent to increase the drying speed of the product, and essentially uses physical blending as a method for improving the quick-drying property of the product, the method requires pre-mixing treatment, and the reactivity of the isophorone diisocyanate or quick-drying 1, 6-hexamethylene diisocyanate trimer which can be improved is limited. Patent DE19752691 uses polyisocyanates based on isophorone diisocyanate and polyisocyanates based on pentamethylene diisocyanate in cold-mix form to improve certain properties of the polyisocyanates, which are also physically modified and are more difficult to achieve with high gloss resulting from chemical bond linkages. The modified polyisocyanate prepared by preparing the modified body of the xylylene diisocyanate and the pentamethylene diisocyanate with different contents in the patent CN107614561A, CN107709389A, CN107709397A improves the reaction speed to a certain extent, but the yellowing resistance of the modified polyisocyanate is insufficient due to the introduction of the xylylene structure, so the modified polyisocyanate is difficult to be used in the field of automobile industry with higher requirements on yellowing performance. In the patent CN114057991a, 1,3 or 1, 4-hydrogenated xylylene diisocyanate is adopted to carry out crosslinking modification on the hexamethylene diisocyanate in the polymerization process, so that the obtained isocyanurate product has good weather resistance and high reactivity, and it is known that the polymer formed by the 1, 3-hydrogenated xylylene diisocyanate has higher glass transition temperature, and the film product is not only brittle and hard, but also has high raw material price, and can not be applied to the field of automobile factory paint or repair paint with extremely severe requirements. Therefore, development of isocyanate curing agents with excellent quick-drying property and chemical resistance is still a problem to be solved in the industry.
Disclosure of Invention
Therefore, the invention aims to overcome the defects of the prior art and provide a modified polyisocyanate composition and a preparation method thereof, which not only improve the quick-drying property of the aliphatic isocyanate curing agent in the prior art, greatly shorten the construction period of the coating and avoid the occurrence of great increase of the viscosity of the product. In addition, the polyurethane varnish has obvious improving effects on chemical resistance and adhesion to metal, and is particularly suitable for the field of automobile repair paint or raw paint.
The invention is realized by the following technical scheme:
in a first aspect, the present invention provides a modified polyisocyanate composition comprising isocyanurate formed by trimerization of pentamethylene diisocyanate and 1, 6-hexamethylene diisocyanate, wherein the composition comprises three isocyanurate mononuclei of structures (A), (B) and (C) at the same time, and the mass ratio of the three mononuclei satisfies the following relationship based on the total mass of the isocyanate composition: (C) (A) > (B),
the modified polyisocyanate composition has good weather resistance of both 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate structures, and can enable the modified 1, 6-hexamethylene diisocyanate to have free NCO groups with higher reactivity and obviously improve the drying speed through a unique isocyanurate polymerization process. On the other hand, it has surprisingly been found that the modified isocyanurate ring formed by 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate is of an incompletely symmetrical structure, so that the cured crosslinking point of the product is greatly improved under the condition that the viscosity of the product is not obviously increased after modification, and the coating has good chemical resistance and adhesive force.
Further, the polyisocyanate composition according to the present invention, wherein the mass ratio of the sum (A) + (B) of the modified isocyanurate mononucleotidic structure (A) and the modified isocyanurate mononucleotidic structure (B) is in the range of 5 to 40%, preferably 5 to 30%.
The invention can ensure the degree of polymerization of the 1, 6-hexamethylene diisocyanate and the pentamethylene diisocyanate together by controlling the mass ratio of the sum of the modified isocyanurate mononuclear structure (A) and the modified isocyanurate mononuclear structure (B) so as to avoid too high product viscosity caused by too much self-polymerization of the pentamethylene diisocyanate with too high content. More importantly, it has been found that when the two materials are sufficiently cross-polymerized and the structural ratio is ensured within this range, the final modified polyisocyanate composition not only has good quick-drying and chemical resistance, but also achieves a lower operating viscosity for the same product.
Further, the modified polyisocyanate composition has a sum of monomer contents of free pentamethylene diisocyanate and 1, 6-hexamethylene diisocyanate of less than 0.5% based on the total mass of the polyisocyanate composition.
