CN117285842A - Modified color paste, bi-component aromatic polyurethane material and preparation method thereof - Google Patents

Modified color paste, bi-component aromatic polyurethane material and preparation method thereof Download PDF

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CN117285842A
CN117285842A CN202311575030.0A CN202311575030A CN117285842A CN 117285842 A CN117285842 A CN 117285842A CN 202311575030 A CN202311575030 A CN 202311575030A CN 117285842 A CN117285842 A CN 117285842A
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color paste
modified color
parts
polyurethane material
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CN117285842B (en
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李宁
孙嘉鹏
董火成
李傲飞
申少伟
陈静
匙丹丹
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Liming Research Institute of Chemical Industry Co Ltd
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Liming Research Institute of Chemical Industry Co Ltd
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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
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • C09D17/004—Pigment pastes, e.g. for mixing in paints containing an inorganic pigment
    • C09D17/005—Carbon black
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802—Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • C08G18/3804—Polyhydroxy compounds
    • C08G18/3812—Polyhydroxy compounds having fluorine atoms
    • 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
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • 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
    • C08G18/65—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
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses a modified color paste, a bi-component aromatic polyurethane material and a preparation method thereof, wherein the modified color paste comprises the following components in percentage by mass: pigment carbon black 5.0-10.0%, isocyanate silane coupling agent 1-5%, polyether polyol 85-94% and organic bismuth catalyst 0.02-0.05%. The modified color paste is added into the A component of the polyurethane material, and the weather-resistant and water-resistant polyurethane material can be prepared by a RIM process, so that the service life of the polyurethane material is long under outdoor strong light and high humidity environment.

Description

Modified color paste, bi-component aromatic polyurethane material and preparation method thereof
Technical Field
The invention belongs to the field of bi-component polyurethane, and in particular relates to a polyurethane reaction injection molding material and a process.
Background
Polyurethane reaction injection molding (Polyurethane-Reaction Injection Molding), abbreviated as PU-RIM, is a process technology for manufacturing complex parts directly from low-viscosity, high-reactivity raw materials through rapid reaction. The two-component raw materials are mutually collided and mixed at high speed immediately before entering the die cavity and react in the die cavity to form a solid polymer in the shape of the die cavity, thus completing a molding cycle. The PU-RIM process is different from the casting polyurethane elastomer, and has the advantages of less energy, rapid reaction and short molding period; in stark contrast to the traditional thermoplastic injection molding principle, RIM is a polymerization reaction in a mold cavity, rather than forming a solid polymer by cooling. The PU-RIM material has good physical and mechanical properties and excellent manufacturability, and can meet the requirement of light weight, so that the PU-RIM material is widely applied to various fields of inner and outer decoration parts of vehicles such as automobiles, trains, airplanes and the like.
The PU material can be divided into two main types of aliphatic and aromatic according to the different isocyanate used, while the aliphatic system material has excellent light aging resistance, the large-scale application of the PU material is limited due to the factors of high price, relatively low reactivity and the like; the aromatic system has the advantages of lower raw material price, better mechanical property, higher reactivity and shorter molding period, and meets the market demand better. However, the existence of the benzene ring structure in the aromatic isocyanate inevitably leads to poor weather resistance of the material and easy aging, and particularly, when the black polyurethane material containing carbon black filler in the formula is degraded and pulverized, the appearance color of the material generates chromatic aberration and the carbon black is separated out on the surface, so that the appearance and partial functionality of the exterior trim part are affected. When the material is applied in a high-humidity environment, water molecules permeate and diffuse, polar hydrophilic groups are associated with water, under the action of the water molecules, the intermolecular interaction is reduced, the molecular distance is increased, swelling and even degradation are gradually generated along with the time, the mechanical property of the material is reduced, and part of using functions are reduced, so that the service life of a product is influenced.