In a second aspect, the present invention further provides a process for preparing the above modified polyisocyanate composition comprising the steps of: under the inert gas atmosphere, 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 45-120 ℃, a catalyst is added, meanwhile, pentamethylene diisocyanate is dropwise added in a continuous dropwise feeding mode, continuous cyclization copolymerization reaction is carried out under the action of the catalyst, after the pentamethylene diisocyanate is dropwise added, the reaction is continued until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 25-65%, 45-55% is preferred, a terminator is added to terminate the reaction, a crude isocyanate mixture solution is obtained, and unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed through distillation, so that the modified polyisocyanate composition is obtained.
In the above preparation method, the inert gas is preferably nitrogen.
Further, the preparation method of the modified polyisocyanate composition comprises the step of adding 5% -35% of pentamethylene diisocyanate by mass based on the total mass of 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate.
Further, in the method for producing the modified polyisocyanate composition, the dropping rate of pentamethylene diisocyanate is not particularly limited, but from the viewpoint of process stability, it is preferable to control the dropping time to be 30 to 120 minutes.
Further, in the method for producing the modified polyisocyanate composition, the catalyst is not particularly limited, but from the viewpoint of process simplicity, a catalyst capable of simultaneously allowing pentamethylene diisocyanate and 1, 6-hexamethylene diisocyanate to form a modified isocyanurate ring structure, such as one or any of trimethyl hydroxyethyl ammonium, tetrabutylammonium hydroxide, triethyl hydroxypropyl ammonium, tetramethyl ammonium acetate, tetrabutyl ammonium acetate, tetramethyl ammonium propionate, tetramethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, benzyl triphenyl phosphorus chloride, 2,4, 6-tris (dimethylamine methyl) phenol, may be preferable.
Further, the terminator is an acid compound, preferably at least one of dimethyl phosphate, diethyl phosphate, dibutyl phosphate, dioctyl phosphate, 2-ethylhexyl phosphate, phosphoric acid, hydrochloric acid, sulfuric acid, acrylic acid, benzenesulfonic acid, p-toluenesulfonic acid, benzoyl chloride and acetyl chloride.
The invention also provides a polyurethane varnish coating, which is prepared by taking the modified polyisocyanate composition as a curing agent.
The polyurethane varnish coating can be prepared by mixing the modified polyisocyanate composition serving as a curing agent and the resin containing active hydrogen groups serving as a reactive resin according to the isocyanate groups/hydroxyl groups (NCO/OH) of 1.0-1.1, and can also be prepared by adding a catalyst and a diluent for promoting the formation of carbamate according to actual construction requirements to adjust the varnish performance.
Further, the resin containing an active hydrogen group may be at least one selected from the group consisting of a hydroxyacrylic resin, a polyether polyol, a polyester polyol, and a polycarbonate polyol.
Further, the catalyst capable of promoting the formation of the carbamate can be at least one selected from dibutyl tin dilaurate and stannous octoate.
Further, the diluent may be at least one selected from ethyl acetate, propylene glycol methyl ether acetate, butyl acetate, xylene, toluene, and S100 solvent.
The technical scheme provided by the invention has the following beneficial effects:
according to the invention, surprisingly, in the process of preparing the 1, 6-hexamethylene diisocyanate isocyanurate, pentamethylene diisocyanate is continuously dripped into the 1, 6-hexamethylene diisocyanate to carry out synchronous cross polymerization, and further, the structural content relation of modified isocyanurate mononucleobodies (A), (B) and (C) in a reaction system is controlled by controlling the dripping amount of pentamethylene diisocyanate, so that a polyisocyanate composition crude product is finally obtained, and unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed to obtain a modified polyisocyanate composition.
Detailed Description
For a better understanding of the technical solution of the present invention, the following examples are further described below, but the present invention is not limited to the following examples.
The following examples and comparative examples of the present invention were prepared from the following raw materials in part by sources:
pentamethylene Diisocyanate (PDI), a company of the chemical group of vanning, inc;
1, 6-Hexamethylene Diisocyanate (HDI), wanhua chemical group Co., ltd;
tetrabutylammonium hydroxide, used as a catalyst, available from New classical chemical Co., ltd;
benzyl trimethylammonium hydroxide, used as a catalyst, available from New classical chemical Co., ltd;
dioctyl phosphate, used as a terminator, available from ala Ding Shiji limited;
t12, dibutyl tin dilaurate, a common drier for polyurethane paint formulations, ara Ding Shiji Co., ltd;
unless otherwise specified, the contents in the present invention are mass contents.
In the following examples and comparative examples of the present invention, the relevant test methods are as follows:
(1) NCO content tests were carried out according to standard GB/T12009.4;
(2) Viscosity test dynamic viscosity at 25℃was measured according to a laminometer (Brookfield DT-2);
(3) The isocyanurate mononuclear body structure content testing method comprises the following steps:
13C nuclear magnetic resonance spectra were measured using AVANCE400 manufactured by Bruker Biospin in a mass concentration of 60%, 100MHz and scanning for 48 hours using deuterated chloroform CDCl3 as a solvent.
In the above measurement, the following characteristic signals were integrated, and the mass ratios of the respective structures (a), (B), and (C) were obtained from the integrated values.
(a) A structure of formula (a): delta 148.3ppm vicinity
(b) A structure of formula (B): delta 148.4ppm vicinity
(c) A structure of formula (C): delta 148.6ppm vicinity
(d) (A) + (B) mass ratio: (Structure of formula A+Structure Signal area of B)/total isocyanurate ring carbon spectrum Signal area.
(4) The sum of the monomer contents of free pentamethylene diisocyanate and 1, 6-hexamethylene diisocyanate is tested, an external standard curve is established by High Performance Liquid Chromatography (HPLC), and the key parameters can be referred to as follows:
chromatographic column: waters XSelect HSS T3 5um 4.6 x 250mm;
automatic sample injector: SIL-20A
Column temperature: 40 DEG C
Sample injection amount: 10 mu L
Detection wavelength: 281nm
Derivatizing reagent: 4% 1-methoxyphenylpiperazine-acetonitrile solution
The respective concentrations are calculated according to the respective peak areas of the pentamethylene diisocyanate and the 1, 6-hexamethylene diisocyanate and the external standard curve, and the sum of the two concentrations is used as the sum of the monomer contents of the free pentamethylene diisocyanate and the 1, 6-hexamethylene diisocyanate in the polyisocyanate composition.
Example 1
Under the inert gas atmosphere, 1000g of 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 55 ℃, then about 0.20g of tetrabutylammonium hydroxide catalyst is added, meanwhile, pentamethylene diisocyanate is dropwise added in a continuous dropwise feeding mode and is subjected to continuous copolymerization reaction under the action of the catalyst, the dropwise addition is stopped after the continuous accumulation of pentamethylene diisocyanate is controlled to be 250g for 75 minutes, the reaction is continuously maintained until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 25%, 0.15g of dioctyl phosphate terminator is added to stop the reaction, an isocyanate mixture solution is obtained, unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed through distillation, and the polyisocyanate composition 1# is obtained, and after analysis, the NCO content of the modified polyisocyanate composition is 22.3%, and the viscosity is: 2917cP/25℃and the sum of the monomer contents of free 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate is 0.42%.
Example 2
Under the inert gas atmosphere, 1000g of 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 120 ℃, then about 0.15g of benzyltrimethylammonium hydroxide catalyst is added, meanwhile, a continuous dropwise addition mode is adopted to dropwise add pentamethylene diisocyanate, continuous copolymerization reaction is carried out under the action of the catalyst, dropwise addition is stopped after the continuous accumulation of pentamethylene diisocyanate is controlled to be 250g for 120 minutes, the reaction is continuously maintained until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 55%, 0.11g of dioctyl phosphate terminator is added to stop the reaction, an isocyanate mixture solution is obtained, unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed through distillation, namely polyisocyanate composition No. 2 is obtained, and the NCO content of the polyisocyanate composition is 22.1 percent and the viscosity is analyzed: the sum of the monomer contents of free 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate was 0.37% at 3774cP/25 ℃.
Example 3
Under the inert gas atmosphere, 1000g of 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 75 ℃, then about 0.14g of benzyltrimethylammonium hydroxide catalyst is added, meanwhile, a continuous dropwise addition mode is adopted to dropwise add pentamethylene diisocyanate, continuous copolymerization reaction is carried out under the action of the catalyst, dropwise addition is stopped after the continuous accumulation of pentamethylene diisocyanate is controlled to be 72g for 75 minutes, the reaction is continuously maintained until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 45%, 0.10g of dioctyl phosphate terminator is added to stop the reaction, an isocyanate mixture solution is obtained, unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed through distillation, namely polyisocyanate composition 3#, and the NCO content of the polyisocyanate composition is 21.9% after analysis, the viscosity is: the sum of the monomer contents of free 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate was 0.39% at 3235cP/25 ℃.