Polyurethane materials are widely used in automobiles, and the main interior trim parts and the exterior trim parts are distinguished from each other from application positions. The material in the automobile cockpit belongs to an interior trim part, and the requirements of the interior trim part on weather resistance and water resistance are relatively low; the parts outside the cockpit are exterior trim parts, such as skylights, large surrounding areas and the like, and have severe requirements on weather resistance and water resistance of materials. At present, the automotive industry generally requires that after 600 hours of accelerated photo-aging test, the color difference delta E is less than 3.0, and the surface is free from precipitation and cracking; after the material is subjected to a long-time soaking test, the loss of mechanical properties is not more than 10%. The aromatic PU material is easy to age in the comprehensive environment of illumination, high temperature and high humidity, and the problems of obvious color difference and performance reduction after aging are obvious, so that the requirements of the exterior trimming parts in use cannot be met. Therefore, improving weather resistance and water resistance helps to widen the application range of the material.
Patent document CN116042163a discloses a weather-resistant single-component polyurethane black sealant and a preparation method thereof. According to the invention, the antioxidant and the silane coupling agent are respectively attached to the halloysite powder by a two-step method, the modified halloysite filler can not only enhance the bonding capability of the modified halloysite filler and other fillers to polyurethane prepolymer, but also has the effect of enhancing the strength index of the sealant, and when the antioxidant enters the tubular structure of the modified halloysite filler, the antioxidant can be continuously and slowly released in an aging environment, and the hydrophobic structure of the modified halloysite filler is matched, so that the aging resistance time and the retention effect of mechanical properties of the sealant are greatly prolonged. However, 15-20 parts of modified halloysite filler is required to be added, the addition amount is too large, the viscosity of feed liquid is too high, and the modified halloysite filler is not matched with a two-component reaction injection molding process, so that the problem of too high viscosity is solved, and 20-30 parts of plasticizer is added in the modified halloysite filler, so that the environmental protection property of the material is affected.
The invention discloses a weather-resistant coating containing graphene-based composite material and a preparation method thereof, wherein the graphene-based composite material is prepared by non-covalent modification of graphene by adopting a pyrene ring, a hydrophilic group and an azobenzene structure compound, and the graphene-based composite material is added into polyurethane as an ultraviolet absorbent, can compete with a light absorption part in polyurethane matrix resin as the ultraviolet absorbent to achieve the purpose of protecting polyurethane, and meanwhile, the high compactness and small-size effect of the graphene material can effectively block other ageing influencing factors such as oxygen, water and the like, so that the weather resistance of the polyurethane is remarkably improved. However, compared with pigment carbon black, the modified graphene-based composite material has insufficient coloring capability, and when the addition amount is too large, the cost is too high, meanwhile, the viscosity is too large, in order to solve the problem of liquid flowability, in the patent, when the graphene-based composite material is used, solvents such as butyl acetate, propylene glycol methyl ether acetate and the like are added, and the solvents can be applied to the field of paint, but have a large influence on the environmental protection of PU-RIM materials.
Patent document CN115894846a discloses a hydrophobic polyurethane, a preparation method and application thereof, and the patent introduces silicon-containing groups with low surface energy into a polyurethane main chain in the form of a silane coupling agent, so that high-density hydrophobic groups (siloxane groups) are formed on a polymer chain, the surface energy is reduced, and the hydrophobicity and the water resistance of the polyurethane can be effectively improved. However, the polyurethane material in the patent is synthesized by four steps of reaction of prepolymerization, chain extension, addition and secondary addition, the silane coupling agent is introduced to a polyurethane chain segment through the addition reaction with a chain extension product and a third organic solvent, the whole process is complex, and the organic solvent is added in each step to prevent excessive viscosity or premature gelation, so that the method cannot be applied to PU-RIM materials.
Patent document CN114149576A, CN116262809A, CN115819710a relates to improving the water resistance of materials by introducing fluorine element into polyurethane structure, and patent document CN114149576a synthesizes a fluorine-containing polycarbonate diol; patent document CN116262809a synthesizes a fluorine-containing polyester diol; the patent CN115819710A synthesizes a fluorine-containing polyether glycol, and the water resistance of the polyurethane material is improved by taking the synthesized fluorine-containing glycol as a soft segment, but the methods have the common defects of longer synthetic route, harsh process conditions and high cost, and when the synthesized fluorine-containing glycol is directly applied to the A component of the PU-RIM material, the crosslinking degree of the material is reduced when the synthesized fluorine-containing glycol reacts with the B component, and the molding demolding time and the mechanical property of the material are influenced.
In the prior art, modified halloysite filler and graphene materials are added to improve the weather resistance of aromatic polyurethane, and the filler can cause excessive viscosity of feed liquid and poor fluidity, so that the modified halloysite filler is not suitable for RIM technology; when the viscosity is reduced by adding the solvent, the environmental protection of the product is affected. While the conventional means only adds a certain amount of auxiliary agents such as ultraviolet absorber, antioxidant, hydrophobing agent and the like into the formula, the conventional means has a certain effect on improving weather resistance and water resistance, but the duration is not ideal. The existing patent introduces silicon and fluorine elements through polyurethane chain segments to improve hydrophobicity, the synthetic route is longer, the process conditions are harsh, a large amount of organic solvents are needed to be introduced, and the synthesized addition product or dihydric alcohol cannot be directly applied to A, B components of the PU-RIM material.
In the prior art, the research on the weather resistance and the water resistance of the black aromatic PU-RIM material is less, the black aromatic PU-RIM material is exposed to the outdoor environment for a long time and is influenced by ultraviolet rays, water vapor, high temperature and weathering, the material is continuously decomposed, the mechanical property is reduced, the surface is pulverized, the color is changed, carbon black is separated out, part of functions are reduced, and the service life is shortened. The reason for this is as follows: (1) The benzene ring structure in aromatic polyurethane leads to the easy aging; (2) The carbon black for coloring has larger specific surface area and higher surface energy, has stronger cohesive force, is difficult to stably and uniformly disperse, and has adverse effect on the comprehensive performance of the material when the carbon black is agglomerated in the material. Therefore, it is extremely important to properly modify the surface of carbon black, which can improve the dispersion stability of carbon black in the system, thereby improving the comprehensive properties of the material and solving the problem that carbon black is easy to precipitate from the material.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified color paste, an aromatic polyurethane material and a preparation method thereof, wherein the modified color paste is added into the A component of the polyurethane material, and the weather-resistant and water-resistant polyurethane material can be prepared through a RIM process, so that the modified color paste has long service life in outdoor strong light and high humidity environment.
The first aspect of the invention provides a modified color paste, which comprises the following components in percentage by mass: pigment carbon black 5.0-10.0%, isocyanate silane coupling agent 1-5%, polyether polyol 85-94% and organic bismuth catalyst 0.02-0.05%.
The preparation method of the modified color paste comprises the following steps: adding pigment carbon black and an isocyanate-based silane coupling agent into an organic solvent, adding the organic solvent and polyether polyol and an organic bismuth catalyst into a reaction vessel for reaction after uniform dispersion, removing the organic solvent after the reaction is finished, cooling to room temperature, and discharging. Preferably, the reaction temperature is 80-90 ℃ and the reaction time is 2-3 h. The organic solvent is selected from one or more of tetrahydrofuran, dichloromethane, carbon tetrachloride and 1, 4-dioxane.
The polyether polyol preferably has a primary hydroxyl content of more than 70% and one or more of ethylene oxide-propylene oxide copolyether triols with a number average molecular weight of 3000-6500. The pigment carbon black is a nanoscale material, and the average primary particle size is preferably 15-60 nm; the coupling agent is an isocyanatosilane coupling agent, and is preferably one or more of gamma-isocyanatopropyl trimethoxysilane, gamma-isocyanatopropyl triethoxysilane, isocyanatopropyl methyl dimethoxy silane and isocyanatopropyl methyl diethoxy silane; the organic bismuth catalyst is selected from one or two of bismuth isooctanoate and bismuth neodecanoate.
The second aspect of the invention provides a two-component aromatic polyurethane material, which consists of a component A and a component B,
the component A comprises the following components in percentage by mass: 50-70% of polyether polyol, 20-30% of modified color paste, 1-10% of chain extender, 1-10% of cross-linking agent, 1-5% of anti-aging agent and 0.5-2% of composite catalyst; the modified color paste is the modified color paste provided by the first aspect of the invention;
the component B comprises the following components in percentage by mass: 90-96% of aromatic isocyanate and 4-10% of modifier. The isocyanate (NCO) content of the component B is 24.0% -30.0%.