Example 4
Under the inert gas atmosphere, 1000g of 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 75 ℃, then about 0.19g of tetrabutylammonium hydroxide catalyst is added, meanwhile, pentamethylene diisocyanate is dropwise added in a continuous dropwise feeding mode and is subjected to continuous copolymerization reaction under the action of the catalyst, the dropwise addition is stopped after the continuous accumulation of pentamethylene diisocyanate is controlled to 453g for 50 minutes, the reaction is continuously maintained until the polymerization conversion rate of 1, 6-hexamethylene diisocyanate reaches 45%, 0.15g of dioctyl phosphate terminator is added to stop the reaction, an isocyanate mixture solution is obtained, unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed through distillation, and polyisocyanate composition 4# is obtained, and the NCO content of the polyisocyanate composition is 22.5% after analysis, the viscosity is: 4312cP/25℃and the sum of the monomer contents of free 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate is 0.31%.
Comparative example 1
Under the inert gas atmosphere, 1000g of 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 75 ℃, then 0.24g of tetrabutylammonium hydroxide catalyst is added, continuous polymerization reaction is carried out under the action of the catalyst until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 45%, 0.17g of dioctyl phosphate terminator is added to terminate the reaction, thus obtaining isocyanate mixture solution, unreacted 1, 6-hexamethylene diisocyanate is further removed by distillation, namely polyisocyanate composition No. 5, the NCO content of the polyisocyanate composition is 21.7% after analysis, and the viscosity is: 2711cP/25℃and a free 1, 6-hexamethylene diisocyanate content of 0.28%.
Comparative example 2
Under the inert gas atmosphere, 1000g of 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 75 ℃, then about 0.21g of tetrabutylammonium hydroxide catalyst is added, meanwhile, pentamethylene diisocyanate is dropwise added in a continuous dropwise feeding mode and is subjected to continuous copolymerization reaction under the action of the catalyst, the dropwise addition is stopped after the continuous accumulation of pentamethylene diisocyanate is controlled to be 750g for 50 minutes, the reaction is continuously maintained until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 45%, 0.14g of dioctyl phosphate terminator is added to stop the reaction, an isocyanate mixture solution is obtained, unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed through distillation, and the polyisocyanate composition 6# is obtained, and is analyzed, the NCO content of the polyisocyanate composition is 22.2%, and the viscosity is: 6700cP/25℃and the sum of the monomer contents of free 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate was 0.43%.
Comparative example 3
Under the inert gas atmosphere, 1000g of 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 75 ℃, then about 0.26g of tetrabutylammonium hydroxide catalyst is added, meanwhile, pentamethylene diisocyanate is dropwise added in a continuous dropwise feeding mode and is subjected to continuous copolymerization reaction under the action of the catalyst, the pentamethylene diisocyanate is stopped dropwise after the continuous accumulation of 100 minutes is controlled to be 570g, the reaction rate is kept until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 45%, 0.17g of dioctyl phosphate terminator is added to stop the reaction, an isocyanate mixture solution is obtained, unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are further removed through distillation, namely polyisocyanate composition No. 7 is obtained, and the NCO content of the polyisocyanate composition is 22.3% after analysis, the viscosity is: the sum of the monomer contents of free 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate was 0.36% at 6221cP/25 ℃.
The modified polyisocyanate compositions prepared in each of examples and comparative examples were analyzed for the content relationship of the structure (a), the structure (B) and the structure (C), and the analysis results are shown in table 1:
TABLE 1 analysis results of modified polyisocyanate compositions
Application example
The modified polyisocyanate compositions 1 to 7# were used as isocyanate components, hydroxyl-containing acrylic resin (trade name: AC1010, from Tonde resin) was used as polyol component, mixed in a ratio of isocyanate group/hydroxyl group (NCO/OH) of 1.02, 50ppm dibutyltin dilaurate was added as a catalyst, and diluted with a diluent (mixed component of ethyl acetate/propylene glycol methyl ether acetate/butyl acetate in a weight ratio of 1:1:1), the coating composition was diluted to 50%, and stirred at 23℃for 5 minutes and sonicated for 5 minutes to obtain a defoamed coating solution.
The coating solutions obtained by the above-described methods were applied to steel plates (model Q235) in such a manner that the dry film thicknesses were 40 μm, respectively. Next, drying was performed at 23℃for 2 hours, and then heat treatment was performed at 80℃for 30 minutes. Then, curing was performed at 23℃and a relative humidity of 55% for 7 days for use.
(1) Touch dry time
The coating solution was applied to a glass plate using an applicator so as to have a thickness of 100 μm (thickness before drying), and after the application, the time until no longer sticking was observed when the glass plate was touched by hand at 23℃and a relative humidity of 30%.