The polyether polyol in the component A is the same as the polyether polyol in the modified color paste, preferably one or more of ethylene oxide-propylene oxide copolyether triols with the primary hydroxyl content more than 70% and the number average molecular weight of 3000-6500.
The chain extender is preferably one or more of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, diethylene glycol and diethanolamine.
The crosslinking agent is preferably one or more of glycerol, trimethylolethane, trimethylolpropane and triethylisocyanurate.
The anti-aging agent comprises one or more of 2- (2 ' -hydroxy-3 ', 5' -di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2 ' -hydroxy-5 ' -methylphenyl) benzotriazole, bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide, bis (1, 2, 6-pentamethyl-4-piperidinyl) sebacate and trioctyl phosphite.
The composite catalyst is prepared by compounding 8-12 parts by mass of bismuth isooctanoate, 1-2 parts by mass of potassium isooctanoate, 13-17 parts by mass of dicycloamidine compound and 8-12 parts by mass of glycerol. Preferably, 10 parts by mass of bismuth isooctanoate, 1-2 parts by mass of potassium isooctanoate, 15 parts by mass of dicycloamidine compound and 10 parts by mass of glycerol;
the bicyclic amidine compounds have the following general formula:
wherein R is 1 =C x H 2x ,x=3~7;R 2 =C y H 2y ，y=2~4。
The aromatic isocyanate is preferably one or more of 4,4' -diphenylmethane diisocyanate (MDI), liquefied MDI and polymethylene polyphenyl isocyanate.
Preferably, the modifier is fluorine-containing dihydric alcohol, selected from 3-fluoro-1, 2-propanediol, 2, 3-tetrafluoro-1, 4-butanediol, 2,3, 4-hexafluoro-1, 5-pentanediol 2,3, 4, 5-octafluoro-1, 6-hexane diol, 1H, 8H-dodecafluoro-1, 8-octanediol perfluoro-1, 9-nonanediol, hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-diol, 1-trifluoro-2-trifluoromethyl-2, 4-pentanediol, perfluoro-1, 10-decanediol.
The third aspect of the invention provides a method for preparing an aromatic polyurethane material, comprising the following steps:
and (3) a component A: adding polyether polyol, modified color paste, a chain extender, a cross-linking agent, an anti-aging agent and a composite catalyst into a reaction container, and uniformly mixing at 25-30 ℃;
and the component B comprises the following components: and adding the aromatic isocyanate and the modifier into a reaction container, heating to 80-90 ℃ under stirring, reacting for 2-3 hours, cooling to room temperature, and discharging.
The polyurethane material is prepared from a component A and a component B by adopting a reaction injection molding process. The mass ratio of the component A to the component B is 100:54+/-4.
Compared with the prior art, the invention has the following beneficial effects:
(1) After modifying the surface of pigment carbon black by adopting an isocyanate-based silane coupling agent, the invention grafts the carbon black on polyether polyol by utilizing the hydroxyl reaction of isocyanate groups and polyether polyol, and the obtained color paste has good dispersion stability; after the carbon black is added into the component A, the carbon black is not easy to agglomerate and delaminate; after the carbon black reacts with the component B to form a PU-RIM material, the carbon black is grafted to a polyurethane chain segment, so that the carbon black has good compatibility with the material and good stability, is not easy to separate out when being used in an outdoor strong light and high humidity environment, and has small color difference after aging;
(2) The invention adopts fluorine-containing dihydric alcohol to modify aromatic isocyanate, the prepared end NCO product is used as a component B, and a polyurethane product is manufactured by a reaction injection molding process with a component A containing active-OH groups, and fluorine is introduced into a polyurethane chain segment, so that the modification process is simple and easy to operate;
(3) The bi-component aromatic polyurethane material is prepared from A, B by a reaction injection molding process, and silicon and fluorine elements are simultaneously introduced into polyurethane molecular chain segments, so that the weather resistance and the water resistance of the material are improved.
Detailed Description
The invention is further illustrated by the following examples, which are given by mass.
Example 1
Preparation of modified color paste: adding 8 parts of pigment carbon black PRINTEX 60,3 parts of gamma-isocyanatopropyl trimethoxy silane into 40 parts of anhydrous tetrahydrofuran, performing airtight ultrasonic dispersion for 2 hours, adding 89 parts of 330N (ethylene oxide-propylene oxide copolyether triol, hydroxyl value of 33.5-36.5 mg KOH/g) and 0.04 part of bismuth isooctanoate into a reaction container, heating to 80-90 ℃ under stirring, reacting for 2 hours, distilling tetrahydrofuran under reduced pressure, cooling to room temperature, and discharging to obtain the required color paste;
preparing a composite catalyst: 10 parts of bismuth isooctanoate, 1 part of potassium isooctanoate, and 1, 8-diazacycloundecene (R 1 =C 5 H 10 ；R 2 =C 3 H 6 ) 15 parts of glycerol and 10 parts of glycerol are fully stirred and uniformly mixed for later use;
and (3) preparation of the component A: 330N:60.8 parts of modified color paste: 25 parts of ethylene glycol: 6 parts of trimethylolpropane: 6 parts of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole: 0.6 part of bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide: 0.4 part of composite catalyst: 1.2 parts of a catalyst, and adding the catalyst into a reaction container, and uniformly stirring and mixing the catalyst at 25-30 ℃;
and (3) preparation of a component B: 4,4' -diphenyl diisocyanate: 92 parts of 2, 3-tetrafluoro-1, 4-butanediol: 8 parts. Adding the mixture into a reaction vessel, heating to 82 ℃ under stirring, reacting for 2 hours, detecting the NCO mass fraction to be 26.7%, cooling to room temperature, and discharging.
Example 2
Preparation of modified color paste: adding 5 parts of pigment carbon black PRINTEX 60,5 parts of gamma-isocyanatopropyl triethoxysilane into 30 parts of anhydrous 1, 4-dioxane, performing airtight ultrasonic dispersion for 2 hours, adding the mixture into a reaction container together with 90 parts of 330N and 0.05 part of bismuth iso-octoate, heating to 80-90 ℃ under stirring, reacting for 2 hours, distilling the 1, 4-dioxane under reduced pressure, cooling to room temperature, and discharging to obtain the required color paste;
and (3) preparation of the component A: 330N:65.8 parts of modified color paste: 20 parts of ethylene glycol: 6 parts of trimethylolpropane: 6 parts of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole: 0.6 part of bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide: 0.4 part of composite catalyst (formulated in example 1): 1.2 parts of a catalyst, and adding the catalyst into a reaction container, and uniformly stirring and mixing the catalyst at 25-30 ℃;
and (3) preparation of a component B: liquified MDI:96 parts of 2, 3-tetrafluoro-1, 4-butanediol: 4 parts. Adding the mixture into a reaction vessel, heating to 82 ℃ under stirring, reacting for 2 hours, detecting the NCO mass fraction to be 26.2%, cooling to room temperature, and discharging.
Example 3
And (3) preparing color paste: adding 10 parts of pigment carbon black PRINTEX 60 and 1 part of gamma-isocyanatopropyl trimethoxy silane into 50 parts of anhydrous tetrahydrofuran, sealing, performing ultrasonic dispersion for 2 hours, adding 89 parts of 330N and 0.04 part of bismuth isooctanoate into a reaction container, heating to 80-90 ℃ under stirring, reacting for 2 hours, distilling tetrahydrofuran under reduced pressure, cooling to room temperature, and discharging to obtain the required color paste;
and (3) preparation of the component A: 330N:55.8 parts of modified color paste: 30 parts of ethylene glycol: 6 parts of trimethylolpropane: 6 parts of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole: 0.6 part of bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide: 0.4 part of composite catalyst (formulated in example 1): 1.2 parts of a catalyst, and adding the catalyst into a reaction container, and uniformly stirring and mixing the catalyst at 25-30 ℃;
and (3) preparation of a component B: 4,4' -diphenyl diisocyanate: 84 parts of methylene polyphenyl isocyanate: 6 parts of 2,3, 4-hexafluoro-1, 5-pentanediol: 10 parts. Adding the mixture into a reaction vessel, heating to 82 ℃ under stirring, reacting for 2 hours, detecting the NCO mass fraction to be 26.1%, cooling to room temperature, and discharging.