(2) Curing drying time
The coating solution was applied to a glass plate using an applicator so as to have a thickness of 100 μm (thickness before drying), and after the application, the time until no fingerprint mark was left by being pressed with a finger with a strong force was measured at 23 ℃ under a relative humidity of 30%.
(3) Resistance to chemical changes test
Spraying the cleaning agent of the carburetor to the surface of the coating sample piece for complete infiltration, respectively staying for 20s,30s and 40s, and then wiping with non-woven fabrics, wherein the evaluation standard is as follows: if a 20s paint film is fogged, the swelling is poor; the paint film is complete for 20s but the paint film has good fogging after 30 s; after 40s, the paint film has no fogging, swelling and other fields.
(4) Adhesion rating: the coated steel plate substrate (type Q235) based coating-containing samples coated as described above were tested for adhesion according to GB/T9286-1998 cross-hatch test of paint films of color paint and varnish.
The test results are shown in table 2:
TABLE 2 modified polyisocyanate composition application Properties index
As can be seen from Table 2, the acrylic polyurethane varnishes prepared in examples 1-4 can improve and ensure excellent chemical resistance and adhesion to metal substrates of the coating while shortening the touch drying time and curing drying time, so that the acrylic polyurethane varnishes are particularly suitable for the fields of high quick drying and chemical resistance of automotive factory paints or repair paints and the like; the acrylic polyurethane varnish sample sheets prepared in comparative examples 1-3 obviously have poor partial indexes and poor comprehensive properties, and are difficult to meet actual demands.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (9)
1. A modified polyisocyanate composition comprises isocyanurate formed by trimerization reaction of pentamethylene diisocyanate and 1, 6-hexamethylene diisocyanate, and the composition comprises three isocyanurate mononuclei of structures (A), (B) and (C), wherein the mass ratio of the three mononuclei satisfies the following relation based on the total mass of the isocyanate composition: (C) (A) > (B),
2. the modified polyisocyanate composition according to claim 1, wherein the sum (a) + (B) of the modified isocyanurate mononucleolar structure (a) and the modified isocyanurate mononucleolar structure (B) is in the range of 5 to 40% by mass, preferably 5 to 30% by mass, based on the total mass of the modified polyisocyanate composition.
3. The modified polyisocyanate composition according to claim 1 or 2, wherein the sum of the monomer contents of free pentamethylene diisocyanate and 1,6 hexamethylene diisocyanate is less than 0.5% based on the total mass of the modified polyisocyanate composition.
4. A process for preparing the modified polyisocyanate composition of any one of claims 1 to 3 comprising the steps of: under the inert gas atmosphere, 1, 6-hexamethylene diisocyanate is firstly added into a reaction vessel and heated to 45-120 ℃, a catalyst is added, meanwhile, pentamethylene diisocyanate is dropwise added in a continuous dropwise feeding mode, continuous copolymerization reaction is carried out under the action of the catalyst, after the pentamethylene diisocyanate is dropwise added, the reaction is continued until the polymerization conversion rate of the 1, 6-hexamethylene diisocyanate reaches 25-65%, 45-55% is preferred, a terminator is added to terminate the reaction, a polyisocyanate mixture solution is obtained, and unreacted 1, 6-hexamethylene diisocyanate and pentamethylene diisocyanate are removed by further reduced pressure distillation, so that the modified polyisocyanate composition is obtained.
5. The method according to claim 4, wherein the total drop mass content of pentamethylene diisocyanate is 5 to 35% based on the total mass of pentamethylene diisocyanate and 1, 6-hexamethylene diisocyanate.
6. The method according to claim 4, wherein the dropping rate of pentamethylene diisocyanate is not particularly limited, but from the viewpoint of process stability, it is preferable to control the dropping time to be 30 to 120 minutes.
7. The method according to claim 4, wherein the catalyst is selected from one or more of trimethyl hydroxyethyl ammonium, triethyl hydroxypropyl ammonium, tetramethyl ammonium acetate, tetrabutyl ammonium acetate, tetramethyl ammonium propionate, tetramethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide, benzyl triphenyl phosphorus chloride, and 2,4, 6-tris (dimethylamine methyl) phenol.
8. A polyurethane clearcoat prepared from the modified polyisocyanate composition of any of claims 1 to 7 as a curing agent.
9. A composite material, characterized in that it is made of the varnish coating of claim 8 and a substrate with a metallic surface.
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