Comparative example 1
Comparative example 1 the modified mill base was prepared without the addition of an isocyanato silane coupling agent, the other steps being the same as in example 1.
Comparative example 2
Comparative example 2 preparation of modified color paste gamma-isocyanatopropyl trimethoxysilane was changed to gamma-glycidoxypropyl trimethoxysilane, and the other steps were the same as in example 1.
Comparative example 3
Preparation of component B in comparative example 32, 3-tetrafluoro-1, 4-butanediol was changed to butylethylpropanediol, and the NCO mass fraction of the prepared component B was 26.0% in the same manner as in example 1.
Comparative example 4
And (3) preparing a component A: 330N:52.8 parts of fluorine-containing polyester diol (obtained by polycondensation of adipic acid and 3-fluoro-1, 2-propanediol, and hydroxyl value of 52.0-58.0 mg KOH/g): 6 parts of modified color paste (prepared in example 1): 25 parts of ethylene glycol: 6 parts of trimethylolpropane: 6 parts of 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole: 0.6 part of bis (3, 5-tert-butyl-4-hydroxyphenyl) sulfide: 0.4 part of composite catalyst (formulated in example 1): 1.2 parts of a catalyst, and adding the catalyst into a reaction container, and uniformly stirring and mixing the catalyst at 25-30 ℃;
the preparation of component B was the same as in comparative example 3.
The A, B component in the above list is prepared into the corresponding PU-RIM material by a high-pressure injection machine.
The process for preparing the PU-RIM material by the component A and the component B through a high-pressure injection machine comprises the following steps:
(1) feeding: adding the component A into a high-pressure machine A tank, and adding the component B into a high-pressure machine B tank;
(2) injection: setting the temperature of the materials, namely the component A, at 30-45 ℃, the component B, at 30-45 ℃ and the mixing ratio A/B of 100: 54+/-4, wherein the injection pressure is 14+/-1 MPa, and injecting the mixture into a die with the die temperature heated to 110-120 ℃;
(3) demolding: demolding 40s after injection is completed; if cracking, deformation, swelling and the like occur during 40s demolding, the demolding time is prolonged.
The A components in example 1, example 2, example 3, comparative example 1 and comparative example 2 were subjected to high-speed centrifugal separation, and the rotational speed of the centrifuge was: 8000r/min, temperature: the longer the time required to record the onset of significant delamination of the a component, the better the stability at 25 ℃. The experimental results are shown in table 1.
Table 1 time taken for the A fractions to separate distinct layers by high-speed centrifugation
The preferred molding release times and mechanical properties of the prepared materials were tested for example 1, example 2, example 3, comparative example 4. The mechanical properties tested included hardness, tensile strength, elongation at break, wherein hardness was carried out according to the method specified in GB/T531.1-2008; tensile strength and elongation at break were carried out according to the methods specified in GB/T528-2009.
TABLE 2 test results of molding release time and mechanical properties of materials
The materials prepared in example 1, example 2, example 3, comparative example 1, comparative example 2, comparative example 3 were subjected to weather resistance and water resistance tests.
Weather resistance was measured according to the test method B-1 specified in GB/T32088-2015, the test period was 600h, wherein the measurement of the color difference Δe was performed in annex B in the reference standard, and the carbon black precipitation and the white scouring pad wiping were observed. The experimental results are shown in table 3.
TABLE 3 weather resistance and carbon black precipitation test results
The water resistance is measured by the change of mechanical properties of the material after soaking in water, and the smaller the change rate is, the better the water resistance is. Wherein, the test conditions are divided into a normal state and a normal state after soaking water: (23+ -2) °c, (50+ -5)% RH,48h; soaking in water: soaking in water at 38deg.C for 120 hr, and standing for 2 hr under normal condition. The test results are shown in the following table.
TABLE 4 results of mechanical property test before and after soaking in Water

Claims (10)

1. The modified color paste comprises the following components in percentage by mass: pigment carbon black 5.0-10.0%, isocyanate silane coupling agent 1-5%, polyether polyol 85-94% and organic bismuth catalyst 0.02-0.05%.
2. The modified mill base of claim 1 wherein the isocyanatosilane coupling agent is selected from one or more of gamma-isocyanatopropyl trimethoxysilane, gamma-isocyanatopropyl triethoxysilane, isocyanatopropyl methyldimethoxysilane, isocyanatopropyl methyldiethoxysilane.
3. The modified color paste according to claim 1, wherein the polyether polyol is one or more of ethylene oxide-propylene oxide copolyether triols with a primary hydroxyl content of > 70% and a number average molecular weight of 3000-6500.
4. The modified color paste according to any one of claims 1 to 3, wherein the preparation method of the modified color paste comprises the following steps: adding pigment carbon black and an isocyanate-based silane coupling agent into an organic solvent, adding the organic solvent and polyether polyol and an organic bismuth catalyst into a reaction vessel for reaction after uniform dispersion, removing the organic solvent after the reaction is finished, cooling to room temperature, and discharging.
5. A bi-component aromatic polyurethane material consists of a component A and a component B,
the component A comprises the following components in percentage by mass: 50-70% of polyether polyol, 20-30% of modified color paste, 1-10% of chain extender, 1-10% of cross-linking agent, 1-5% of anti-aging agent and 0.5-2% of composite catalyst; the modified color paste is the modified color paste of any one of claims 1-4;
the component B comprises the following components in percentage by mass: 90-96% of aromatic isocyanate and 4-10% of modifier.
6. The aromatic polyurethane material according to claim 5, wherein the chain extender is one or more of ethylene glycol, 1, 4-butanediol, 1, 3-butanediol, diethylene glycol, and diethanolamine; the cross-linking agent is one or more of glycerol, trimethylolethane, trimethylolpropane and triethylisocyanurate.
7. The aromatic polyurethane material according to claim 5, wherein the composite catalyst is formed by compounding 8-12 parts by mass of bismuth isooctanoate, 1-2 parts by mass of potassium isooctanoate, 13-17 parts by mass of dicycloamidine compound and 8-12 parts by mass of glycerol;
the bicyclic amidine compounds have the following general formula:
wherein R is 1 =C x H 2x ,x=3~7;R 2 =C y H 2y ，y=2~4。
8. The aromatic polyurethane material of claim 5, wherein the aromatic isocyanate is one or more of 4,4' -diphenylmethane diisocyanate (MDI), liquefied MDI, polymethylene polyphenyl isocyanate.
9. The aromatic polyurethane material according to claim 5, wherein the modifier is a fluorine-containing diol, selected from 3-fluoro-1, 2-propanediol, 2, 3-tetrafluoro-1, 4-butanediol, 2,3, 4-hexafluoro-1, 5-pentanediol 2,3, 4, 5-octafluoro-1, 6-hexane diol, 1H, 8H-dodecafluoro-1, 8-octanediol perfluoro-1, 9-nonanediol, hexafluoro-2, 3-bis (trifluoromethyl) -2, 3-diol, 1-trifluoro-2-trifluoromethyl-2, 4-pentanediol, perfluoro-1, 10-decanediol.
10. A method of preparing the aromatic polyurethane material of any one of claims 5 to 9, comprising the steps of:
(1) And (3) a component A: adding polyether polyol, modified color paste, a chain extender, a cross-linking agent, an anti-aging agent and a composite catalyst into a reaction container, and uniformly mixing at 25-30 ℃;
(2) And the component B comprises the following components: and adding the aromatic isocyanate and the modifier into a reaction vessel, heating to 80-90 ℃ under stirring, reacting for 2-3 hours, cooling to room temperature, and discharging, wherein the content of isocyanate (NCO) of the component B is 24.0-30.0%.
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